CN110512308B - Linear bicomponent filaments, fibres or tapes - Google Patents
Linear bicomponent filaments, fibres or tapes Download PDFInfo
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- CN110512308B CN110512308B CN201910429397.9A CN201910429397A CN110512308B CN 110512308 B CN110512308 B CN 110512308B CN 201910429397 A CN201910429397 A CN 201910429397A CN 110512308 B CN110512308 B CN 110512308B
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Images
Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/22—Formation of filaments, threads, or the like with a crimped or curled structure; with a special structure to simulate wool
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/04—Heat-responsive characteristics
- D10B2401/046—Shape recovering or form memory
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/061—Load-responsive characteristics elastic
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Multicomponent Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
本发明提供一种线形或基本线形的双组分长丝、纤维或带，其包括第一弹性体组分和第二形状记忆聚合物组分，该第一弹性体组分的横截面积至少大于或小于该长丝、纤维或带的约50％，并且具有约‑125摄氏度至‑10摄氏度的玻璃化转变温度，该第二形状记忆聚合物组分的横截面积至少小于或大于约50％，并选自一种或多种热塑性聚酯型或者基于聚醚型的形状记忆聚氨酯。该第二形状记忆聚合物组分位于该双组分长丝、纤维或带内，使得该第二形状记忆聚合物组分的区域相对于该双组分长丝、纤维或带的中央芯不对称地设置。该第二形状记忆聚合物组分具有选择性设计的、在约25℃至90℃之间的形状回复温度Tr。
The present invention provides a linear or substantially linear bicomponent filament, fiber or tape comprising a first elastomeric component and a second shape memory polymer component, the first elastomeric component having a cross-sectional area of at least greater than or less than about 50% of the filament, fiber or ribbon and having a glass transition temperature of about -125 degrees Celsius to -10 degrees Celsius, the cross-sectional area of the second shape memory polymer component is at least less than or greater than about 50 %, and is selected from one or more thermoplastic polyester-based or polyether-based shape memory polyurethanes. The second shape memory polymer component is located within the bicomponent filament, fiber or tape such that regions of the second shape memory polymer component are not located relative to the central core of the bicomponent filament, fiber or tape Set symmetrically. The second shape memory polymer component has a selectively engineered shape recovery temperature Tr between about 25°C and 90°C.
Description
Cross Reference to Related Applications
This application claims priority from U.S. provisional patent application serial No. 62/762,815 filed on day 22, 5, 2018 and U.S. provisional patent application serial No. 62/702,337 filed on day 23, 7, 2018, the disclosures of both provisional patent applications being incorporated herein by reference in their entireties.
Technical Field
The present invention relates to substantially linear bicomponent filaments, fibers or tapes and methods of use thereof.
Background
Shape memory polymers are materials that have a first "permanent" shape and a second "temporary" shape caused by deformation of the material. Upon receiving an external stimulus (e.g., heat, solvent, electrical current, light, a change in magnetic field or pH, thermal stimulus), the material returns to its "permanent shape". That is, the material "remembers" its original shape and returns to that shape after being subjected to an external stimulus.
To date, the most well studied shape memory polymers are thermally triggered shape memory polymers, which typically include two phases, a hard phase that defines a permanent shape and a soft phase that allows the formation of a temporary shape. The mechanism of shape change between hard and soft phases requires an elastic network that can return the material to a previous strain state upon application of a stimulus and a switching structure that can be at the phase transition temperature (i.e., the glass transition temperature (T)g) Or melting temperature (T)m) ) reversibly change from inelastic to movable. For typical shape memory polymer production, it is common to chemically bind the elastic network and the switch structure to a polymer or macromolecule. However, there are some disadvantages such as those that chemically cross-linked shape memory polymers are not recyclable, age after a long time, or that chemical processes for mass production are complicated.
Since the 60's of the 20 th century, bicomponent filaments and fibers have been developed as synthetic fibers. By this technique, two different polymers of suitable viscosity and composition are co-extruded through a spinneret from two separate extenders (extenders) together into one filament. The cross-section of the filaments can be of different types including concentric sheath/core, eccentric sheath/core, side-by-side, pie wedge, island/sea mode, depending on the application requirements. For example, chinese patent application publication No. CN104342802A discloses a bicomponent conjugate elastic fiber. The disclosed fiber is an elongated filament, which is formed by parallel composite spinning of polybutylene terephthalate and polyethylene terephthalate according to the weight ratio of (70:30) - (30:70), the number of crimps of the fiber is 55-75/25mm, and the crimp radius is less than 1.0 mm. After heat treatment, the elastic elongation of the fiber is 80-120%, and the elastic recovery rate of the fiber is higher than 92%. Another chinese patent application publication No. CN101126180A discloses a side-by-side bicomponent elastic fiber and a method of making the same. In this chinese application, by using shrink PET, PBT or PTT, any two juxtaposed composite polymers can produce a spring-like coiled structure with better elasticity after prolonged heat treatment due to the difference in shrink properties. PCT application publication No. WO2009099548a2 describes a process for producing self-crimping fluoropolymer and perfluoropolymer filaments comprising: heating said fluoropolymer and/or said perfluoropolymer to a molten state, extruding said fluoropolymer and/or said perfluoropolymer under pressure through a spinneret orifice to produce filaments which exhibit differential die expansion as molten polymer, wherein said filaments expand as molten polymer stepwise and continuously along their longitudinal length, and wherein said spinneret orifice comprises a round hole shape with elliptical peninsulas creating an elliptical concave gap in one section of said filaments which acts as molten polymer and differential die expansion on opposite sides of said elliptical concave gap closing the gap creating a seam between said opposite sides such that differential die expansion around said elliptical concave gap creates non-uniform stress along a portion of the resulting filaments causing said filaments to curl, etc. in a preferential manner toward said seam, Bending, deforming and/or twisting. U.S. patent No. 4424257 discloses a self-crimping multicomponent polyamide filament and a process for producing the filament. In its simplest form, the filament is composed of two components, each component comprising a polyamide of the same chemical composition, wherein one component contains a minor amount of a polyolefin mixed with the polyamide. The components are coextruded to form conjugate filaments, which are attenuated in the molten state, solidified and then collected to form filaments. Thinning of the filaments in the molten state imparts self-crimpability and molecular orientation to the filaments.
In view of the shortcomings of the prior art self-curling polymeric filaments, there is a need for a fiber, filament or tape having a stable, controllable and adjustable curl shape under different conditions.
Disclosure of Invention
Accordingly, a first aspect of the present invention provides a linear or substantially linear bicomponent filament, fiber or tape. The filament, fiber or tape comprises a first elastomeric component having a cross-sectional area at least greater than about 50% of the filament, fiber or tape and having a glass transition temperature of about-125 to-10 degrees celsius, and a second shape memory polymer component having a cross-sectional area at least less than about 50% and selected from one or more shape memory polyurethanes of the thermoplastic polyester or polyether type, wherein the polyether based shape memory polymer comprises a polycaprolactone based polymer. The second shape memory polymer component is located within the bicomponent filament, fiber or ribbon such that the region of the second shape memory polymer component is asymmetrically disposed with respect to the central core of the bicomponent filament, fiber or ribbon. The second shape memory polymer component has an optionally designed shape recovery temperature T between about 25 ℃ and 90 ℃rAnd wherein said first elastomer component has a greater elasticity than said second shape memory polymer component at or below said selectively designed shape recovery temperature.
A second aspect of the invention provides a linear or substantially linear bicomponent filament, fiber or tape. The filament, fiber or tape comprises a first elastomeric component having a cross-sectional area of at least less than about 50% of the filament, fiber or tape and having a glass transition temperature of about-125 degrees Celsius to-10 degrees Celsius and a second shape memory polymer component having a cross-sectional area of at least greater than about 50% and selected from one or more shape memory polyurethanes of the thermoplastic polyester or polyether typeAn ester, wherein the polyether-based shape memory polymer comprises a polycaprolactone-based polymer. The second shape memory polymer component is located within the bicomponent filament, fiber or ribbon such that the region of the second shape memory polymer component is asymmetrically disposed with respect to the central core of the bicomponent filament, fiber or ribbon. The second shape memory polymer component has an optionally designed shape recovery temperature T between about 25 ℃ and 90 ℃rAnd wherein said first elastomer component has a greater elasticity than said second shape memory polymer component at or below said selectively designed shape recovery temperature.
In one embodiment, the bicomponent filament, fiber or tape is configured to assume a substantially helical configuration upon release after elongation of about 50% to about 300%, the number of helices per centimeter increasing relative to the increase in the percent elongation or the elongation time.
In another embodiment, the bicomponent filament, fiber or tape is heated to a selectively designed shape recovery temperature TrIt returns to a substantially linear shape.
Alternatively, for the first and second aspects of the invention, the proportions of the first elastomeric component and the second shape memory polymer component in the bicomponent filaments, fibers or tapes of the invention may be defined by their respective weight ratios. That is, the first elastomeric component is in the range of 10 to 90 weight percent of the total weight of the bicomponent filament, fiber or tape and the second shape memory polymer component is in the range of 90 to 10 weight percent of the total weight of the bicomponent filament, fiber or tape, wherein the weight ratio between the first elastomeric component and the second shape memory polymer component is 1-9:9-1, as long as the positioning of the first elastomeric component and the second shape memory polymer component with respect to the cross-section of the bicomponent filament, fiber or tape remains asymmetric.
A third aspect of the invention provides a method of making the linear or substantially linear bicomponent filaments, fibers or tapes of the invention, including any polymer fiber forming technique, such as wet spinning, dry spinning, gel spinning, electrospinning, draw spinning, by single extrusion or multiple extrusion. Details of the manufacturing method are described below by way of embodiments or examples.
Drawings
Embodiments of the invention are described in more detail below with reference to the accompanying drawings, in which:
fig. 1A to 1C show, from cross-sectional views, different embodiments of the invention according to different arrangements of elastomer and shape memory polymer, which result in different three-dimensional structures of the invention: FIG. 1A shows an asymmetric side-by-side arrangement of an elastomer and a shape memory polymer according to one embodiment of the present invention; FIG. 1B illustrates an asymmetric eccentric arrangement of an elastomer and a shape memory polymer according to one embodiment of the present invention; FIG. 1C illustrates an asymmetric and approximately rectangular arrangement of an elastomer and a shape memory polymer according to one embodiment of the present invention;
fig. 2A to 2E show, from a cross-sectional perspective, the structure of a bicomponent filament or fiber according to various embodiments of the present invention; FIG. 2A shows a cross-section of a bicomponent filament or fiber with a ratio of elastomer to shape memory polymer of about 2: 1; FIG. 2B shows a cross-section of a bicomponent filament or fiber with a ratio of elastomer to shape memory polymer of about 3: 1; FIG. 2C shows a cross-section of a bicomponent filament or fiber with a ratio of elastomer to shape memory polymer of about 3: 2; FIG. 2D shows a cross-section of a bicomponent filament or fiber with a ratio of elastomer to shape memory polymer of about 2: 1; FIG. 2E shows a cross-section of a bicomponent filament or fiber with a ratio of elastomer to shape memory polymer of about 3: 1;
FIG. 3 is an image showing the procedure of "drawing" and "releasing" bicomponent filaments, fibers or tapes according to one embodiment of the present invention;
figure 4A shows that the spiral diameter of examples 2 to 4 decreases with increasing percentage of elongation and the number of spirals per cm increases with increasing percentage of elongation;
FIG. 4B shows that the spiral diameter of examples 5 to 7 decreases with increasing percent elongation and the number of spirals per centimeter increases with increasing percent elongation;
FIG. 5A is an image showing one embodiment of a bicomponent filament, labeled with estimated measurements of helix diameter and pitch;
fig. 5B is an image showing another embodiment of bicomponent filaments labeled with estimated measurements of filament diameter, helix diameter, and thread pitch.
Detailed Description
Definition of
The term "linear" as used herein to describe the state of the bicomponent filaments, fibers or tapes of the present invention refers to the near or substantially linear state of the formed bicomponent filaments, fibers or tapes of the present invention, which state can be visually observed or qualitatively and/or quantitatively determined. In other words, the phrase "linear or substantially linear bicomponent filament, fiber or tape" or similar terms as used herein may refer to a formed bicomponent filament, fiber or tape which is found, qualitatively and/or quantitatively, to be in a straight or nearly straight arrangement or along a straight or nearly straight line.
The terms "filament" and "fiber" (sometimes used interchangeably herein) as used herein refer to a three-dimensional structure having an elongated morphology. In certain contexts, the term "filament" or "fiber" may also refer to a fine, filamentous object or article.
As used herein, the term "elastomer" or "elastomer component" (or sometimes they are used interchangeably) refers to a material that exhibits the properties of elasticity, low young's modulus (i.e., the ratio of tensile stress to tensile strain), and is capable of deforming when stress is applied and returning to its original shape (i.e., length, volume, shape, etc.) when the stress is removed. Examples of elastomers useful in the present invention include, but are not limited to, polyester or polyether-based polyurethanes.
The terms "shape memory polymer" or "shape memory polymer component" (or sometimes they are used interchangeably) as used herein refer to a unique class of polymers or materials that have the ability to fix a temporary shape and then return to a previous state due to an external stimulus (e.g., heat, radiation, solvent, electrical current, light, magnetic field, or a change in pH). Examples of shape memory polymers useful in the present invention include, but are not limited to, polyester-based or polyether-based shape memory polyurethanes, including, but not limited to, polycaprolactone-based shape memory polymers.
The scope of the invention is not limited by any of the following descriptions. The following examples or embodiments are provided for illustration only.
Reference will now be made in detail to the accompanying drawings. Fig. 1A to 1C schematically depict examples of the configuration of linear bicomponent filaments, fibers or tapes of the present invention. A linear bicomponent filament, fiber or ribbon includes an elastomeric portion and a shape memory polymer portion such that the filament undergoes a deformation-based (stretch-induced) crimp, assuming a substantially helical configuration after being elongated by about 50% to about 300%. Upon heating to a temperature above the recovery temperature, the material reverts to a permanent, approximately linear configuration.
Fig. 1A and 1B show a cross-section of a filament or fiber 100 and fig. 1C shows a cross-section of a tape 200. In each of these arrangements, the shape memory polymer region is indicated by reference numeral 10 and the elastomeric component is indicated by reference numeral 20.
As shown in fig. 1A to 1C, the bicomponent filaments of the present invention can take a variety of configurations. For example, in FIG. 1A, the shape memory polymer 10 is formed in a region offset from the core of the fiber or filament; similarly, in FIG. 1B, the shape memory polymer 10 is also offset from the central core region of the belt. That is, the shape memory polymer region 10 is always asymmetrically positioned with respect to the center of the cross-sectional area of the filament, fiber or tape. In these embodiments, the bicomponent filaments may be made from a weight ratio of 90% to 10% to 90% of a thermoplastic polyurethane elastomer (TPU) and a shape memory polymer. The cross-section may be side-by-side (fig. 1A) or eccentric sheath/core (fig. 1B). For the two-component tape of the present invention (e.g., FIG. 1C), it can also be made from a thermoplastic polyurethane elastomer (TPU) and a shape memory polymer in a weight ratio of 90%: 10% to 10%: 90%.
Fig. 2A-2E illustrate some embodiments of placing or positioning the elastomer and shape memory polymer asymmetrically from a cross-sectional perspective to form a bicomponent filament or fiber. In these embodiments, each of the elastomeric fibers and the shape memory polymer fibers are longitudinally aligned with one another, and the number of fibers between the two polymer fibers is not equal, e.g., in a ratio of 2:1, 3:1, 4:1, 1:2, 1:3, 1:4, etc. In other words, the ratio of elastomeric fibers to shape memory polymer fibers is x: y or y: x, where x is at least 1 less or greater than y in these embodiments. It should be understood that the ratio between the elastomeric fibers and the shape memory polymer fibers need not be an integer in terms of weight ratio. A prerequisite for forming the bicomponent filaments, fibers or tapes of the present invention is to asymmetrically position or arrange the elastomer and shape memory polymer relative to the cross-section of the bicomponent filament, fiber or tape such that the bicomponent filament, fiber or tape of the present invention assumes a linear or substantially linear state or shape in the absence of a corresponding external stimulus, curls and forms a corresponding number of spirals upon being held for a time and released after being stretched or elongated by about 50% to about 300% of its original length, and upon being heated to about 25 to about 90oC is capable of returning to its linear or substantially linear state or shape when the shape returns to temperature.
The present invention relates to a process for the production of filaments, fibres, tapes made of co-extruded shape memory polymers and elastomers having the function of "stretch induced crimp and heat induced de-crimp". This intelligent function stems from a bicomponent filament structure in which the elastomer portion retains good elasticity at various temperatures from room temperature to 90 degrees Celsius, while the shape memory polymer remains below TrProvides pseudoplasticity at a temperature above TrProvides elasticity at the temperature of (a). Therefore, at room temperature (below T)r) After stretching and release, the pseudoplasticity on the shape memory polymer side tends to remain elongated while the elasticity on the elastomeric side is more or less reduced. Thus, self-curling is caused. Subsequently, if the crimped filament, fiber or tape is heated to TrIn the above, the pseudoplasticity of the shape memory polymer is removed and becomes elastic, whichThe pushed coil shape immediately straightens.
As shown in fig. 3, the bicomponent filaments of the present invention are immediately formed into a coiled shape from a substantially linear shape by stretching to a certain value, for example, 50% to 300%, at room temperature and then releasing it to a free-standing state (301). Subsequently, for a coiled shape, the de-coiling process can be easily achieved by heating the filament above the shape recovery temperature of the shape memory polymer (302). In the present invention, the shape-memory polymer used has a shape-recovery temperature higher than room temperature, for example, 25 to 90 degrees celsius.
For bicomponent filament extrusion, a spinneret with a side-by-side or eccentric sheath/core bicomponent configuration is used. TPU with excellent elasticity would be suitable candidates, for example Elastollan C80A10, C85A10, Estane S385A. The shape memory polymer may include Tg(glass transition as trigger temperature) type, e.g. Diaplex 2520, 3520, 4520, or Tm(melting point as trigger temperature) type, e.g. polycaprolactone based shape memory polymers, such as Zhu, Y., Hu, J.,&yeung, K. (2009) ("Effect of soft segment crystallization and hard segment physical crosslinking on shape memory function of antibacterial segmented polyurethane ionomers") ",Acta Biomaterialia5(9), 3346), which is incorporated herein by reference in its entirety. Since curling is caused by stretching, stretching ability and thermoplasticity are prerequisites.
The following examples illustrate the invention in more detail:
estane S385A was selected for the elastomer portion. The hardness was 85A. The ultimate elongation was 780%. Such as literature (Zhu, y., Hu, j.,& Yeung, K. (2009), “Effect of soft segment crystallization and hard segment physical crosslink on shape memory function in antibacterial segmented polyurethane ionomers”, Acta Biomaterialia5(9), 3346) using a shape memory polymer based on polycaprolactone diol (Mn =10000) in the portion of the shape memory polymerThe polymer comprises MDI (4, 4' -methylene bis (phenyl isocyanate)), BDO (1, 4-butanediol) or N, N-bis (2-hydroxyethyl) -isonicotinamide (BIN) in a hard chain segment. T of the shape memory Polymer usedrIs 48 degrees celsius, or the shape memory polymer portion may be T having a temperature of 45 degrees celsiusgDiaplex MM 4520.
Table 1 physical properties of example 1 to example 7.
| Examples | Shape of | Elastic body | SMP (shape memory Polymer) | Elastomer to SMP weight ratio | After diameter (filament) thickness Degree (with) | Elongation% | Diameter of the helix | Number of spirals per centimeter | Shape recovery temperature |
| 1 | Filament yarn | Estane®S385A | Based on the interior of poly-hexaneEster SMP-1 | 7:3 | 1.2mm | 100 | 3mm | 9 | 48℃ |
| 2 | Filament yarn | Estane®S385A | **SMP-2 | 8:2 | 1.2mm | 100 | 5mm | 10 | 45℃ |
| 3 | Filament yarn | Estane®S385A | **SMP-2 | 8:2 | 1.2mm | 150 | 4mm | 11 | 45℃ |
| 4 | Filament yarn | Estane®S385A | **SMP-2 | 8:2 | 1.2mm | 200 | 3mm | 12 | 45℃ |
| 5 | Belt | Estane®S385A | Polycaprolactone-based SMP-3 | 6:4 | 0.7mm | 100 | 7mm | 7 | 43℃ |
| 6 | Belt | Estane®S385A | Polycaprolactone-based SMP-3 | 6:4 | 0.7mm | 200 | 5mm | 9 | 43℃ |
| 7 | Belt | Estane®S385A | Polycaprolactone-based SMP-3 | 6:4 | 0.7mm | 300 | 3mm | 13 | 43℃ |
| 8 | Belt | Estane®S385A | Polycaprolactone-based SMP-3 | 7:3 | 0.9mm | 100 | 3mm | 13 | 80℃ |
| 9 | Filament yarn | Estane®S385A | #SMP-4 | 55:45 | 0.100mm | 100 | 0.508mm | 32 | 40℃ |
| 10 | Filament yarn | Estane®S385A | Based on polyhexamethylene adipate SMP-5 | 55:45 | 0.105mm | 100 | 0.509mm | 28 | 40℃ |
Note that: -
Polycaprolactone-based SMP-1 was obtained from: zhu, Y., Hu, J.,& Yeung, K., “Effect of soft segment crystallization and hard segment physical crosslink on shape memory function in antibacterial segmented polyurethane ionomers”, Acta Biomaterialia, 2009, 5(9), 3346；
SMP-2 is Diaplex ™ SMP 4520;
polycaprolactone-based SMP-3 was obtained from: zhu Y, Hu J, Choi K F, et al, Crystallization and differentiation of the Crystallization soft segment in a shape-memory polyurethane ion meter [ J]. Journal of Applied Polymer Science, 2008, 107(1):599-609；
#SMP-4 was a dual SMP blend using Diaplex ™ SMP4520 and 3520 in a weight ratio of 50/50;
##SMP-5 is obtained from: chen S., Hu J., Liu Y., et al, Effect of SSL and HSC on morphology and properties of PHA-based SMPU synthesized by bulk polymerization method [ J]. Journal of Polymer Science Part B: Polymer Physics, 2007, 45, 444。
Example 1
For bicomponent filaments with a diameter of 1.2mm, the elastomer Estane S385A and the polycaprolactone-based shape memory polymer were coextruded at a weight ratio of 7:3 (melt flow pump control) using side-by-side nozzles. All pellets must be dried at 104 degrees celsius for 2-4 hours before processing. The barrel temperature of the extruder is 180-195 ℃ (zone 1), 185-200 ℃ (zone 2), 190-205 ℃ (zone 3) and 190-200 ℃ (mold zone). The screw rotation speed is 180-200 rpm. The filaments were cooled from the nozzle by cold water at a temperature of about 15 degrees celsius without any drawing process. The bicomponent filaments prepared may exhibit a "smart-spiral" function wherein upon stretching to 100% elongation and release may yield a coiled shape of 9 spirals per cm with a spiral diameter of 3mm, heating to a shape that returns to straight at about 48-80 degrees celsius.
Example 2
For pairs with a diameter of 1.2mmComponent filaments, elastomer Estane using eccentric nozzle®S385A was coextruded with Diaplex MM4520 shape memory polymer at a weight ratio of 8:2 (melt flow pump control). All pellets must be dried at 104 degrees celsius for 2-4 hours before processing. The barrel temperature of the extruder is 180-195 ℃ (zone 1), 185-200 ℃ (zone 2), 190-205 ℃ (zone 3) and 190-200 ℃ (mold zone). The screw rotation speed is 180-200 rpm. The filaments were cooled from the nozzle by cold water at a temperature of about 15 degrees celsius without any drawing process. The bicomponent filaments prepared may exhibit a "smart-coil" function wherein upon stretching to 100% elongation and release may produce a coiled shape of 10 coils per cm with a coil diameter of 5mm, heating to about 45-50 degrees celsius to return to a straight shape.
Example 3
For bicomponent filaments of 1.2MM diameter, the elastomers Estane S385A and Diaplex MM4520 shape memory polymer were coextruded in a weight ratio of 8:2 (melt flow pump control) using an eccentric nozzle. All pellets must be dried at 104 degrees celsius for 2-4 hours before processing. The barrel temperature of the extruder is 180-195 ℃ (zone 1), 185-200 ℃ (zone 2), 190-205 ℃ (zone 3) and 190-200 ℃ (mold zone). The screw rotation speed is 180-200 rpm. The filaments were cooled from the nozzle by cold water at a temperature of about 15 degrees celsius without any drawing process. The bicomponent filaments prepared may exhibit a "smart-coil" function wherein upon stretching to 150% elongation and release may yield a coiled shape of 11 coils per cm with a coil diameter of 4mm, heating to about 45 degrees celsius to return to a straight shape.
Example 4
For bicomponent filaments with a diameter of 1.2mm, the elastomer Estane was extruded using an eccentric nozzle®S385A was coextruded with Diaplex MM4520 shape memory polymer at a weight ratio of 8:2 (melt flow pump control). All pellets must be dried at 104 degrees celsius for 2-4 hours before processing. The barrel temperature of the extruder is 180-195 ℃ (zone 1), 185-200 ℃ (zone 2), 190-205 ℃ (zone 3)190-. The screw rotation speed is 180-200 rpm. The filaments were cooled from the nozzle by cold water at a temperature of about 15 degrees celsius without any drawing process. The bicomponent filaments prepared may exhibit a "smart-spiral" function wherein upon stretching to 200% elongation and release may yield a coiled shape with a spiral diameter of 3mm, 12 spirals per cm, heating to a shape that returns to straight at about 45-60 degrees celsius.
For elastomer Estane using an eccentric nozzle®S385A and polyurethane based shape memory polymer bicomponent filaments with a diameter of 1.2mm were coextruded at a weight ratio of 8:2 (melt flow pump control), the helix diameter and the number of helices per cm were measured (fig. 4A). The helix diameter decreases from 5mm to 3mm and the number of helices per cm increases from 10 to 12 as the elongation percentage is from 100 to 200%.
Example 5
For a two-component tape having a thickness of 0.7mm, the elastomer Estane was grooved using a layer-by-layer grooved die®S385A was coextruded with a polycaprolactone-based shape memory polymer at a weight ratio of 6:4 (melt flow pump control). All pellets must be dried at 104 degrees celsius for 2-4 hours before processing. The barrel temperature of the extruder is 180-195 ℃ (zone 1), 185-200 ℃ (zone 2), 190-205 ℃ (zone 3) and 190-200 ℃ (mold zone). The screw rotation speed is 180-200 rpm. The tape was cooled from the nozzle by cold water at a temperature of about 15 c without any stretching process. The prepared two-component tape may exhibit a "smart-spiral" function, wherein upon stretching to 100% elongation and release may yield a coiled shape with 7 spirals per cm with 7mm spiral diameter, heating to about 43 degrees celsius to return to a straight shape.
Example 6
For a bi-component tape having a thickness of 0.7mm, elastomeric Estane S385A and polycaprolactone-based shape memory polymer were coextruded using a layer-by-layer slot die in a weight ratio of 6:4 (melt flow pump control). All pellets must be dried at 104 degrees celsius for 2-4 hours before processing. The barrel temperature of the extruder is 180-195 ℃ (zone 1), 185-200 ℃ (zone 2), 190-205 ℃ (zone 3) and 190-200 ℃ (mold zone). The screw rotation speed is 180-200 rpm. The tape was cooled from the nozzle by cold water at a temperature of about 15 c without any stretching process. The prepared two-component tape may exhibit a "smart-spiral" function, wherein stretching to 200% elongation and release may yield a coiled shape with a spiral diameter of 5mm, 9 spirals per cm, heating to about 43 degrees celsius to return to a straight shape.
Example 7
For a bi-component tape having a thickness of 0.7mm, elastomeric Estane S385A and polycaprolactone-based shape memory polymer were coextruded using a layer-by-layer slot die in a weight ratio of 6:4 (melt flow pump control). All pellets must be dried at 104 degrees celsius for 2-4 hours before processing. The barrel temperature of the extruder is 180-195 ℃ (zone 1), 185-200 ℃ (zone 2), 190-205 ℃ (zone 3) and 190-200 ℃ (mold zone). The screw rotation speed is 180-200 rpm. The tape was cooled from the nozzle by cold water at a temperature of about 15 c without any stretching process. The prepared two-component tape may exhibit a "smart-spiral" function, wherein stretching to 300% elongation and release may yield a coiled shape with a spiral diameter of 3mm, 13 spirals per cm, heating to about 43 degrees celsius to return to a straight shape.
The spiral diameter and the number of spirals per centimeter were measured on bicomponent tapes of 0.7mm thickness coextruded with elastomer Estane S385A and polycaprolactone-based shape memory polymer in a weight ratio of 6:4 (melt flow pump control) using a layer-by-layer slot die (FIG. 4B). The helix diameter decreases from 7mm to 3mm and the number of helices per cm increases from 7 to 13 as the elongation percentage is from 100 to 200%.
Example 8
For a bi-component tape having a thickness of 0.9mm, elastomeric Estane S385A and polycaprolactone-based shape memory polymer were coextruded using a layer-by-layer slot die in a weight ratio of 7:3 (melt flow pump control). All pellets must be dried at 104 degrees celsius for 2-4 hours before processing. The barrel temperature of the extruder is 180-195 ℃ (zone 1), 185-200 ℃ (zone 2), 190-205 ℃ (zone 3) and 190-200 ℃ (mold zone). The screw rotation speed is 180-200 rpm. The tape was cooled from the nozzle by cold water at a temperature of about 15 c without any stretching process. The prepared two-component tape may exhibit a "smart-spiral" function, wherein upon stretching to 100% elongation and release may yield a coiled shape with a spiral diameter of 3mm, 13 spirals per cm, heating to a shape that returns to straight at about 40-80 degrees celsius.
Example 9
For bicomponent filaments of 0.1mm diameter, elastomer Estane S385A was co-extruded with 50/50 weight ratio of Diaplex shape memory polymer 4520 and 3520 double shape memory polymer blends in a weight ratio of 55:45 (melt flow pump control) using side-by-side nozzles. All pellets must be dried at 104 degrees celsius for 2-4 hours before processing. The barrel temperature of the extruder is 180-195 ℃ (zone 1), 185-200 ℃ (zone 2), 190-205 ℃ (zone 3) and 190-200 ℃ (mold zone). The screw rotation speed is 180-200 rpm. The filaments were cooled from the nozzle by cold water at a temperature of about 15 degrees celsius without any drawing process. The bicomponent filaments prepared may exhibit a "smart-spiral" function wherein upon stretching to 100% elongation and release may yield a coiled shape of 32 spirals per centimeter having a spiral diameter of 0.508 mm, heating to a shape that returns to straight at about 40 degrees celsius.
Example 10
For bicomponent filaments with a diameter of 0.105mm, the elastomer Estane S385A and the shape memory polymer based on polyhexamethylene adipate were coextruded using a side-by-side nozzle in a weight ratio of 55:45 (melt flow pump control). All pellets must be dried at 104 degrees celsius for 2-4 hours before processing. The barrel temperature of the extruder is 180-195 ℃ (zone 1), 185-200 ℃ (zone 2), 190-205 ℃ (zone 3) and 190-200 ℃ (mold zone). The screw rotation speed is 180-200 rpm. The filaments were cooled from the nozzle by cold water at a temperature of about 15 degrees celsius without any drawing process. The bicomponent filaments prepared may exhibit a "smart-spiral" function wherein upon stretching to 100% elongation and release may yield a coiled shape of 28 spirals per centimeter having a spiral diameter of 0.508 mm, heating to a shape that returns to straight at about 40 degrees celsius.
It will be apparent to those skilled in the art that many more modifications besides those already described are possible without departing from the inventive concepts herein. The inventive subject matter, therefore, is not to be restricted except in the spirit of the present disclosure. Moreover, in interpreting the disclosure, all terms should be interpreted in the broadest possible manner consistent with the context. In particular, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a reference to an element, component, or step is intended to refer to that element, component, or step as it may exist, or utilized, or combined with other elements, components, or steps that are not expressly referenced.
Claims (7)
1. A linear bicomponent filament, fiber or tape, comprising:
a first elastomeric component having a cross-sectional area at least greater than 50% of the filament, fiber or tape and having a glass transition temperature of from-125 degrees Celsius to-10 degrees Celsius;
a second shape memory polymer component having a cross-sectional area of at least less than 50% and selected from one or more thermoplastic polyester-or polyether-based shape memory polyurethanes, wherein the thermoplastic polyester-or polyether-based shape memory polyurethane comprises a polycaprolactone-based polymer;
wherein the second shape memory polymer component is located within the bicomponent filament, fiber or ribbon such that the region of the second shape memory polymer component is asymmetrically disposed with respect to the central core of the bicomponent filament, fiber or ribbon;
and wherein the shape memory polymer has a selectively designed shape recovery temperature T between 25 ℃ and 90 ℃r；
Wherein the first elastomeric component has a greater elasticity than the second shape memory polymer component at or below the selectively designed shape recovery temperature;
wherein the bicomponent filament, fiber or tape is configured to assume a substantially helical configuration upon 50% to 300% elongation and release, the number of helices per centimeter increasing with respect to the increase in percent elongation or elongation time, and upon heating to the selectively designed shape recovery temperature TrIt returns to a substantially linear shape.
2. A linear bicomponent filament, fiber or tape, comprising:
a first elastomeric component having a cross-sectional area of at least less than 50% of the filament, fiber or tape and a glass transition temperature of from-125 degrees Celsius to-10 degrees Celsius;
a second shape memory polymer component having a cross-sectional area of at least greater than 50% and selected from one or more thermoplastic polyester-or polyether-based shape memory polyurethanes, wherein the thermoplastic polyester-or polyether-based shape memory polyurethane comprises a polycaprolactone-based polymer;
wherein the second shape memory polymer component is located within the bicomponent filament, fiber or ribbon such that the region of the second shape memory polymer component is asymmetrically disposed with respect to the central core of the bicomponent filament, fiber or ribbon;
and wherein the shape memory polymer has a selectively designed shape recovery temperature T between 25 ℃ and 90 ℃r;
Wherein the first elastomeric component has a greater elasticity than the second shape memory polymer component at or below the selectively designed shape recovery temperature;
wherein the bicomponent filament, fiber or tape is configured to assume a substantially helical configuration upon 50% to 300% elongation and release, the number of helices per centimeter increasing relative to the increase in percent elongation or elongation time, and upon heating to the selectively designed shapeReturn temperature TrIt returns to a substantially linear shape.
3. The linear bicomponent filament, fiber, or tape according to claim 1 or 2, wherein the bicomponent filament, fiber, or tape is configured to assume a substantially helical configuration after 50% to 300% elongation and upon release, wherein the helix diameter is 0.5 to 7 mm.
4. The linear bicomponent filament, fiber, or tape according to claim 1 or 2, wherein the bicomponent filament, fiber, or tape is configured to assume a substantially helical configuration after being elongated by 50% to 300% and released, wherein the number of helices per centimeter is from 7 to 32.
5. The linear bicomponent filament, fiber, or tape according to claim 1 or 2, wherein the polycaprolactone-based shape memory polymer is a polycaprolactone diol-based shape memory polymer having hard segments selected from 4,4' -methylenebis (phenyl isocyanate), 1, 4-butanediol, or N, N-bis (2-hydroxyethyl) -isonicotinamide.
6. The linear bicomponent filament, fiber or tape according to claim 1 or 2, wherein the first elastomeric component is in the range of 10 to 90 weight percent of the total weight of the bicomponent filament, fiber or tape and the second shape memory polymer component is in the range of 90 to 10 weight percent of the total weight of the bicomponent filament, fiber or tape, wherein the weight ratio between the first elastomeric component and the second shape memory polymer component is 1-9:9-1, as long as the positioning of the first elastomeric component and the second shape memory polymer component with respect to the cross section of the bicomponent filament, fiber or tape remains asymmetric.
7. The linear bicomponent filament, fiber, or tape according to claim 1 or 2, wherein the first elastomer component comprises one or more of a polyester and a polyether-based polyurethane.
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| US16/404701 | 2019-05-06 | ||
| US16/404,701 US20190360125A1 (en) | 2018-05-22 | 2019-05-06 | Linear bi-component filament, fiber, or tape, and method of using thereof |
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| US20220160940A1 (en) * | 2019-03-04 | 2022-05-26 | Global Surgical Innovations Pty Ltd | An attachment means for attaching a medical device to tissue, a system for attaching a medical device to tissue, a medical device having an attachment means, a method of attaching a medical device to tissue, and a method of manufacturing an attachment means |
| WO2023153459A1 (en) * | 2022-02-14 | 2023-08-17 | 東レ株式会社 | Crimped fibers |
| CN118292142A (en) * | 2024-03-14 | 2024-07-05 | 浙江新维狮合纤股份有限公司 | Multifunctional double-component composite short fiber |
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