CN112663171B - Degradable sheath-core polymer, high-melt-index degradable polymer, degradable composite fiber mesh fabric, and preparation method and application thereof - Google Patents

Degradable sheath-core polymer, high-melt-index degradable polymer, degradable composite fiber mesh fabric, and preparation method and application thereof Download PDF

Info

Publication number
CN112663171B
CN112663171B CN202011296812.7A CN202011296812A CN112663171B CN 112663171 B CN112663171 B CN 112663171B CN 202011296812 A CN202011296812 A CN 202011296812A CN 112663171 B CN112663171 B CN 112663171B
Authority
CN
China
Prior art keywords
degradable
polymer
gas
melt
polylactic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011296812.7A
Other languages
Chinese (zh)
Other versions
CN112663171A (en
Inventor
史佳林
朱艳青
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui Jinganrun Bio Tech Co ltd
Original Assignee
Anhui Jinganrun Bio Tech Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anhui Jinganrun Bio Tech Co ltd filed Critical Anhui Jinganrun Bio Tech Co ltd
Priority to CN202011296812.7A priority Critical patent/CN112663171B/en
Publication of CN112663171A publication Critical patent/CN112663171A/en
Application granted granted Critical
Publication of CN112663171B publication Critical patent/CN112663171B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

The invention discloses a degradable sheath-core polymer, a high-melt-index degradable polymer, a degradable composite fiber mesh fabric, and a preparation method and application thereof. The degradable skin-core polymer comprises a core layer polymer and a skin layer polymer coated on the surface of the core layer polymer, the skin layer polymer is prepared from raw materials including first polylactic acid, polycaprolactone and polybutylene adipate, and the core layer polymer is prepared from raw materials including second polylactic acid, polyhydroxyalkanoate and polybutylene terephthalate adipate. The invention can make full use of the compatibility among different raw materials, makes up the defect of single component, further prepares the biodegradable environment-friendly material with excellent mechanical property, leads the raw materials to be mixed more uniformly by carrying out the melting process in the back-mixing type reactor, does not need the granulating and drying process, avoids the thermal degradation phenomenon and reduces the energy consumption.

Description

Degradable sheath-core polymer, high-melt-index degradable polymer, degradable composite fiber mesh fabric, and preparation method and application thereof
Technical Field
The invention belongs to the field of melt direct spinning and multi-component multilayer degradable composite fiber mesh fabric high polymer materials, and relates to a degradable skin-core polymer and a preparation method and application thereof, a high-melting-index degradable polymer and a preparation method and application thereof, a degradable composite fiber mesh fabric and a preparation method and application thereof.
Background
The polymer composite fiber refers to two or more unmixed polymer fibers existing on the same fiber section, and is a physically modified fiber developed in the sixties of the twentieth century. Bicomponent fibers having two polymer properties can be obtained by a composite fiber production technique, and mainly include sheath-core type, side-by-side type, and sea-island type fibers. The sheath-core composite fiber is formed by mutually coating two components layer by layer and compounding the two components along the axial direction of the fiber, and generally refers to a concentric type, and in addition, an eccentric type, a special shape, a multilayer sheath-core type and the like are also available.
The skin layer and the core layer of the existing degradable polymer composite fiber are mostly made of single materials. Of these, the core layer material generally has a high melting point and a high strength, but has a problem of being relatively brittle and not easily crystallized. The skin layer material generally requires a lower melting point, but is not easy to realize production, and has higher requirements on enterprise production technology.
With the development of non-woven fabrics, higher requirements are put on the processing performance of degradable polymers, and the spinning process, the melt-blowing process, the high-speed spinning process and the superfine fiber process all require that the degradable polymers have good melt flow performance. Some pigments and additives which are not high in temperature resistance need degradable polymers with low processing temperature as carriers. These require that the degradable polymeric material have an ultra-high melt index at lower temperatures.
CN107805856B discloses a polylactic acid composite fiber and a preparation method thereof, wherein the polylactic acid and polycaprolactone blend is used as a skin layer, and polypropylene is used as a core layer to prepare the composite fiber, the polypropylene component in the composite fiber prepared by the method is non-degradable and loses the meaning of a degradable material, and in the method, the polypropylene and the polylactic acid are incompatible, and the melt can cause low strength, short elongation, poor spinnability and unsuitability for post-processing procedures of the fiber due to viscosity difference, flow index difference, crystallization rate difference and other factors when a spinneret plate is stretched.
CN101851830A discloses a fully degradable polylactic acid fiber SMS composite non-woven fabric and a manufacturing method thereof, and the material manufactured by the method has the defects of lumps, poor fluidity, large fiber brittleness and high elongation at break only reaching 12% due to lower melt index and incomplete drafting of partial melt filaments, and cannot realize the technical effects of high elongation and high toughness.
CN107304287A discloses a high heat-resistant high-fluidity polylactic resin composition, which comprises polylactic resin, a lubricant, an antioxidant, a flow modifier and an inorganic filling material. The fluidity of the polylactic resin is increased by adding the flow modifier into the formula, and the melt index of the obtained polylactic resin polymer can reach 85g/10min. In addition, the largest polylactic acid resin supplier worldwide, natureWorks company, polylactic acid melt index (such as 3251D, 6252D, 6361D) in industrial production is usually up to 85g/10min (210 ℃,2.16 kg). The polylactic acid resin can be applied to the fields of sewing, weaving, carpet backing, needle felt and the like, but cannot meet the requirement of high melt index of the invention.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a degradable sheath-core polymer, a degradable polymer with high melt index, a degradable composite fiber mesh fabric, a preparation method and application thereof, in particular to application in the technical field of environmental protection. The degradable sheath-core polymer and the degradable polymer with high melt index prepared by the invention are prepared by adopting multi-component raw materials, the defect of single component can be made up by utilizing the compatibility among different raw materials, the raw materials are more uniformly mixed by carrying out each melting process in the back-mixing type reactor, the spinning and spraying can be directly carried out without being granulated and dried, and the energy consumption is reduced.
The invention provides a degradable skin-core polymer, which comprises a core layer polymer and a skin layer polymer coated on the surface of the core layer polymer, wherein the raw materials for preparing the skin layer polymer comprise first polylactic acid, polycaprolactone (PCL) and polybutylene adipate succinate (PBSA), and the raw materials for preparing the core layer polymer comprise second polylactic acid, polyhydroxyalkanoate (PHA) and polybutylene terephthalate adipate (PBAT).
According to some embodiments of the degradable core-sheath polymer of the present invention, the content of the core layer polymer is 50 to 80 wt% and the content of the skin layer polymer is 20 to 50 wt% based on the total weight of the degradable core-sheath polymer. Also, the sheath-core polymer may be made as a bicomponent or multicomponent.
According to the specific embodiment of the degradable sheath-core polymer, the content of the sheath polymer is 29 wt% and the content of the core polymer is 71 wt% based on the total weight of the degradable sheath-core polymer.
According to the specific embodiment of the degradable core-sheath polymer, the content of the core layer polymer is 60 wt% and the content of the skin layer polymer is 40 wt% based on the total weight of the degradable core-sheath polymer.
According to some embodiments of the degradable core-sheath polymer of the present invention, the skin layer polymer is prepared from 50 to 60 wt% of the first polylactic acid, 10 to 20 wt% of the polycaprolactone, and 20 to 30 wt% of the polybutylene adipate succinate.
According to the embodiment of the degradable core-sheath polymer of the invention, the raw materials for preparing the sheath polymer comprise 50 wt% of first polylactic acid, 20 wt% of polycaprolactone and 30 wt% of polybutylene adipate succinate.
According to some embodiments of the degradable core-sheath polymer of the present invention, the core polymer is prepared from 60-70 wt% of the second polylactic acid, 20-30 wt% of the polyhydroxyalkanoate, and 5-15 wt% of polybutylene terephthalate adipate.
According to a preferred embodiment of the degradable core-sheath polymer, the core-layer polymer is prepared from 60-70 wt% of second polylactic acid, 20-30 wt% of polyhydroxyalkanoate and 10 wt% of polybutylene terephthalate adipate.
According to the specific embodiment of the degradable core-sheath polymer of the invention, the raw materials for preparing the core-layer polymer comprise 70 wt% of the second polylactic acid, 20 wt% of the polyhydroxyalkanoate and 10 wt% of polybutylene terephthalate adipate.
According to some embodiments of the degradable core-sheath polymer of the invention, the first polylactic acid is a low melting polylactic acid and the second polylactic acid is a high melting polylactic acid. The polylactic acid with the low melting point is low-melting-point amorphous polylactic acid (COPLA), and the polylactic acid with the high melting point is polylactic acid (PLA) with any crystal form. For example, the first polylactic acid in the present invention is available from model 6260D from Nature Works, inc., and the second polylactic acid in the core layer is available from model 6201D from Nature Works, inc.
According to a preferred embodiment of the degradable sheath-core polymer of the invention, the melting point of the low-melting polylactic acid is 125-135 ℃, and the melting point of the high-melting polylactic acid is 155-170 ℃.
According to a preferred embodiment of the degradable core-sheath polymer of the present invention, the polyhydroxyalkanoate is Polyhydroxybutyrate (PHB).
According to some embodiments of the degradable core-sheath polymer of the present invention, the polycaprolactone has a melting point of 59 to 64 ℃ and a glass transition temperature of-60 ℃ to-40 ℃. For example, the polycaprolactone of the present invention was obtained from solvay corporation as model 6500.
According to a preferred embodiment of the degradable core-sheath polymer of the present invention, the melting point of the polycaprolactone is 60 ℃ and the glass transition temperature is-60 ℃.
According to some embodiments of the degradable sheath-core polymer of the present invention, the weight ratio of the polycaprolactone to the first polylactic acid in the sheath polymer is 0.5-1: 2.5 to 3. For example, 1:2.5, 0.5:2.5, 1:3, and any value in between.
Due to the low melting point of polycaprolactone, the processing window of the polycaprolactone as a single component polymer is narrow, and the strength of the fiber is low. However, after the polycaprolactone and the polylactic acid are blended and then prepared into fibers, the brittleness, toughness and hydrophobicity of the polylactic acid can be effectively improved, and the strength and flexibility of the skin layer polymer obtained by compounding the polycaprolactone and the polylactic acid can be improved.
According to some embodiments of the degradable core-sheath polymer of the present invention, the polybutylene adipate succinate has a melting point of 110-115 ℃ and a glass transition temperature of-30 ℃. For example, polybutylene adipate succinate in the present invention is available from BASF as C2300FP.
According to some embodiments of the degradable core-sheath polymer of the present invention, in the sheath polymer, the weight ratio of polybutylene adipate succinate to the first polylactic acid is 1-1.5: 2.5 to 3. For example, 1.5:2.5, 1:2.5, 1:3. 1.5:3, and any value in between.
The relative molecular mass of the poly (butylene adipate succinate) is far less than that of the polylactic acid, the poly (butylene adipate succinate) can play a role in plasticization after being compounded with the polylactic acid, the crystallization of the polylactic acid is promoted, and when the poly (butylene adipate succinate) added into the skin layer polymer reaches 20 weight percent, the impact strength of the compounded material can reach 14.9kJ/m 2 The impact strength of the polylactic acid is 7.5 times of that of the pure polylactic acid, and the toughening effect is very obvious. The poly (butylene adipate succinate) is used as one of the components of the skin layer polymer, and is beneficial to improving the strength.
According to some embodiments of the degradable core-sheath polymer of the present invention, the polyhydroxyalkanoate has a melting point of 155 to 210 ℃ and a glass transition temperature of-45 to 4 ℃.
According to some embodiments of the degradable core-sheath polymer of the present invention, the weight ratio of the polyhydroxyalkanoate to the second polylactic acid in the core polymer is 1 to 1.5:3 to 3.5.
According to a preferred embodiment of the degradable sheath-core polymer of the present invention, the weight ratio of the polyhydroxyalkanoate to the second polylactic acid in the core polymer is 1 to 1.5:3.
the polyhydroxyalkanoate has the problems of narrow thermal processing window, easy thermal degradation, poor melt fluidity, sticky spinning and the like in the processing process of spinning and the like, and is not suitable for single-component processing. The polylactic acid and the polyhydroxyalkanoate have good biodegradability and biocompatibility after being compounded, the mixture of the polylactic acid and the polyhydroxyalkanoate has better thermal stability and spinnability, and the obtained product has high softness, good hand feeling and higher mechanical strength. From thermodynamic stability analysis, compared with pure polyhydroxyalkanoate, the initial thermal decomposition temperature is obviously improved after the polyhydroxyalkanoate is blended with polylactic acid.
The thermal decomposition mechanism of the polylactic acid is complex, reversible ester exchange reaction can occur in and among macromolecules of the polylactic acid, when the polyhydroxy fatty acid ester and the polylactic acid are blended and thermally decomposed, the ester exchange reaction possibly exists among macromolecule chains, so that the generation of the active center in the polyhydroxy fatty acid ester macromolecule chains can be inhibited, the initial thermal decomposition temperature of the polyhydroxy fatty acid ester is increased, and meanwhile, the thermal degradation of the polylactic acid can be promoted, and the initial thermal decomposition temperature of the polylactic acid can be reduced. Particularly, when the weight ratio of the polyhydroxyalkanoate to the second polylactic acid is 1:3 or 1:2, the initial thermal decomposition temperature of the polyhydroxyalkanoate is increased by 60 ℃. Particularly, the weight ratio of the two is 1: at 3, the initial thermal decomposition temperature of the polyhydroxyalkanoate was increased by 65 ℃.
Therefore, after the polyhydroxyalkanoate is blended with the polylactic acid, the thermal stability of the polyhydroxyalkanoate can be improved, and the processing window can be widened.
According to some embodiments of the degradable core-sheath polymer of the present invention, the polybutylene terephthalate adipate has a melting point of 110 to 135 ℃ and a glass transition temperature of-29 ℃.
According to some embodiments of the degradable sheath-core polymer of the present invention, the weight ratio of polybutylene terephthalate adipate to the second polylactic acid in the core polymer is 1:6 to 7.
The molecular chain of the polybutylene terephthalate adipate contains a flexible aliphatic chain and a rigid aromatic bond, when the polybutylene terephthalate is blended with the polylactic acid, the Young modulus of the polybutylene terephthalate and polylactic acid blend is reduced along with the increase of the content of the polybutylene terephthalate adipate, the breaking tensile strain and the impact strength are gradually increased, and the brittleness of the polylactic acid can be obviously improved.
The degradable skin-core polymer material provided by the invention can be used for sanitary materials, and particularly can be used for disposable sanitary materials such as diapers, sanitary towels, facial masks and the like. In addition, the degradable sheath-core polymer material can be spun to prepare fibers according to requirements, and the obtained fibers have soft self-crimping hand feeling.
The invention provides a preparation method of a degradable skin-core polymer, which comprises the following steps:
a1, mixing and melting first polylactic acid, polycaprolactone and poly (butylene adipate succinate) to obtain a skin layer polymer melt;
step B1, mixing and melting second polylactic acid, polyhydroxyalkanoate and polybutylene terephthalate adipate to obtain a core layer polymer melt;
and C1, respectively sending the skin layer polymer melt as a skin layer and the core layer polymer melt as a core layer into a spinning composite die head for spinning and spraying to obtain the degradable skin-core polymer.
According to some embodiments of the preparation method of the present invention, the content of the skin layer polymer is 20 to 50 wt% and the content of the core layer polymer is 50 to 80 wt% based on the total weight of the degradable skin-core polymer. Also, the sheath-core polymer may be made as a bicomponent or multicomponent.
According to a specific embodiment of the preparation method of the present invention, the content of the skin layer polymer is 29 wt% and the content of the core layer polymer is 71 wt% based on the total weight of the degradable skin-core polymer.
According to a specific embodiment of the preparation method of the present invention, the content of the skin layer polymer is 40 wt% and the content of the core layer polymer is 60 wt% based on the total weight of the degradable skin-core polymer.
According to some embodiments of the method of manufacturing of the present invention, the raw material for manufacturing the skin layer polymer includes 50 to 60 wt% of the first polylactic acid, 10 to 20 wt% of the polycaprolactone, and 20 to 30 wt% of the polybutylene adipate succinate.
According to an embodiment of the preparation method of the present invention, the raw materials for preparing the skin layer polymer comprise 50 wt% of the first polylactic acid, 20 wt% of the polycaprolactone and 30 wt% of the polybutylene adipate succinate.
According to some embodiments of the method of manufacturing of the present invention, the raw materials for manufacturing the core layer polymer include 60 to 70 wt% of the second polylactic acid, 20 to 30 wt% of the polyhydroxyalkanoate, and 5 to 15 wt% of polybutylene terephthalate.
According to a preferred embodiment of the preparation method of the present invention, the raw materials for preparing the core layer polymer include 60 to 70 wt% of the second polylactic acid, 20 to 30 wt% of the polyhydroxyalkanoate, and 10 wt% of polybutylene terephthalate adipate.
According to an embodiment of the preparation method of the present invention, the raw materials for preparing the core layer polymer include 70 wt% of the second polylactic acid, 20 wt% of the polyhydroxyalkanoate, and 10 wt% of polybutylene terephthalate adipate.
According to some embodiments of the method of manufacturing of the present invention, the first polylactic acid is a low melting point polylactic acid, and the second polylactic acid is a high melting point polylactic acid. The polylactic acid with the low melting point is low-melting-point amorphous polylactic acid, and the polylactic acid with the high melting point is polylactic acid with any crystallization form.
According to a preferred embodiment of the production method of the present invention, the melting point of the low-melting polylactic acid is 125 to 135 ℃, and the melting point of the high-melting polylactic acid is 155 to 170 ℃.
According to a preferred embodiment of the production method of the present invention, polyhydroxybutyrate is used as the polyhydroxyfatty acid ester.
According to some embodiments of the preparation method of the present invention, in the skin layer polymer, the weight ratio of the polycaprolactone to the first polylactic acid is 0.5-1: 2.5 to 3. For example, 1:2.5, 0.5:2.5, 1:3, and any value in between.
According to some embodiments of the preparation method of the present invention, in the skin layer polymer, the weight ratio of the polybutylene adipate succinate to the first polylactic acid is 1 to 1.5:2.5 to 3. For example, 1.5:2.5, 1:2.5, 1:3. 1.5:3, and any value in between.
According to some embodiments of the preparation method of the present invention, in the core layer polymer, the weight ratio of the polyhydroxyalkanoate to the second polylactic acid is 1 to 1.5:3 to 3.5.
According to a preferred embodiment of the preparation method of the present invention, in the core layer polymer, the weight ratio of the polyhydroxyalkanoate to the second polylactic acid is 1 to 1.5:3.
according to some embodiments of the preparation method of the present invention, in the core layer polymer, the weight ratio of polybutylene terephthalate adipate to the second polylactic acid is 1:6 to 7.
According to some embodiments of the method of manufacturing of the present invention, the mixing melting conditions in step A1 include: the temperature is 110-150 ℃, the vacuum degree is 30-45 kPa, the time is 10-40 min, and the rotating speed of a stirring paddle is 10-30 RPM.
According to a specific embodiment of the preparation method of the present invention, the mixing and melting conditions in step A1 include: the temperature was 150 ℃, the vacuum was 45kPa, the time was 30min, and the rotational speed of the stirring paddle was 20RPM.
According to some embodiments of the method of manufacturing of the present invention, the mixing melting conditions in step B1 include: the temperature is 155-210 ℃, the vacuum degree is 30-45 kPa, the time is 20-40 min, and the rotating speed of a stirring paddle is 15-35 RPM.
According to a specific embodiment of the preparation method of the present invention, the mixing and melting conditions in step B1 include: the temperature was 210 ℃, the vacuum was 30kPa, the time was 25min, and the rotational speed of the stirring paddle was 25RPM.
According to some embodiments of the method of making of the present invention, the sheath polymer melt and the core polymer melt have apparent viscosity values of 1.2Pa.s or less.
In the spinning process, if the apparent viscosity difference between the skin layer polymer melt and the core layer polymer melt is too large, the melt can bend to the side with high viscosity in the spinning process, and can even adhere to the surface of a spinneret plate in serious conditions, so that the skin layer and the core layer are unevenly distributed.
According to some embodiments of the method of making, the skin layer polymer melt is fed to the spin-compounding die at a temperature of 120 to 150 ℃.
According to some embodiments of the method of making of the present invention, the core polymer melt is fed to the spin-compounding die at a temperature of 160 to 210 ℃.
According to some embodiments of the method of making of the present invention, the conditions under which the spinning jet process is performed in the spin composite die member include: the temperature of the die head is 160-210 ℃, the number of holes of the spinneret plate is 500-2000, and the width of the die head is less than or equal to 6m.
According to a preferred embodiment of the preparation method of the present invention, the width of the die in the spinning composite die member is 1.6 to 6m.
According to some embodiments of the method of making described herein, the spinneret hole pitch in the spun composite die piece is 3 to 5mm.
In various embodiments of the present invention, control of the spinning die temperature is critical during the spinning jet. When the skin layer polymer melt and the core layer polymer melt are respectively fed into the spinning composite die head, the skin layer polymer melt and the core layer polymer melt are respectively and independently conveyed in different pipelines, and the different pipelines in which the two components are arranged are respectively controlled by the invention in consideration of the different characteristics of the skin layer polymer and the core layer polymer. For example, the temperature of the pipe in which the skin layer polymer melt is present is controlled to be 120 to 150 ℃ and the temperature of the pipe in which the core layer polymer melt is present is controlled to be 160 to 210 ℃.
According to some embodiments of the preparation method of the present invention, the first polylactic acid, the polycaprolactone and the polybutylene adipate are fed into the first mixing device for premixing before the mixing and melting of the step A1.
According to some embodiments of the preparation method of the present invention, the second polylactic acid, the polyhydroxyalkanoate, and the polybutylene terephthalate adipate are fed into the second mixing device to be premixed before the mixing melting of step B1 is performed.
According to a preferred embodiment of the preparation process according to the invention, the mixing and melting process of step A1 is carried out in a first back-mixed reactor. The mixing and melting process of step B1 is carried out in a second back-mixed reactor.
According to an embodiment of the preparation method, the first back-mixing type reactor and the second back-mixing type reactor are at least one of a vertical full-mixing internal heating type reactor, a horizontal full-mixing internal heating type reactor and a cross-over disc type pipeline reactor.
In the preparation method of the invention, the defects of difficulty and high cost of a linear reactor in processing a large amount of reaction heat can be avoided by selecting the back-mixing type reactor, and the preparation method has the following advantages: (1) the residence time of the melt reaction can be made to be more than 30min. And (2) the requirement of high exothermic energy reaction can be met. And (4) direct melt spinning can be realized.
According to some embodiments of the preparation method of the present invention, in step C1, before the spinning jet, the skin layer polymer melt and the core layer polymer melt are respectively sequentially fed into the spinning compound die by weight ratio through a pressure reducing valve, a booster pump, a filter and a metering device to be spun and jetted.
According to the preparation method of the degradable skin-core polymer, the skin layer raw material and the core layer raw material are independently melted through the back-mixing reactor to obtain corresponding melts, the raw materials are uniformly mixed under the stirring of the blades in the melting process, the melts obtained through melting can be directly spun and sprayed without being granulated and dried, the problem that the multi-component polymer obtained through melting and mixing under the condition of double-screw high shear in the traditional process is prone to thermal degradation is solved, the spinnability of the degradable skin-core polymer is improved, and the energy consumption can be reduced by 30-40%.
The third aspect of the invention provides a high-melt-index degradable polymer, which is prepared from the raw materials including polyester and additives, wherein the polyester comprises third polylactic acid, polybutylene terephthalate adipate and polyhydroxyalkanoate.
According to some embodiments of the high melt index degradable polymer of the present invention, the polyester comprises 60 to 70 wt% of the third polylactic acid, 10 to 20 wt% of polybutylene terephthalate adipate and 15 to 30 wt% of polyhydroxyalkanoate.
According to a specific embodiment of the high melt index degradable polymer of the present invention, the polyester comprises 70 wt% of the third polylactic acid, 10 wt% of polybutylene terephthalate adipate and 20 wt% of polyhydroxyalkanoate.
According to some embodiments of the high melt index degradable polymer of the present invention, the weight ratio of the additive to the polyester is 1 to 7:100.
according to some embodiments of the high melt index degradable polymer of the present invention, the third polylactic acid has a melting point of 125 to 175 ℃, a melt index of 30 to 85g/10min, and a relative viscosity of 2.5 to 3. For example, the third polylactic acid in the present invention is selected from at least one of the polylactic acid resins manufactured by NatureWorks corporation under the trade name of 6361D, 6260D and 6252D, or from L105 and/or LX530 manufactured by dadalke bi en corporation, or from the polylactic acid resin manufactured by zhejiang sea biomaterial corporation under the trade name of revolute 190.
According to some embodiments of the high melt index degradable polymer of the present invention, the polybutylene terephthalate adipate has a melting point of 110 to 135 ℃, a melt index of 10 to 20g/10min, and a relative viscosity of 2 to 3. For example, the polybutylene terephthalate adipate in the present invention is selected from C1200FP of BASF corporation and/or TH801T of Tunghe of Xinjiang province.
According to some embodiments of the high-melt-index degradable polymer of the present invention, the weight ratio of the polybutylene terephthalate-co-adipate to the third polylactic acid is 0.5-1: 3 to 3.5. For example, 0.5:3.5, 0.5:3. 1:3. 1:3.5, and any value in between.
According to some embodiments of the high-melt-index degradable polymer of the present invention, the polyhydroxyalkanoate has a melting point of 130 to 155 ℃, a melt index of 20 to 60g/10min, and a relative viscosity of 2 to 3. For example, the polyhydroxyalkanoate in the present invention is selected from at least one of KANEKA TY04118, RWDC SOLON1200, and METABOLIX F1700, japan.
According to some embodiments of the high-melt-index degradable polymer of the present invention, the weight ratio of the polyhydroxyalkanoate to the third polylactic acid is 1.5-3: 6 to 7. For example, 2: 7. 1:2. 1.5: 7. 1: 4. 3:7, and any value in between.
According to a preferred embodiment of the high-melt-index degradable polymer, the weight ratio of the polyhydroxyalkanoate to the third polylactic acid is 1:3 to 3.5.
According to some embodiments of the high melt index degradable polymer of the present invention, the additives comprise catalysts, initiators, antioxidants, plasticizers and electret modifiers. In addition, when various additives are added, solvents are not needed to be used for preparing the solution, and because the commonly used solvents such as dichloromethane, trichloromethane, tetrahydrofuran, ethyl acetate and the like have high toxicity, the recovery cost of the solvents is high, and the requirements of environmental protection are not met.
According to some embodiments of the high melt index degradable polymer of the present invention, the catalyst is obtained by compounding a first catalyst and a second catalyst. Wherein the first catalyst is an active hydroxyl-containing metal catalyst. The second catalyst is tetrabutyl titanate and/or stannous octoate.
According to a preferred embodiment of the high melt index degradable polymer according to the invention, the first catalyst is a titanocene compound.
According to some embodiments of the high-melt-index degradable polymer, the weight ratio of the first catalyst to the second catalyst is 5-7: 3 to 5.
According to a preferred embodiment of the high-melt-index degradable polymer, the weight ratio of the first catalyst to the second catalyst is 7:3 or 6:4 or 5:5.
according to some embodiments of the high melt index degradable polymer of the present invention, the initiator is an organic peroxide.
According to a preferred embodiment of the high-melt-index degradable polymer of the present invention, the initiator is a high-temperature organic peroxide (temperature of 100 ℃ or higher).
According to the embodiment of the high-melting index degradable polymer, the initiator is at least one selected from di-tert-butyl peroxide, dicumyl peroxide, carbonic ester peroxide and dibenzoyl peroxide, and is more preferably 2,5-dimethylhexane-2,5-di-tert-butyl peroxide and/or bis (2,4-dichlorobenzoyl) peroxide.
According to a specific embodiment of the high-melting-index degradable polymer, the antioxidant is octa- [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] tripentaerythritol ester and/or tetra- [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester. Preferably, the antioxidant is pentaerythritol tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010).
According to a specific embodiment of the high-melt-index degradable polymer of the present invention, the plasticizer is at least one selected from the group consisting of tributyl citrate, epoxidized soybean oil and polyethylene glycol.
According to a specific embodiment of the high melt index degradable polymer of the present invention, the electret modifier is selected from an organic additive (o-electric) and/or an inorganic additive, preferably nano-silica. For example, the electret modifier in the present invention is nano-silica.
According to some embodiments of the high melt index degradable polymer of the present invention, the weight ratio of the catalyst to the polyester is 0.1-2: 100. for example, 0.1: 100. 0.5:100. 1:100. 1.5:100. 2:100, and any value in between.
According to some embodiments of the high melt index degradable polymer of the present invention, the weight ratio of the initiator to the polyester is 0.1-1: 100. for example, 0.1: 100. 0.4: 100. 0.5:100. 1:100, and any value in between.
According to some embodiments of the high melt index degradable polymer of the present invention, the weight ratio of the antioxidant to the polyester is 0.2-2: 100. for example, 0.2: 100. 1:100. 1.5:100. 2:100, and any value in between.
According to some embodiments of the high melt index degradable polymer of the present invention, the weight ratio of the plasticizer to the polyester is 0.1-0.5: 100. for example, 0.1: 100. 0.2: 100. 0.3: 100. 0.4: 100. 0.5:100, and any value in between.
According to some embodiments of the high melt index degradable polymer of the present invention, the weight ratio of the electret modifier to the polyester is 0.5 to 1.5:100. for example, 0.5:100. 0.6: 100. 1:100. 1.5:100, and any value in between.
The high-melt-index degradable polymer obtained by the invention has the melt index of 500-1000 g/10min and the fiber fineness of less than or equal to 2 mu m under the conditions of 200 ℃ and 2.16kg, can overcome the defects of large brittleness, low melt index, poor fluidity, thick fiber fineness and poor compactness of a single degradable polymer, and has the advantages of excellent barrier property and good filtering effect.
The high-melt-index degradable polymer obtained by the invention can be used for environment-friendly masks and surgical protective clothing, and is particularly suitable for medical environment-friendly masks.
The invention provides a preparation method of a degradable polymer with high melt index, which comprises the following steps:
step A2, mixing polyester and additives, and carrying out a melt reaction to prepare a high-melt-index degradable polymer precursor, wherein the polyester comprises third polylactic acid, polybutylene terephthalate adipate and polyhydroxyalkanoate;
and B2, sending the high-melt-index degradable polymer precursor into a melt-blown spinning die head for spinning and spraying to obtain the high-melt-index degradable polymer.
According to some embodiments of the preparation process of the present invention, the melt reaction is carried out in a third back-mixed reactor.
According to some embodiments of the method of manufacturing of the present invention, the polyester includes 60 to 70% by weight of the third polylactic acid, 10 to 20% by weight of polybutylene terephthalate adipate, and 15 to 30% by weight of polyhydroxyalkanoate.
According to a specific embodiment of the preparation method of the present invention, the polyester includes 70 wt% of the third polylactic acid, 10 wt% of polybutylene terephthalate adipate and 20 wt% of polyhydroxyalkanoate.
According to some embodiments of the method of preparation of the present invention, the weight ratio of the additive to polyester is 1 to 7:100.
according to some embodiments of the method of preparing of the present invention, the third polylactic acid has a melting point of 125 to 175 ℃, a melt index of 30 to 85g/10min, and a relative viscosity of 2.5 to 3. For example, the third polylactic acid in the present invention is selected from at least one of the polylactic acid resins manufactured by NatureWorks corporation under the trade name of 6361D, 6260D and 6252D, or from L105 and/or LX530 manufactured by dadalke bi en corporation, or from the polylactic acid resin manufactured by zhejiang sea biomaterial corporation under the trade name of revolute 190.
According to some embodiments of the preparation method of the present invention, the polybutylene terephthalate adipate has a melting point of 110 to 135 ℃, a melt index of 10 to 20g/10min, and a relative viscosity of 2 to 3. For example, the polybutylene terephthalate adipate in the present invention is selected from C1200FP of BASF corporation and/or TH801T of Tunghe of Xinjiang province.
According to some embodiments of the method of the present invention, the weight ratio of the polybutylene terephthalate to the third polylactic acid is 0.5-1: 3 to 3.5. For example, 0.5:3.5, 0.5:3. 1:3.5, 1:3.5, and any value in between.
According to some embodiments of the method of the present invention, the polyhydroxyalkanoate has a melting point of 130 to 155 ℃, a melt index of 20 to 60g/10min, and a relative viscosity of 2 to 3. For example, the polyhydroxyalkanoate in the present invention is at least one selected from KANEKA TY04118, RWDC SOLON1200, singapore and METABOLIX F1700, japan.
According to some embodiments of the preparation method of the present invention, the weight ratio of the polyhydroxyalkanoate to the third polylactic acid is 1.5 to 3:6 to 7. For example, 2: 7. 1:2. 1.5: 7. 1: 4. 3:7, and any value in between.
According to a preferred embodiment of the preparation method of the present invention, the weight ratio of the polyhydroxyalkanoate to the third polylactic acid is 1:3 to 3.5.
According to some embodiments of the method of making of the present invention, the additives include catalysts, initiators, antioxidants, plasticizers, and electret modifiers.
In the preparation method, when various additives are added, a solvent is not required to be used for preparing a solution, because the commonly used solvents such as dichloromethane, trichloromethane, tetrahydrofuran, ethyl acetate and the like have high toxicity, the recovery cost of the solvent is high, and the preparation method does not meet the requirement of environmental protection. In the invention, the PCL program is used for controlling the micro-distributor batching system, so that the accurate proportioning requirement of various added additives is met.
According to some embodiments of the method of manufacturing of the present invention, step A2 comprises: adding polyester into a first metering bin, adding various additives into a second metering bin, and respectively sending the polyester into a third back-mixing type reactor for melt reaction from the first metering bin and the second metering bin according to the proportion through a PLC (programmable logic controller) set program.
According to some embodiments of the method of preparing of the present invention, the catalyst is obtained by compounding a first catalyst and a second catalyst. Wherein the first catalyst is an active hydroxyl-containing metal catalyst. The second catalyst is tetrabutyl titanate and/or stannous octoate.
According to a preferred embodiment of the preparation method of the present invention, the first catalyst is a titanocene compound.
According to some embodiments of the preparation method of the present invention, the weight ratio of the first catalyst to the second catalyst is 5 to 7:3 to 5.
According to a preferred embodiment of the preparation method of the present invention, the weight ratio of the first catalyst to the second catalyst is 7:3 or 6:4 or 5:5.
according to some embodiments of the method of preparing of the present invention, the initiator is an organic peroxide.
According to a preferred embodiment of the production method of the present invention, the initiator is a high-temperature type (temperature of 100 ℃ or higher) organic peroxide.
According to the specific embodiment of the preparation method, the initiator is selected from one or more of di-tert-butyl peroxide, dicumyl peroxide, 2,5-dimethylhexane-2,5-di-tert-butyl peroxide, peroxycarbonate, dibenzoyl peroxide and bis (2,4-dichlorobenzoyl) peroxide.
According to a specific embodiment of the preparation method, the antioxidant is octa [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] tripentaerythritol ester and/or tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
According to a specific embodiment of the preparation method of the present invention, the plasticizer is at least one selected from the group consisting of tributyl citrate, epoxidized soybean oil, and polyethylene glycol.
According to a particular embodiment of the preparation method of the present invention, the electret modifier is selected from an organic auxiliary agent (o-electret) and/or an inorganic auxiliary agent, preferably nanosilica. For example, the electret modifier in the present invention is nano silica.
According to some embodiments of the method of the present invention, the weight ratio of the catalyst to the polyester is 0.1 to 2:100. for example, 0.1: 100. 0.5:100. 1:100. 1.5:100. 2:100, and any value in between.
According to some embodiments of the method of the present invention, the weight ratio of the initiator to the polyester is 0.1 to 1:100. for example, 0.1: 100. 0.4: 100. 0.5:100. 1:100, and any value in between.
According to some embodiments of the method of the present invention, the weight ratio of the antioxidant to the polyester is 0.2 to 2:100. for example, 0.2: 100. 1:100. 1.5:100. 2:100, and any value in between.
According to some embodiments of the method of the present invention, the weight ratio of the plasticizer to the polyester is 0.1 to 0.5:100. for example, 0.1: 100. 0.2: 100. 0.3: 100. 0.4: 100. 0.5:100, and any value in between.
According to some embodiments of the method of the present invention, the weight ratio of the electret modifier to the polyester is 0.5 to 1.5:100. for example, 0.5:100. 0.6: 100. 1:100. 1.5:100, and any value in between.
According to some embodiments of the method of manufacturing of the present invention, the conditions of the mixing and melting include: the temperature is 155-210 ℃, the vacuum degree is 30-45 kPa, the time is 20-40 min, and the stirring speed is 5-25 RPM.
According to a specific embodiment of the production method of the present invention, the conditions of the mixing and melting include: the temperature was 210 deg.C, the vacuum 30kPa, the time 40min, and the stirring speed 25RPM.
According to the specific embodiment of the preparation method, the high-melt-index degradable polymer has a melt index of 500-1300 g/10min at 200 ℃ and 2.16 kg.
According to some embodiments of the method of manufacturing of the present invention, the conditions under which the spinning jet is carried out in the meltblowing spinning die head comprise: the temperature of the die head is 150-210 ℃, the number of holes of the spinneret plate is 500-2000, the width of the die head is less than or equal to 6m, the air flow traction speed is 1500-2500 m/min, and the temperature of the compressed air is 200-350 ℃.
According to a preferred embodiment of the preparation method of the present invention, the spinning ejection process is performed under a high temperature air flow condition, wherein a high temperature high speed air flow drawing speed is 1500-2500 m/min, and a high temperature compressed air temperature is 200-350 ℃.
According to a preferred embodiment of the production method of the present invention, in the melt-blown spinning die, the die width is 1.6 to 6m.
According to some embodiments of the process of the present invention, the melt-blown spinning die has a spinneret pitch of 0.7 to 1mm.
The third back-mixing type reactor in the invention is at least one selected from a vertical full-mixing internal heating type reactor, a horizontal full-mixing internal heating type reactor and a cross-over disc type pipeline reactor.
In the preparation method of the invention, the defects of difficulty and high cost of a linear reactor in treating a large amount of reaction heat can be avoided by selecting the back-mixing type reactor, and the preparation method has the following advantages: (1) the residence time of the melt reaction can be made to be more than 30min. And (2) the requirement of high exothermic energy reaction can be met. (3) The influence of the initial feeding, the final product performance and the like on the preparation of the degradable polymer with high melt index can be avoided. And (4) direct melt spinning can be realized.
According to the invention, through carrying out the melting process in the back-mixing type reactor, the raw materials can be mixed more uniformly under the stirring action of the blades, the melt obtained by melting can be directly spun and sprayed without being granulated and dried, the problem that the thermal degradation phenomenon of the multi-component polymer molten and mixed under the condition of double screw high shear in the traditional process is easy to occur is solved, and the energy consumption is reduced.
Further, multiple layers of the high melt index degradable polymer can be prepared simultaneously according to different working requirements in different embodiments of the invention. Specifically, the high-melt-index degradable polymer precursor obtained in the step A2 is sent into an equal distributor which is divided into two parts or three parts or four parts after passing through a pressure reducing valve and a booster pump, and then is sent into a plurality of corresponding melt-blown spinning die heads for spinning and spraying.
The fifth aspect of the invention provides a degradable composite fiber mesh fabric, which is a layered structure and comprises an upper layer, a lower layer and at least one intermediate layer, wherein the upper layer and the lower layer are the degradable skin-core polymer or the degradable skin-core polymer prepared by the method, and the intermediate layer is the high-melt-index degradable polymer or the high-melt-index degradable polymer prepared by the method.
According to some embodiments of the degradable composite web fabric of the invention, the longitudinal strength of the degradable composite web fabric is 80 to 200N/5cm, preferably 132 to 200N/5cm; the longitudinal elongation at break is 60 to 120 percent, and preferably 96 to 120 percent; the transverse strength is 60-170N/5 cm, preferably 124-170N/5 cm; the elongation at break in the transverse direction is 50 to 110%, preferably 79 to 110%.
According to the preferable embodiment of the degradable composite fiber net fabric, the surface density of the degradable composite fiber net fabric is 10-150 g/m 2 . Such as 10, 30, 50, 80, 90, 100, 120, 140, 150, and any value therebetween.
The degradable composite fiber mesh fabric provided by the invention has excellent mechanical property, good barrier property, antibiosis, flame retardance and biodegradability, and can be widely applied to environment-friendly interior trim of traffic tools such as aviation, railway, highway and the like and environment-friendly fields such as clothing, home decoration, medical treatment, tissue engineering, filtering materials, sanitary materials and the like.
The invention provides a preparation method of a degradable composite fiber mesh fabric, which comprises the following steps:
a3, sequentially carrying out spinning, airflow traction, cooling, splitting and lapping on the degradable skin-core polymer to obtain a lower-layer spun-bonded composite fiber net, wherein the degradable skin-core polymer is the degradable skin-core polymer or the degradable skin-core polymer prepared by the method;
b3, sequentially carrying out spinning, air flow traction, cooling and wire dividing and lapping on the high-melt-index degradable polymer to obtain a middle-layer melt-blown fiber net, wherein the high-melt-index degradable polymer is the high-melt-index degradable polymer or the high-melt-index degradable polymer prepared by the method;
step C3, sequentially carrying out spinning, airflow traction, cooling, splitting and lapping on the degradable skin-core polymer to obtain an upper layer of spun-bonded composite fiber net, wherein the degradable skin-core polymer is the degradable skin-core polymer or the degradable skin-core polymer prepared by the method;
and D3, superposing the lower-layer spun-bonded composite fiber net, at least one middle-layer melt-blown fiber net and the upper-layer spun-bonded composite fiber net, and then carrying out hot rolling to obtain the degradable composite fiber net fabric.
According to some embodiments of the method of making of the present invention, the degradable composite web fabric has a machine direction tenacity of 80 to 200N/5cm, a machine direction elongation at break of 60 to 120%, a cross direction tenacity of 60 to 170N/5cm, and a cross direction elongation at break of 50 to 110%.
According to a preferred embodiment of the preparation method of the present invention, the surface density of the degradable composite fiber web fabric is 10 to 150g/m 2 . Such as 10, 30, 50, 80, 90, 100, 120, 140, 150, and any value therebetween.
According to some embodiments of the method of manufacturing of the present invention, the air flow drawing speed in step A3 is 1500-2500 m/min, and the dividing and lapping speeds are 200-1200 m/min.
According to some embodiments of the method of manufacturing of the present invention, the conditions of the gas flow pulling process in step B3 include: the air flow speed is 1500-2500 m/min, and the air flow temperature is 200-350 ℃; the speed of dividing and lapping is 200-1200 m/min.
According to some embodiments of the method of manufacturing of the present invention, the air flow drawing speed in step C3 is 1500 to 2500m/min, and the dividing and lapping speeds are 200 to 1200m/min.
According to some embodiments of the method of manufacturing of the present invention, the hot rolling temperature in the step D3 is 60 to 120 ℃.
According to some embodiments of the method of making of the present invention, the number of layers of the middle layer meltblown web is 1 to 5. Preferably, step B3 further comprises, before spinning: and feeding the high-melt-index degradable polymer into an equal divider which is divided into two parts or three parts or four parts for distribution.
According to some embodiments of the method of manufacturing of the present invention, step D3 further comprises: and respectively spraying the middle-layer melt-blown fiber web, the lower-layer spun-bonded composite fiber web and the upper-layer spun-bonded composite fiber web onto three or more groups of cooling rolls by using high-temperature and high-pressure air jet flow to cool and form a web, and performing consolidation, superposition and hot rolling.
The seventh aspect of the present invention provides an application of the above degradable skin-core polymer, the above degradable skin-core polymer preparation method, the above high melt index degradable polymer preparation method, the above degradable composite fiber mesh fabric or the above degradable composite fiber mesh fabric preparation method in the field of environmental protection technology, more preferably in vehicle interior trim, clothing, home decoration, medical treatment, tissue engineering, filter materials and sanitary materials. But is not limited thereto.
The invention has the beneficial effects that:
(1) The degradable sheath-core polymer and the degradable polymer with high melt index are prepared from multi-component raw materials, the compatibility among different raw materials can be fully utilized by adjusting the proportion of the raw materials, the defect of a single component is made up by compounding the raw materials, and the biodegradable environment-friendly material with excellent mechanical property is prepared.
(2) According to the invention, through carrying out each melting process in the back-mixing type reactor, each raw material can be mixed more uniformly under the stirring action of the paddle, the melt obtained by melting can be directly spun and sprayed without being granulated and dried, the problem that the multi-component polymer molten and mixed under the condition of double screw high shear in the traditional process is easy to have a thermal degradation phenomenon is solved, and the energy consumption is reduced.
Drawings
Fig. 1 is a schematic flow chart of a preparation process of a degradable composite fiber web fabric provided by an embodiment of the invention.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
The sources of the reagents in the invention are as follows:
(1) The first polylactic acid in the skin layer was purchased from model 6260D from Nature Works, inc.
(2) The second polylactic acid in the core layer was purchased from Nature Works corporation, model 6201D.
(3) Polycaprolactone was purchased from solvay corporation as model 6500.
(4) Polybutylene adipate succinate was purchased from BASF C2300FP.
(5) The third polylactic acid in the high melt index degradable polymer was purchased from the Nature Works company model 3100D.
(6) The polyhydroxyalkanoate is selected from TY04118 from KANEKA, japan.
(7) The polybutylene terephthalate adipate was selected from the C1200FP model from BASF corporation.
The remaining reagents of the present invention are also commercially available.
[ example 1 ]
In this example, the blending ratio of the raw materials for preparing the degradable sheath-core polymer is shown in table 1, and the blending ratio of the raw materials for preparing the degradable polymer with high melt index is shown in table 2. The contents of each component in tables 1 and 2 are weight contents.
TABLE 1
Figure BDA0002785655390000181
TABLE 2
Figure BDA0002785655390000191
Wherein, the catalyst in table 2 is titanocene and tetrabutyl titanate according to the weight ratio of 7:3, the initiator is 2,5-dimethylhexane-2,5-di-tert-butyl peroxide, the antioxidant is antioxidant 1010, the plasticizer is tributyl citrate, and the electret modifier is nano silicon dioxide.
The preparation method is shown in figure 1 and specifically comprises the following steps:
(1) Preparing the skin layer of the degradable skin-core polymer: the raw materials of the skin layer are placed into a first mixing device for premixing according to the components in the table 1, and the mixed raw materials of the skin layer are placed into a first back-mixing type reactor for melting, wherein the melting temperature is 150 ℃, the vacuum degree is 45kPa, the rotating speed of a stirring paddle is 20RPM, and the melting time is 30min, so that a skin layer polymer melt is obtained.
(2) Preparing a core layer of the degradable skin-core polymer: the core layer raw materials are placed into a second mixing device according to the components in the table 1 for premixing, and the mixed core layer raw materials are placed into a second back-mixing type reactor for melting, wherein the melting temperature is 210 ℃, the vacuum degree is 30kPa, the rotating speed of a stirring paddle is 25RPM, and the melting time is 25min, so that a core layer polymer melt is obtained.
(3) Preparation of high melt index degradable polymers: the three polyesters were fed to a first metering silo according to the composition of table 2 and the additives were fed to a second metering silo. And setting a program by a PLC (programmable logic controller), and respectively feeding the catalyst, the initiator, the antioxidant, the plasticizer and the electret modifier which correspond to 50kg/h of polyester into a third back-mixing reactor for melt reaction from a first metering bin and a second metering bin according to the proportion of 500g/h, 250g/h, 500g/h, 100g/h and 300g/h, wherein the stirring speed in the melt process is 25RPM, the reaction time is 40min, the temperature is 210 ℃, and the vacuum degree is 30kPa. The melt index of the degradable polymer precursor with the high melt index is 933g/10min.
(4) Preparing degradable skin-core polymer: the method comprises the following steps of conveying a skin layer polymer melt and a core layer polymer melt to an upper skin layer spinning box body, a lower skin layer spinning box body and a core layer spinning box body respectively through a pressure reducing valve, a booster pump and a filter in sequence, converging the two melts into a composite spinning die head through a one-inlet and multi-outlet melt metering pump according to the weight ratio in the table 1, spinning and spraying, longitudinally drawing tows through high-pressure air to fall onto a roller with a cooling air suction device and a conveying chain plate, dividing and lapping, finishing lapping and conveying, and obtaining an upper layer spunbonded composite fiber web and a lower layer spunbonded composite fiber web. Wherein the rotating speed of the metering pump is 45RPM. The temperature of a composite spinning die head is 210 ℃, the high-speed airflow traction speed is 1500m/min, 1000 holes are selected for a composite spun-bonded spinning assembly, the width of the die head is 2.4 meters, and the web forming speed is as follows: the lower layer of the spun-bonded roller has a conveying speed of 200m/min, and the upper layer of the spun-bonded roller has a conveying speed of 600m/min.
(5) Preparing a degradable composite fiber mesh fabric: the method comprises the steps of conveying a high-melting-index degradable polymer precursor into a melt-blown spinning box body through a pressure reducing valve, a booster pump and a filter, directly entering a melt-blown spinning die head through a metering pump for spinning and spraying, then cooling and drawing through longitudinal high-temperature high-speed air flow, falling onto a lower-layer spun-bonded composite fiber net on an air-suction yarn-separating lapping net, conveying to an upper-layer spun-bonded air-suction yarn-separating lapping net to be covered by an upper-layer spun-bonded composite fiber net, and then hot rolling through a hot roller to reinforce a net fabric material to obtain the degradable composite fiber net fabric. Wherein the rotating speed of a metering pump is 40RPM, the temperature of a melt-blown spinning die head is 210 ℃, the traction speed of high-speed air flow is 2000m/min, the temperature of high-pressure air is 260 ℃, 1500 holes are selected for a melt-blown spinning assembly, the width of the die head is 2.4 meters, and the web forming speed is 500m/min.
The three-layer multi-component degradable composite fiber mesh fabric material obtained in the embodiment is tested, and the areal density of the mesh fabric material is 30g/m 2 Longitudinal strength 132N/5cm, longitudinal elongation at break 96%, transverse strength 124N/5cm, and transverse elongation at break 79%.
[ example 2 ] A method for producing a polycarbonate
In this example, the blending ratio of the raw materials for preparing the degradable sheath-core polymer is shown in table 3, and the blending ratio of the raw materials for preparing the degradable polymer with high melt index is shown in table 4. The component contents in tables 3 and 4 are weight contents.
TABLE 3
Figure BDA0002785655390000201
TABLE 4
Figure BDA0002785655390000211
Wherein, the catalyst in table 4 is titanocene and stannous octoate according to the weight ratio of 6:4, the initiator is di (2,4-dichlorobenzoyl) peroxide, the antioxidant is antioxidant 1010, the plasticizer is epoxidized soybean oil, and the electret modifier is nano silicon dioxide.
The preparation process comprises the following steps:
(1) Preparing the skin layer of the degradable skin-core polymer: the raw materials of the skin layer are placed into a first mixing device for premixing according to the components shown in the table 3, and the mixed raw materials of the skin layer are placed into a first back-mixing type reactor for melting, wherein the melting temperature is 150 ℃, the vacuum degree is 45kPa, the rotating speed of a stirring paddle is 20RPM, and the melting time is 30min, so that a skin layer polymer melt is obtained.
(2) Preparing a core layer of the degradable sheath-core polymer: and (3) putting the raw materials of the core layer into a second mixing device according to the components in the table 3 for premixing, and putting the mixed raw materials of the core layer into a second back-mixing type reactor for melting, wherein the melting temperature is 210 ℃, the vacuum degree is 30kPa, the rotating speed of a stirring paddle is 25RPM, and the melting time is 25min, so as to obtain a core layer polymer melt.
(3) Preparation of high melt index degradable polymers: the three polyesters were fed to a first metering silo according to the composition of table 4 and the additives were fed to a second metering silo. Through a PLC set program, the 50kg/h polyester corresponding catalyst, initiator, antioxidant, plasticizer and electret modifier are respectively 750g/h, 200g/h, 750g/h, 150g/h and 500g/h and are sent into a third back-mixing reactor from a first metering bin and a second metering bin for melt reaction, wherein the stirring speed in the melt process is 25RPM, the reaction time is 40min, the temperature is 210 ℃, and the vacuum degree is 30kPa. The melt index of the degradable polymer precursor with the high melt index is 1231g/10min.
(4) Preparing degradable skin-core polymer: the method comprises the following steps of conveying a skin layer polymer melt and a core layer polymer melt to an upper skin layer spinning box body, a lower skin layer spinning box body and a core layer spinning box body respectively through a pressure reducing valve, a booster pump and a filter in sequence, converging the melts into a composite spinning die head according to the weight ratio in the table 3 through a one-inlet and multi-outlet melt metering pump, spinning and spraying, longitudinally drawing tows through high-pressure air, falling onto a roller with a cooling air suction device and a conveying chain plate, dividing and lapping, completing lapping and conveying, and obtaining an upper layer spunbond composite fiber web and a lower layer spunbond composite fiber web. Wherein the rotating speed of the metering pump is 45RPM. The temperature of a composite spinning die head is 210 ℃, the high-speed air flow traction speed is 1800m/min, 1000 holes are selected for a composite spun-bonded spinning assembly, the width of the die head is 3.2 meters, and the web forming speed is as follows: the conveying speed of the lower layer of the spun-bonded roller is 200m/min, and the conveying speed of the upper layer of the spun-bonded roller is 800m/min.
(5) Preparing a degradable composite fiber mesh fabric: the method comprises the steps of conveying a high-melting-index degradable polymer precursor into a melt-blown spinning box body through a pressure reducing valve, a booster pump and a filter, directly entering a melt-blown spinning die head through a metering pump for spinning and spraying, then cooling and drawing through longitudinal high-temperature high-speed air flow, falling onto a lower-layer spun-bonded composite fiber net on an air-suction yarn-separating lapping net, conveying to an upper-layer spun-bonded air-suction yarn-separating lapping net to be covered by an upper-layer spun-bonded composite fiber net, and then hot rolling through a hot roller to reinforce a net fabric material to obtain the degradable composite fiber net fabric. Wherein the rotation speed of a metering pump is 40RPM, the temperature of a melt-blown spinning die head is 210 ℃, the traction speed of high-speed air flow is 2500m/min, the temperature of high-pressure air is 280 ℃, a melt-blown spinning assembly selects 2000 holes, the width of the die head is 3.2 meters, and the web forming speed is 600m/min.
The three-layer multi-component degradable composite fiber mesh fabric material obtained in the embodiment is tested, and the areal density of the mesh fabric material is 20g/m 2 145N/5cm of longitudinal strength, 104% of longitudinal elongation at break, 135N/5cm of transverse strength and 88% of transverse elongation at break.
It can be seen from the comparison between example 1 and example 2 that increasing the weight ratio of the sheath polymer and increasing the proportion of PHA in the high melt index degradable polymer is beneficial to increasing the fiber strength and also has a great increase in elongation.
[ example 3 ]
In this example, the blending ratio of the raw materials for preparing the degradable sheath-core polymer is shown in table 5, and the blending ratio of the raw materials for preparing the degradable polymer with high melt index is shown in table 6. The contents of each component in tables 5 and 6 are weight contents.
TABLE 5
Figure BDA0002785655390000221
Figure BDA0002785655390000231
TABLE 6
Figure BDA0002785655390000232
Wherein, the catalyst in table 6 is titanocene and stannous octoate according to the weight ratio of 5:5, the initiator is dicumyl peroxide, the antioxidant is antioxidant 1010, the plasticizer is tributyl citrate, and the electret modifier is nano silicon dioxide.
The preparation process comprises the following steps:
(1) Preparing the skin layer of the degradable skin-core polymer: the raw materials of the skin layer are placed into a first mixing device for premixing according to the components in the table 5, and the mixed raw materials of the skin layer are placed into a first back-mixing type reactor for melting, wherein the melting temperature is 150 ℃, the vacuum degree is 45kPa, the rotating speed of a stirring paddle is 20RPM, and the melting time is 30min, so that a skin layer polymer melt is obtained.
(2) Preparing a core layer of the degradable skin-core polymer: the core layer raw materials are placed into a second mixing device according to the components in the table 5 for premixing, and the mixed core layer raw materials are placed into a second back-mixing type reactor for melting, wherein the melting temperature is 210 ℃, the vacuum degree is 30kPa, the rotating speed of a stirring paddle is 25RPM, and the melting time is 25min, so that a core layer polymer melt is obtained.
(3) Preparation of high melt index degradable polymers: the three polyesters were fed to a first metering silo according to the composition of table 6 and the additives were fed to a second metering silo. Setting a program through a PLC (programmable logic controller), and respectively feeding 1500g/h, 400g/h, 1500g/h, 300g/h and 1000g/h of a catalyst, an initiator, an antioxidant, a plasticizer and an electret modifier corresponding to 100kg/h of polyester into a third back-mixing reactor for melt reaction from a first metering bin and a second metering bin, wherein the stirring speed in the melt process is 25RPM, the reaction time is 40min, the temperature is 210 ℃, and the vacuum degree is 30kPa. The melt index of the degradable polymer precursor with the high melt index is 1206g/10min.
(4) Preparing degradable skin-core polymer: the sheath polymer melt and the core polymer melt are respectively conveyed to an upper sheath spinning box body, a lower sheath spinning box body and a core spinning box body sequentially through a pressure reducing valve, a booster pump and a filter, and then are converged into a composite spinning die head for spinning and spraying through a one-inlet and multi-outlet melt metering pump according to the weight ratio in the table 5, and then tows are longitudinally pulled by high-pressure air to fall onto a roller with a cooling air suction device and a conveying chain plate for separating and lapping, so that the lapping and conveying are completed, and the upper layer spunbonded composite fiber web and the lower layer spunbonded composite fiber web are obtained. Wherein the rotating speed of the metering pump is 45RPM. The temperature of a composite spinning die head is 210 ℃, the high-speed air flow traction speed is 1800m/min, 1000 holes are selected for a composite spun-bonded spinning assembly, the width of the die head is 3.2 meters, and the web forming speed is as follows: the lower layer of the spun-bonded roller has a conveying speed of 200m/min, and the upper layer of the spun-bonded roller has a conveying speed of 800m/min.
(5) Preparing a degradable composite fiber mesh fabric: the method comprises the steps of conveying a high-melting-index degradable polymer precursor into two different melt-blown spinning boxes through a pressure reducing valve, a booster pump, a filter and a dividing distribution pipeline, respectively, then respectively entering two different melt-blown spinning die heads through two different metering pumps to perform spinning spraying, respectively falling onto a lower-layer spunbond composite fiber net on an induced draft sub-fiber lapping net through longitudinal high-temperature high-speed airflow cooling and drafting, respectively, obtaining a first melt-blown fiber net and a second melt-blown fiber net, simultaneously conveying three-layer lapping fibers to an upper-layer spunbond air-draft sub-fiber lapping net to be covered by the upper-layer spunbond composite fiber net, and then reinforcing a web material through hot rolling of a hot rolling roll to obtain the degradable composite fiber net fabric. Wherein the rotating speed of a metering pump is 40RPM, the temperature of a melt-blown spinning die head is 210 ℃, the high-speed air flow traction speed is 2500m/min, the temperature of high-pressure air is 280 ℃, 2000 holes are selected for a melt-blown spinning assembly, the width of the die head is 3.2 meters, and the web forming speed is 800m/min.
The four-layer multi-component degradable composite fiber mesh fabric material obtained in the embodiment is tested, and the areal density of the mesh fabric material is 30g/m 2 Longitudinal strength 160N/5cm, longitudinal elongation at break 110%, transverse strength 155N/5cm, and transverse elongation at break 98%.
Comparative example 1
The process of example 1 is followed with the exception that: in the step (1), polycaprolactone (PCL) in Table 1 is not added when preparing the skin layer polymer melt of the degradable skin-core polymer.
The material obtained in the comparative example was tested to have an areal density of 15g/m 2 Longitudinal strength 124N/5cm, longitudinal elongation at break 66%, transverse strength 85N/5cm, and transverse elongation at break 68%.
Comparative example 2
The process of example 1 is followed with the exception that: in the step (1), poly butylene adipate succinate (PBSA) in Table 1 is not added when preparing the skin layer polymer melt of the degradable skin-core polymer.
The material obtained in the comparative example was tested to have an areal density of 12g/m 2 The longitudinal strength is 108N/5cm, the longitudinal elongation at break is 54%, the transverse strength is 82N/5cm, and the transverse elongation at break is 48%.
Comparative example 3
The process of example 1 is followed with the exception that: in the step (2), when the core layer polymer melt of the degradable skin-core type polymer is prepared, the Polyhydroxyalkanoate (PHA) in table 1 is not added.
The material obtained in the comparative example was tested to have an areal density of 9.2g/m 2 The longitudinal strength is 121N/5cm, the longitudinal elongation at break is 69%, the transverse strength is 75N/5cm, and the transverse elongation at break is 72%.
Comparative example 4
The process of example 1 is followed with the exception that: in the step (2), polybutylene terephthalate adipate (PBAT) in table 1 is not added in the preparation of the core polymer melt of the degradable sheath-core polymer.
The material obtained in the comparative example was tested to have an areal density of 8.9g/m 2 Longitudinal strength 132N/5cm, longitudinal elongation at break 82%, transverse strength 79N/5cm, and transverse elongation at break 67%.
Comparative example 5
The process of example 1 is followed with the exception that: in the step (3), in the preparation of the high-melt-index degradable polymer, polybutylene terephthalate adipate (PBAT) in table 2 is not added.
The material obtained in the comparative example was tested to have an areal density of 8.7g/m 2 The longitudinal strength is 74N/5cm, the longitudinal elongation at break is 55%, the transverse strength is 60N/5cm, and the transverse elongation at break is 47%.
[ COMPARATIVE EXAMPLE 6 ]
The process of example 1 is followed with the exception that: in the step (3), when the high melt index degradable polymer is prepared, the Polyhydroxyalkanoate (PHA) in table 2 is not added.
The material obtained in the comparative example was tested, and the areal density of the material was 9.1g/m 2 The longitudinal strength is 68N/5cm, the longitudinal elongation at break is 54%, the transverse strength is 59N/5cm, and the transverse elongation at break is 45%.
Comparative example 7
The process of example 1 is followed with the exception that: and (3) only preparing one layer of spun-bonded composite fiber web in the step (4), and omitting the step of covering the upper layer of spun-bonded composite fiber web in the step (5) to finally obtain the two-layer composite fiber web fabric material.
The material obtained in the comparative example is tested, and the areal density of the material is 8.6g/m 2 The longitudinal strength is 75N/5cm, the longitudinal elongation at break is 58%, the transverse strength is 62N/5cm, and the transverse elongation at break is 51%.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent variations and modifications can be made by those skilled in the art based on the technical teaching provided by the present invention, and the protection scope of the present invention should be considered.

Claims (45)

1. The degradable skin-core polymer comprises a core layer polymer and a skin layer polymer coated on the surface of the core layer polymer, and is characterized in that the skin layer polymer is prepared from raw materials including first polylactic acid, polycaprolactone and polybutylene adipate, and the core layer polymer is prepared from raw materials including second polylactic acid, polyhydroxyalkanoate and polybutylene terephthalate adipate; the content of the skin layer polymer is 20-50 wt% based on the total weight of the degradable skin-core polymer; the content of the core layer polymer is 50-80 wt%; and/or the presence of a gas in the atmosphere,
the preparation raw materials of the skin layer polymer comprise 50-60 wt% of first polylactic acid, 10-20 wt% of polycaprolactone and 20-30 wt% of poly (butylene adipate succinate); and/or the presence of a gas in the gas,
the raw materials for preparing the core layer polymer comprise 60-70 wt% of second polylactic acid, 20-30 wt% of polyhydroxyalkanoate and 5-15 wt% of polybutylene terephthalate adipate;
the first polylactic acid is low-melting-point polylactic acid, and the second polylactic acid is high-melting-point polylactic acid; the melting point of the low-melting-point polylactic acid is 125-135 ℃, and the melting point of the high-melting-point polylactic acid is 155-170 ℃.
2. The degradable sheath-core polymer of claim 1, wherein the polycaprolactone has a melting point of 59-64 ℃ and a glass transition temperature of-60 to-40 ℃; and/or the presence of a gas in the gas,
the melting point of the poly (butylene adipate succinate) is 110-115 ℃, and the glass transition temperature is-30 ℃; and/or the presence of a gas in the gas,
the melting point of the polyhydroxyalkanoate is 155-210 ℃, and the glass transition temperature is-45-4 ℃; and/or the presence of a gas in the atmosphere,
the melting point of the polybutylene terephthalate adipate is 110-135 ℃, and the glass transition temperature is-29 ℃; and/or the presence of a gas in the gas,
in the skin layer polymer, the weight ratio of polycaprolactone to first polylactic acid is 0.5-1: 2.5 to 3; the weight ratio of the poly (butylene adipate) to the first polylactic acid is 1-1.5: 2.5 to 3; and/or the presence of a gas in the gas,
in the core layer polymer, the weight ratio of the polyhydroxyalkanoate to the second polylactic acid is 1-1.5: 3 to 3.5; the weight ratio of polybutylene terephthalate adipate to the second polylactic acid is 1:6 to 7.
3. A method for preparing the degradable core-sheath polymer of claim 1 or 2, comprising the steps of:
a1, mixing and melting first polylactic acid, polycaprolactone and poly (butylene adipate succinate) to obtain a skin layer polymer melt;
b1, mixing and melting second polylactic acid, polyhydroxyalkanoate and polybutylene terephthalate adipate to obtain a core layer polymer melt;
and C1, respectively sending the skin layer polymer melt as a skin layer and the core layer polymer melt as a core layer into a spinning composite die head for spinning and spraying to obtain the skin-core polymer.
4. The method according to claim 3, wherein the mixing and melting conditions in step A1 include: the temperature is 110-150 ℃, the vacuum degree is 30-45 kPa, and the time is 10-40 min; and/or the presence of a gas in the gas,
the mixing and melting conditions in the step B1 comprise the following steps: the temperature is 155-210 ℃, the vacuum degree is 30-45 kPa, and the time is 20-40 min; and/or the presence of a gas in the gas,
the temperature of the skin layer polymer melt when the skin layer polymer melt is sent into a spinning composite die head is 120-150 ℃, and the temperature of the core layer polymer melt when the core layer polymer melt is sent into the spinning composite die head is 160-210 ℃; and/or the presence of a gas in the gas,
the conditions for the spinning and spraying process in the spinning composite die piece comprise: the temperature of the die head is 160-210 ℃, the number of holes of the spinneret plate is 500-2000, and the width of the die head is less than or equal to 6m.
5. A degradable composite web fabric, which is a layered structure comprising an upper layer, a lower layer and at least one intermediate layer, wherein the upper layer and the lower layer are the degradable core-sheath polymer of claim 1 or 2 or the degradable core-sheath polymer prepared by the method of claim 3 or 4, and the intermediate layer is a high-melt-index degradable polymer;
the high-melt-index degradable polymer is prepared from polyester and additives, wherein the polyester comprises third polylactic acid, polybutylene terephthalate adipate and polyhydroxyalkanoate; the polyester comprises 60-70 wt% of third polylactic acid, 10-20 wt% of polybutylene terephthalate adipate and 15-30 wt% of polyhydroxyalkanoate, and the weight ratio of the additive to the polyester is 1-7: 100.
6. the degradable composite fiber mesh fabric of claim 5, wherein the degradable composite fiber mesh fabric has a machine direction strength of 80-200N/5 cm, a machine direction elongation at break of 60-120%, a cross direction strength of 60-170N/5 cm, and a cross direction elongation at break of 50-110%.
7. The degradable composite web fabric of claim 5, wherein the third polylactic acid has a melting point of 125-175 ℃, a melt index of 30-85 g/10min, and a relative viscosity of 2.5-3; and/or the presence of a gas in the gas,
the melting point of the polybutylene terephthalate adipate is 110-135 ℃, the melt index is 10-20 g/10min, and the relative viscosity is 2-3; and/or the presence of a gas in the gas,
the weight ratio of the polybutylene terephthalate adipate to the third polylactic acid is 0.5-1: 3 to 3.5; and/or the presence of a gas in the gas,
the melting point of the polyhydroxyalkanoate is 130-155 ℃, the melt index is 20-60 g/10min, and the relative viscosity is 2-3; and/or the presence of a gas in the gas,
the weight ratio of the polyhydroxyalkanoate to the third polylactic acid is 1:3 to 3.5.
8. The degradable composite web fabric of claim 5, wherein the additives include catalysts, initiators, antioxidants, plasticizers, and electret modifiers.
9. The degradable composite web fabric of claim 8, wherein the catalyst is obtained by compounding a first catalyst and a second catalyst; the first catalyst is an active hydroxyl-containing metal catalyst.
10. The degradable composite web fabric of claim 9, wherein the first catalyst is a titanocene compound.
11. The degradable composite web fabric of claim 9, wherein the second catalyst is tetrabutyl titanate and/or stannous octoate; and/or the presence of a gas in the gas,
the weight ratio of the first catalyst to the second catalyst is 5-7: 3 to 5.
12. The degradable composite web fabric of claim 11, wherein the weight ratio of the first catalyst to the second catalyst is 7:3 or 6:4 or 5:5.
13. the degradable composite web fabric of claim 8, wherein the initiator is an organic peroxide.
14. The degradable composite web fabric of claim 13, wherein the initiator is selected from at least one of di-t-butyl peroxide, dicumyl peroxide, peroxycarbonate, and dibenzoyl peroxide.
15. The degradable composite web fabric of claim 14, wherein the initiator is 2,5-dimethylhexane-2,5-di-tert-butyl peroxide and/or bis (2,4-dichlorobenzoyl) peroxide.
16. The degradable composite web fabric of claim 8, wherein the antioxidant is octa [ β - (3,5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ] tripentaerythritol ester and/or tetrakis [ β - (3,5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ] pentaerythritol ester; and/or the presence of a gas in the gas,
the plasticizer is selected from at least one of tributyl citrate, epoxidized soybean oil and polyethylene glycol; and/or the presence of a gas in the gas,
the electret modifier is selected from organic additives and/or inorganic additives; and/or the presence of a gas in the gas,
the weight ratio of the catalyst to the polyester is 0.1-2: 100, respectively; and/or the presence of a gas in the gas,
the weight ratio of the initiator to the polyester is 0.1-1: 100; and/or the presence of a gas in the gas,
the weight ratio of the antioxidant to the polyester is 0.2-2: 100, respectively; and/or the presence of a gas in the gas,
the weight ratio of the plasticizer to the polyester is 0.1-0.5: 100, respectively; and/or the presence of a gas in the gas,
the weight ratio of the electret modifier to the polyester is 0.5-1.5: 100.
17. the degradable composite web fabric of claim 16, wherein the electret modifier is selected from nanosilica.
18. The degradable composite web fabric of any one of claims 7-17, wherein the preparation method of the high melt index degradable polymer comprises:
step A2, mixing polyester and additives, and carrying out a melt reaction to prepare a high-melt-index degradable polymer precursor, wherein the polyester comprises third polylactic acid, polybutylene terephthalate adipate and polyhydroxyalkanoate;
and B2, sending the high-melt-index degradable polymer precursor into a melt-blown spinning die head for spinning and spraying to obtain the high-melt-index degradable polymer.
19. The degradable composite web fabric of claim 18, wherein the melt reaction conditions in step A2 comprise: the temperature is 155-210 ℃, the vacuum degree is 30-45 kPa, the time is 20-40 min, and the stirring speed is 5-25 RPM.
20. The degradable composite web fabric of claim 18, wherein the high melt index degradable polymer has a melt index of 500-1300 g/10min at 200 ℃ and 2.16 kg.
21. The degradable composite web fabric of claim 18, wherein the conditions for the spinning jet in the melt-blown spinning die head comprise: the temperature of the die head is 150-210 ℃, the number of holes of the spinneret plate is 500-2000, the width of the die head is less than or equal to 6m, the air flow traction speed is 1500-2500 m/min, and the temperature of the compressed air is 200-350 ℃.
22. A method for preparing a degradable composite fiber mesh fabric, which is characterized by comprising the following steps:
a3, sequentially carrying out spinning, airflow traction, cooling, splitting and lapping on the degradable skin-core polymer to obtain a lower layer of spun-bonded composite fiber net, wherein the degradable skin-core polymer is the degradable skin-core polymer in claim 1 or 2 or the degradable skin-core polymer prepared by the method in claim 3 or 4;
step B3, sequentially carrying out spinning, airflow traction, cooling and filament separation and net laying on the high-melting-index degradable polymer to obtain a middle-layer melt-blown fiber net, wherein the preparation raw materials of the high-melting-index degradable polymer comprise polyester and additives, and the polyester comprises third polylactic acid, polybutylene terephthalate adipate and polyhydroxyalkanoate; the polyester comprises 60-70 wt% of third polylactic acid, 10-20 wt% of polybutylene terephthalate adipate and 15-30 wt% of polyhydroxyalkanoate, and the weight ratio of the additive to the polyester is 1-7: 100;
step C3, sequentially carrying out spinning, air flow traction, cooling and split-silk lapping on the degradable skin-core polymer to obtain an upper layer of spun-bonded composite fiber net, wherein the degradable skin-core polymer is the degradable skin-core polymer in claim 1 or 2 or the degradable skin-core polymer prepared by the method in claim 3 or 4;
and D3, superposing the lower-layer spun-bonded composite fiber net, at least one middle-layer melt-blown fiber net and the upper-layer spun-bonded composite fiber net, and then carrying out hot rolling to obtain the degradable composite fiber net fabric.
23. The method as claimed in claim 22, wherein the air flow drawing speed in step A3 is 1500-2500 m/min, and the dividing and lapping speeds are 200-1200 m/min.
24. The method as claimed in claim 22, wherein the conditions of the air flow pulling process in step B3 include: the air flow speed is 1500-2500 m/min, and the air flow temperature is 200-350 ℃; the speed of dividing and lapping is 200-1200 m/min.
25. The method as claimed in claim 22, wherein the air flow drawing speed in step C3 is 1500-2500 m/min, and the dividing and lapping speeds are 200-1200 m/min.
26. The production method according to claim 22, wherein the hot rolling temperature in the step D3 is 60 to 120 ℃.
27. The method of claim 22, wherein the number of layers of the middle layer meltblown web is 1 to 5.
28. The method of claim 22, wherein step B3 further comprises, before spinning: and feeding the high-melt-index degradable polymer into an equal divider which is divided into two parts or three parts or four parts for distribution.
29. The method of claim 22, wherein,
the melting point of the third polylactic acid is 125-175 ℃, the melt index is 30-85 g/10min, and the relative viscosity is 2.5-3; and/or the presence of a gas in the gas,
the melting point of the polybutylene terephthalate adipate is 110-135 ℃, the melt index is 10-20 g/10min, and the relative viscosity is 2-3; and/or the presence of a gas in the atmosphere,
the weight ratio of the polybutylene terephthalate adipate to the third polylactic acid is 0.5-1: 3 to 3.5; and/or the presence of a gas in the gas,
the melting point of the polyhydroxyalkanoate is 130-155 ℃, the melt index is 20-60 g/10min, and the relative viscosity is 2-3; and/or the presence of a gas in the atmosphere,
the weight ratio of the polyhydroxyalkanoate to the third polylactic acid is 1:3 to 3.5.
30. The method of claim 22, wherein the additives include catalysts, initiators, antioxidants, plasticizers, and electret modifiers.
31. The method of claim 30, wherein the catalyst is prepared by compounding a first catalyst and a second catalyst; the first catalyst is an active hydroxyl-containing metal catalyst.
32. The method of claim 31, wherein the first catalyst is a titanocene compound.
33. The method of claim 31, wherein the second catalyst is tetrabutyl titanate and/or stannous octoate; and/or the presence of a gas in the atmosphere,
the weight ratio of the first catalyst to the second catalyst is 5-7: 3 to 5.
34. The method of claim 33, wherein the weight ratio of the first catalyst to the second catalyst is 7:3 or 6:4 or 5:5.
35. a method as claimed in claim 30, wherein said initiator is an organic peroxide.
36. The method of claim 35, wherein the initiator is at least one selected from the group consisting of di-t-butyl peroxide, dicumyl peroxide, peroxycarbonate, and dibenzoyl peroxide.
37. The method of claim 36, wherein the initiator is 2,5-dimethylhexane-2,5-di-tert-butyl peroxide and/or bis (2,4-dichlorobenzoyl) peroxide.
38. The method of claim 30, wherein the antioxidant is octa [ β - (3,5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ] tripentaerythritol ester and/or tetrakis [ β - (3,5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ] pentaerythritol ester; and/or the presence of a gas in the gas,
the plasticizer is selected from at least one of tributyl citrate, epoxidized soybean oil and polyethylene glycol; and/or the presence of a gas in the gas,
the electret modifier is selected from an organic auxiliary agent and/or an inorganic auxiliary agent; and/or the presence of a gas in the atmosphere,
the weight ratio of the catalyst to the polyester is 0.1-2: 100, respectively; and/or the presence of a gas in the gas,
the weight ratio of the initiator to the polyester is 0.1-1: 100, respectively; and/or the presence of a gas in the gas,
the weight ratio of the antioxidant to the polyester is 0.2-2: 100, respectively; and/or the presence of a gas in the gas,
the weight ratio of the plasticizer to the polyester is 0.1-0.5: 100; and/or the presence of a gas in the gas,
the weight ratio of the electret modifier to the polyester is 0.5-1.5: 100.
39. the method of claim 30, wherein the electret modifier is selected from nanosilica.
40. The method of claim 22, wherein the method of preparing the high melt index degradable polymer comprises:
step A2, mixing polyester and additives, and carrying out a melt reaction to prepare a high-melt-index degradable polymer precursor, wherein the polyester comprises third polylactic acid, polybutylene terephthalate adipate and polyhydroxyalkanoate;
and B2, sending the high-melt-index degradable polymer precursor into a melt-blown spinning die head for spinning and spraying to obtain the high-melt-index degradable polymer.
41. The method according to claim 40, wherein the melt reaction conditions in the step A2 include: the temperature is 155-210 ℃, the vacuum degree is 30-45 kPa, the time is 20-40 min, and the stirring speed is 5-25 RPM.
42. The preparation method according to claim 40, wherein the high melt index degradable polymer has a melt index of 500-1300 g/10min at 200 ℃ and 2.16 kg.
43. The method of claim 40, wherein the conditions for the spinning jet in the meltblowing spinning die head comprise: the temperature of the die head is 150-210 ℃, the number of holes of the spinneret plate is 500-2000, the width of the die head is less than or equal to 6m, the air flow traction speed is 1500-2500 m/min, and the temperature of the compressed air is 200-350 ℃.
44. Use of the degradable skin-core polymer of claim 1 or 2, the method of preparing the degradable skin-core polymer of claim 3 or 4, the degradable composite fiber web fabric of any one of claims 5 to 21, or the method of preparing the degradable composite fiber web fabric of any one of claims 22 to 43 in the field of environmental protection technology.
45. Use of the degradable skin-core polymer of claim 1 or 2, the method of producing the degradable skin-core polymer of claim 3 or 4, the degradable composite web fabric of any one of claims 5 to 21 or the method of producing the degradable composite web fabric of any one of claims 22 to 43 in vehicle trim, apparel, home furnishings, medical applications, tissue engineering, filtration materials and hygiene materials.
CN202011296812.7A 2020-11-18 2020-11-18 Degradable sheath-core polymer, high-melt-index degradable polymer, degradable composite fiber mesh fabric, and preparation method and application thereof Active CN112663171B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011296812.7A CN112663171B (en) 2020-11-18 2020-11-18 Degradable sheath-core polymer, high-melt-index degradable polymer, degradable composite fiber mesh fabric, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011296812.7A CN112663171B (en) 2020-11-18 2020-11-18 Degradable sheath-core polymer, high-melt-index degradable polymer, degradable composite fiber mesh fabric, and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112663171A CN112663171A (en) 2021-04-16
CN112663171B true CN112663171B (en) 2022-11-22

Family

ID=75403427

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011296812.7A Active CN112663171B (en) 2020-11-18 2020-11-18 Degradable sheath-core polymer, high-melt-index degradable polymer, degradable composite fiber mesh fabric, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112663171B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113293517B (en) * 2021-05-27 2022-05-13 河南驼人医疗器械研究院有限公司 Polylactic acid elastic superfine fiber non-woven material and preparation method and application thereof
CN114672895A (en) * 2022-03-31 2022-06-28 何建桦 Biomass composite fiber and its production method
CN115182099B (en) * 2022-07-25 2024-07-12 苏州优力凯新材料科技有限公司 Preparation method and application of bi-component degradable elastic polylactic acid spunbonded nonwoven material
CN116121907B (en) * 2022-12-12 2024-03-01 东华大学 PBAT/PLA sheath-core composite fiber and preparation method thereof
CN116371084A (en) * 2023-02-22 2023-07-04 苏州大学 Degradable spun-bonded filter material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010095667A (en) * 2008-10-19 2010-04-30 New Japan Chem Co Ltd Process of producing polylactic acid-based resin molded product and polylactic acid-based resin composition

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6905987B2 (en) * 2001-03-27 2005-06-14 The Procter & Gamble Company Fibers comprising polyhydroxyalkanoate copolymer/polylactic acid polymer or copolymer blends
AU2007358034B2 (en) * 2007-08-22 2014-01-23 Kimberly-Clark Worldwide, Inc. Multicomponent biodegradable filaments and nonwoven webs formed therefrom
CN102212896A (en) * 2011-05-27 2011-10-12 东华大学 High-efficiency antibacterial mildew-proof PLA (poly lactic acid) fiber with skin-core structure and preparation method thereof
CN105133082A (en) * 2015-07-24 2015-12-09 北京普利玛科技有限责任公司 Low-melting-point sheath-core-type polylactic acid composite fiber and preparation method thereof
CN105220264B (en) * 2015-09-13 2017-10-13 天津工业大学 A kind of modified polylactic acid fiber and preparation method thereof
US20180223454A1 (en) * 2017-02-07 2018-08-09 Earth Renewable Technologies Bicomponent fiber additive delivery composition
CN107805856B (en) * 2017-09-30 2020-06-26 同济大学 Polylactic acid composite fiber and preparation method thereof
CN107881792A (en) * 2017-11-02 2018-04-06 福建恒安卫生材料有限公司 Biological degradation nonwoven cloth and preparation method thereof
WO2019122195A1 (en) * 2017-12-21 2019-06-27 Beaulieu International Group Nv Biodegradable fabric and use of such fabric
CN109853083B (en) * 2018-12-28 2022-05-31 青岛科凯达橡塑有限公司 Water-soluble degradable fiber and preparation method thereof
CN110396289A (en) * 2019-08-27 2019-11-01 青岛润兴塑料新材料有限公司 Superelevation melt index polylactic resin and its preparation method and application

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010095667A (en) * 2008-10-19 2010-04-30 New Japan Chem Co Ltd Process of producing polylactic acid-based resin molded product and polylactic acid-based resin composition

Also Published As

Publication number Publication date
CN112663171A (en) 2021-04-16

Similar Documents

Publication Publication Date Title
CN112663171B (en) Degradable sheath-core polymer, high-melt-index degradable polymer, degradable composite fiber mesh fabric, and preparation method and application thereof
US6197856B1 (en) Copolymer binder fibers
DE69033492T2 (en) Process for the production of porous molded articles made of synthetic resin, of ultrafine fibers and of nonwovens with ultrafine fibers
DE60012014T2 (en) POLYESTER WITH CONTROLLED MELTING POINT AND FIBERS THEREOF
DE69817212T2 (en) COPOLYESTER-BINDER FIBERS
AU742248B2 (en) Degradable polymer fibers; preperation; product; and methods of use
EP2201162B1 (en) Polylactide stereocomplex conjugate fibers
CN110699854B (en) Antistatic non-woven fabric and manufacturing process thereof
JPH0551852A (en) Polyethylene terephthalate-based melt blown nonwoven fabric and its production
CN102146597A (en) Degradable fiber containing PHBV (polyhydroxybutyrate-hydroxyvalerate) and preparation method of degradable fiber
CN103981593A (en) Preparation method of polyvinyl alcohol melt-spun ultrafine fiber
EP2844791B1 (en) Process for making non-woven fabrics using polylactide resin blends
KR102395895B1 (en) Biodegradable composite fiber and non-woven fabric including the same
CN110965209A (en) Production process of colored polyester filament non-woven fabric
WO2018219714A1 (en) Method for the production of polyester fibres
CN115467045B (en) Full-bio-based degradable composite elastic fiber and preparation method thereof
KR102037496B1 (en) Improved Plasticity Spunbonded Nonwoven for Primary Carpet Backing, and Method for Manufacturing the Same
JPH06248551A (en) Aliphatic polyester melt-blown nonwoven fabric and its production
JP6030380B2 (en) Atmospheric pressure dyeable polyethylene terephthalate meltblown nonwoven fabric and method for producing the same
JP2011084837A (en) Spun-bonded nonwoven fabric and method for producing the same
CN116219636A (en) Preparation method of high-strength high-toughness degradable melt-blown nonwoven material
JP7560569B2 (en) Spunbond nonwoven fabric and tile carpet using same
JP4687719B2 (en) Safety net
CN118773918A (en) Softener for super-soft degradable spun-bonded non-woven fabric, and preparation method and application thereof
KR20240102082A (en) Manufacturing method of biodegradable polymer for melt-blown nonwoven with improved flowability

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant