CN115613216B - Degradable elastic material, nonwoven material and preparation method thereof - Google Patents
Degradable elastic material, nonwoven material and preparation method thereof Download PDFInfo
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- CN115613216B CN115613216B CN202211318723.7A CN202211318723A CN115613216B CN 115613216 B CN115613216 B CN 115613216B CN 202211318723 A CN202211318723 A CN 202211318723A CN 115613216 B CN115613216 B CN 115613216B
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4391—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres
- D04H1/43912—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres fibres with noncircular cross-sections
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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
- 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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- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/4358—Polyurethanes
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/56—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/061—Load-responsive characteristics elastic
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/12—Physical properties biodegradable
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2509/00—Medical; Hygiene
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2509/00—Medical; Hygiene
- D10B2509/02—Bandages, dressings or absorbent pads
- D10B2509/026—Absorbent pads; Tampons; Laundry; Towels
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Nonwoven Fabrics (AREA)
- Absorbent Articles And Supports Therefor (AREA)
Abstract
The application provides a degradable elastic material, a non-woven material and a preparation method thereof. Wherein, the preparation of the degradable elastic material comprises the following steps: the thermoplastic polyurethane is prepared from PBAT, meltable TPU and polyethylene glycol serving as raw materials in proportion by a blending forming method. According to the preparation method of the degradable elastic material, the PBAT particles and the modified TPU are melt-blended through modification to prepare the degradable elastic material, so that the prepared degradable elastic material can be rapidly biodegraded in soil or outside the soil, and the elastic material is degraded into a nontoxic compound. According to the preparation method of the nonwoven material, the extrusion swelling phenomenon can be counteracted by extruding the melted degradable elastic material polymer melt from the petal-shaped spinneret orifice, so that the fiber stretching is stable, the broken ends are reduced, the fiber is uniform in the production process, and the product has good mechanical properties.
Description
Technical Field
The application relates to the technical field of materials, in particular to a degradable elastic material, a non-woven material and a preparation method thereof.
Background
The elastic nonwoven material is mainly applied to sanitary materials, is suitable for being applied to civil engineering materials such as masks, protective clothing, tissue engineering materials, membrane materials, geotextiles and the like, and sanitary materials such as adult incontinence products, female sanitary products, paper diapers and the like, and keeps two-digit growth in recent years. However, the existing elastic nonwoven material is a non-degradable material, and can cause 'white pollution' when being discarded at will, so that the ecological environment is destroyed, and the classification recycling and reutilization difficulty of PP melt-blown cloth is great, and if the PP melt-blown cloth is treated in a burning energy recycling way, toxic and harmful gas can be generated.
Thermoplastic Polyurethane (TPU), which is one of elastic nonwoven materials, has excellent physical properties and processability due to its unique chain structure and aggregate structure, and is also widely used in various aspects of industrial and agricultural production, but the waste polyurethane is eventually buried or burned, but since polyurethane is also not degradable, and also has environmental pollution problems. With the increasing awareness of environmental protection, the degradable elastic meltblown nonwoven materials have received more attention, and it is desirable to prepare the degradable elastic meltblown nonwoven materials to reduce energy consumption and environmental pollution.
TPU has become one of the important thermoplastic elastomer materials as a degradable material with its excellent properties and wide range of applications. However, the TPU melt has a strong recoverable elastic deformation during flow, which causes a significant die swell during melt blown extrusion, which directly affects the dimensional accuracy, quality and appearance of the polymer extrusion molded articles, and if the swell is too severe, it may result in fiber doubling, increasing the average diameter and average pore size of the melt blown nonwoven fibers, thereby reducing product quality. Therefore, the improvement of the situation is very important in the process of preparing the degradable elastic melt-blown nonwoven material, which is beneficial to controlling the parameters of the preparation process and also ensures that the fiber uniformity is good and the mechanical property of the produced product is excellent.
Disclosure of Invention
The application aims to solve the defects in the prior art and provide a degradable elastic material and a non-woven material which can be degraded and have elasticity and a preparation method thereof.
A method of making a degradable elastomeric material comprising:
the thermoplastic polyurethane is prepared from PBAT, meltable TPU and polyethylene glycol serving as raw materials in proportion by a blending forming method.
Further, the preparation method as described above comprises:
(1) Preparation of modified TPU: preparing modified TPU by taking polyethylene glycol and meltable TPU as raw materials according to a proportion by a blending forming method;
(2) Preparation of modified PBAT: taking PBAT particles as raw materials, blending and stirring polyethylene glycol solution and the PBAT particles under certain conditions, uniformly coating the polyethylene glycol solution on the surfaces of the PBAT particles, and cooling and shaping to form modified PBAT particles;
(3) Melt blending and molding the modified PBAT particles and the modified TPU; blending the modified PBAT particles in the step (2) and the modified TPU in proportion, and sending the blend into a screw extruder for blending, thereby finally preparing the degradable elastic material.
Further, according to the preparation method, the PBAT is a high-melt-index PBAT with a melt index higher than 100g/10 min.
A degradable elastomeric material prepared by any one of the methods described above.
A method of making a nonwoven material using the degradable elastomeric material prepared above, comprising:
extruding a molten polymer melt of the degradable elastic material through petal-shaped spinneret orifices, and taking the extruded degradable elastic material as a basis for preparing a non-woven material.
Further, in the method described above, the petal-shaped spinneret is a hexapetal-shaped spinneret orifice.
Further, the method as described above, further comprising: the degradable elastic material extruded from the petal-shaped spinneret orifices is subjected to a melt-blown forming process to obtain a PBAT elastic fiber melt-blown fiber web;
and carrying out multistage hot drawing treatment on the PBAT elastic fiber melt-blown fiber web by a hot drawing device, and finally preparing the nonwoven material.
A nonwoven material prepared by any of the methods described above.
The non-woven material prepared by the method can be applied to the preparation of diaper, sanitary towel, operating gown, cover cloth and the like.
The beneficial effects are that:
according to the degradable elastic material, the nonwoven material and the preparation method thereof, the PBAT particles and the modified TPU are melt-blended through modification to prepare the degradable elastic material, so that the prepared degradable elastic material can be rapidly biodegraded in soil or outside the soil, and the elastic material is degraded into a nontoxic compound.
According to the method provided by the application, the melt of the degradable elastic material in the melt state is extruded from the petal-shaped spinneret orifice, so that the extrusion swelling phenomenon can be counteracted, the fiber stretching is stable, the broken ends are reduced, the fiber is uniform in the production process, and the product has good mechanical properties.
Drawings
FIG. 1 is a schematic diagram of a hexapetaloid spinneret orifice structure.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present application more apparent, the technical solutions in the present application will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1:
the embodiment provides a preparation method of a degradable elastic material, which comprises the following steps:
(1) Preparation of polyethylene glycol/meltable TPU blend solution: polyethylene glycol and meltable TPU are taken as raw materials, and a polyethylene glycol/TPU blending solution is prepared in proportion by a blending forming method;wherein the mass ratio of polyethylene glycol to meltable TPU The method comprises the following steps: (1-2): (2-4).
(2) Preparation of polyethylene glycol/poly (adipic acid)/polybutylene terephthalate) blend particles: taking poly adipic acid/butylene terephthalate (PBAT) particles as raw materials, blending and stirring polyethylene glycol and the PBAT particles,blending and stirring bar The piece is: at 80-100 deg.c, inert gas is used to protect,uniformly coating polyethylene glycol solution on the surface of the PBAT particles, and then rapidly cooling and shaping to form polyethylene glycol/PBAT blended particles;wherein, the mass ratio of PBAT to polyethylene glycol is: (6-7): (1-2)。
(3) Melt blending and molding the PBAT blend particles and the modified TPU; mixing the polyethylene glycol/PBAT blend particles in the step (2) and the modified TPU according to the ratioExample blending, feeding into a screw extruder to blend into a polymer melt, i.e. the degradable elastomeric material.Wherein, the mass ratio of the PBAT blend particles to the modified TPU is as follows: (6-7): (2-4).
The poly (butylene adipate/terephthalate) (PBAT) and polyethylene glycol described in this example were used to prepare biodegradable additives. The PBAT used is high melt index PBAT with the melt index higher than 100g/10 min; the higher the melt index, the better the fluidity, and the lower the apparent viscosity of the melt is influenced by temperature, shear rate and shear stress; under the action of the same shear rate, the extrusion swelling ratio is reduced along with the increase of the PBAT melt index, so that the special PBAT material for high-melt-index melt-blowing is selected when the degradable elastic material is prepared, the extrusion swelling of the melt-blown material at a die is reduced, the fiber doubling is prevented, and the quality of the melt-blown nonwoven material is improved.
In the method provided by the application, as the TPU has elasticity, the PBAT has degradability, and the polyethylene glycol is used for promoting the fusion of the polymers. According to the application, the PBAT blending particles and the modified TPU are fully mixed in a molten state by using a screw extruder, and the PBAT and the TPU are well compatible with polyethylene glycol, so that the finally prepared elastic material has degradability and elasticity from outside to inside and can be fully degraded.
The degradable elastic material prepared by the embodiment of the application can be applied to masks, protective clothing, tissue engineering materials, membrane materials, geotextiles and other civil engineering materials, adult incontinence products, female sanitary products, paper diapers and other sanitary materials.
Example 2:
the embodiment provides a method for preparing a nonwoven material, which comprises the following steps:
(1) Extruding the polymer melt prepared in the embodiment 1 through hexapetaline spinneret orifices, and obtaining a PBAT elastic fiber melt-blown fiber web through a melt-blown molding process; FIG. 1 is a schematic diagram of a hexapetaloid spinneret orifice structure.
(2) And (3) carrying out multistage hot drawing treatment on the PBAT elastic fiber melt-blown fiber web obtained in the step (1) through a hot drawing device to obtain the PBAT/modified TPU nonwoven material with the characteristics of strength, elasticity and biodegradability.
The spinneret orifices of the melt-blowing device in this embodiment are newly designed, the cross section of the spinneret orifices is in the shape of a flower with six circular petals, and the spinneret orifices are uniformly distributed on the spinneret plate body. During extrusion processing, the molten polymer is forced to flow through a geometrically configured die runner, the rheological properties of the polymeric material must be affected by the runner geometry, and the extrudate cross-sectional size and shape are different from the die cross-sectional size and shape due to the viscoelastic properties of the melt, and the hexapetaline orifices utilize die swell itself to improve the extruded polymer melt. Because the extrusion swell value is smaller when the extrudate is just extruded and released from the die; the swell value of the extrudate gradually increases over time and after a certain period of time the die swell remains at a relatively constant value. At the position where the six circular petals of the spinneret orifice are connected in pairs, as the parts have poorer wall conditions and narrower pore channels compared with other parts of the six circular petals, the speed of polymer melt ejection rapidly rises along with the shrinkage of the pore channels, and the extrusion swelling phenomenon of the parts is more obvious than that of other parts due to the higher extrusion speed, and the melt of the shrinkage part of the pore channels can be filled just after the extrusion swelling is stable, so that the extrusion swelling effect is eliminated. The application utilizes this effect to control the fineness and uniformity of the fibers as the polymer melt is extruded,by controlling the extrusion process Parameters (set extrusion speed of melt-blown machine to 65-90 g/10 min)Thereby improving the quality of polymer extrusion products.
The non-woven material prepared by the embodiment can be widely used for products such as diaper, sanitary towel, operation gown, cover cloth and the like.
Compared with the prior art, the application has the following beneficial effects:
(1) The application prepares a biodegradable elastic nonwoven material by combining a melt-blown nonwoven forming technology with a multistage hot drawing process, and the biodegradable elastic nonwoven material is an elastic fiber nonwoven material with strength, elasticity and biodegradability. The material is nontoxic, odorless, reliable in method and low in production cost, and has the advantage of large-scale application.
(2) The polymer melt extruded from the hexapetaloid spinneret orifices can well keep the fibers in the melt-blowing process uniform, so that the fibers are ensured to be stretched stably, broken ends are reduced, the surface quality of the extrudate is good, and the extrudate has good mechanical properties.
(3) The application overcomes the defect of single material of the non-woven fabric in the prior art, and expands the application range of the non-woven fabric: the biodegradable elastic nonwoven material can be applied to the application field of traditional melt-blown nonwoven materials on one hand, and can replace the traditional petroleum-based melt-blown nonwoven materials, such as PP nonwoven fabrics which are widely used in the market; on the other hand, the medical sanitary towel can meet the requirements of medical and health materials and packaging materials by virtue of excellent mechanical properties and biodegradability, and can be widely used for products such as diaper, sanitary napkins, surgical gowns, covering cloths and the like.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and are not limiting; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present application.
Claims (8)
1. A method of making a degradable elastomeric material comprising:
the PBAT adhesive is prepared from PBAT particles, meltable TPU and polyethylene glycol serving as raw materials in proportion by a blending forming method;
(1) Preparation of modified TPU: preparing modified TPU by taking polyethylene glycol and meltable TPU as raw materials according to a proportion by a blending forming method;
(2) Preparation of modified PBAT particles: taking PBAT particles as raw materials, blending and stirring polyethylene glycol solution and the PBAT particles under certain conditions, uniformly coating the polyethylene glycol solution on the surfaces of the PBAT particles, and cooling and shaping to form modified PBAT particles; the certain conditions are as follows: the temperature is 80-100 ℃, and inert gas is added for protection;
(3) Melt blending and molding the modified PBAT particles and the modified TPU in the step (2) according to the following steps: and (6-7) blending the materials in the mass ratio of (2-4), and feeding the materials into a screw extruder for blending to finally prepare the degradable elastic material.
2. The method of making a degradable elastic material according to claim 1, wherein the PBAT particles are high melt index PBAT with a melt index higher than 100g/10 min.
3. A degradable elastomeric material prepared by the method of any one of claims 1-2.
4. A method of making a nonwoven material using the degradable elastomeric material made of claim 3, comprising:
extruding a molten polymer melt of the degradable elastic material through petal-shaped spinneret orifices, and taking the extruded degradable elastic material as a basis for preparing a non-woven material.
5. The method of claim 4, wherein the petal-shaped orifices are hexapetal-shaped orifices.
6. The method according to claim 4 or 5, further comprising: the degradable elastic material extruded from the petal-shaped spinneret orifices is subjected to a melt-blown forming process to obtain a PBAT elastic fiber melt-blown fiber web;
and carrying out multistage hot drawing treatment on the PBAT elastic fiber melt-blown fiber web by a hot drawing device, and finally preparing the nonwoven material.
7. A nonwoven material prepared by the method of any one of claims 4-6.
8. Use of a nonwoven material prepared by the method of any one of claims 4-6 for preparing diaper, sanitary napkins, gowns, drapes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211318723.7A CN115613216B (en) | 2022-10-26 | 2022-10-26 | Degradable elastic material, nonwoven material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211318723.7A CN115613216B (en) | 2022-10-26 | 2022-10-26 | Degradable elastic material, nonwoven material and preparation method thereof |
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| CN115613216A CN115613216A (en) | 2023-01-17 |
| CN115613216B true CN115613216B (en) | 2023-09-12 |
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| CN113185820A (en) * | 2021-04-29 | 2021-07-30 | 赵若飞 | Degradable packaging material, packaging film bag and preparation method |
| CN114687066A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Degradable oil absorption material and preparation method thereof |
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2022
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775705A (en) * | 2009-12-29 | 2010-07-14 | 东华大学 | Manufacture method of biodegradable non-woven material |
| CN202482508U (en) * | 2012-03-12 | 2012-10-10 | 浙江正凯化纤有限公司 | Cross profile spinneret |
| CN102659333A (en) * | 2012-05-15 | 2012-09-12 | 江苏博特新材料有限公司 | Coarse fiber for concrete and preparation method of coarse fiber |
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| CN107447272A (en) * | 2017-06-08 | 2017-12-08 | 宁海德宝立新材料有限公司 | The preparation method of profiled filament with rough surface and obtained fiber and application |
| CN107779966A (en) * | 2017-11-30 | 2018-03-09 | 新凤鸣集团股份有限公司 | A kind of preparation method of compound Silk PFY |
| CN112048167A (en) * | 2020-09-18 | 2020-12-08 | 深圳市百奥降解材料科技有限公司 | Degradable thermoplastic elastomer and preparation method thereof |
| CN114687066A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Degradable oil absorption material and preparation method thereof |
| CN113185820A (en) * | 2021-04-29 | 2021-07-30 | 赵若飞 | Degradable packaging material, packaging film bag and preparation method |
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| CN115613216A (en) | 2023-01-17 |
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