CN109930238B - Crosslinked styrene block copolymer mixture elastic fiber and manufacturing method thereof - Google Patents
Crosslinked styrene block copolymer mixture elastic fiber and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to a method for manufacturing a crosslinked styrene block copolymer mixture elastic fiber, which comprises the following steps: a) providing a styrenic block copolymer mixture comprising at least one styrenic block copolymer a, and at least one ethylene copolymer B by blending; b) melt spinning the styrenic block copolymer mixture to obtain an elastic fiber; c) carrying out irradiation crosslinking on the obtained elastic fiber; wherein the styrene block copolymer A is an unsaturated styrene block copolymer, the styrene/rubber ratio is 10:90 to 45:55, the melt index (200 ℃/5.0kg) is 1-50 g/10min, and the density of the ethylene copolymer B is 0.855-0.890 g/cm3The melt index (190 ℃/2.16kg) is 0.5-10 g/10min, and the ratio of the styrene block copolymer A to the ethylene copolymer B is 85: 15-15: 85.
Description
Technical Field
The present invention relates to a method for producing a crosslinked styrene block copolymer mixture elastic fiber; and a styrene block copolymer mixture elastic fiber produced using the production method; and the application of the elastic fiber in the fields of various textile fabrics or elastic ropes and the like.
Background
The requirements of comfort, fit, shape keeping, crease resistance and fitting sports are important attributes of elastic fibers to fabrics or clothes and the development direction of the fabrics or the clothes, in the future, the fabrics or the clothes are not cloth and cannot stretch, and the elasticity of the elastic fabrics or the fabrics is mainly realized by adding the elastic fibers into the fabrics of the clothes.
Spandex (the scientific name of polyurethane elastic fiber, including dry-process spandex, wet-process spandex and melt-spun spandex) in the existing elastic fiber accounts for nearly 90% of the market share and is in the domination position in the field of textile or elastic cords, but the spandex has the defects of easy aging degradation, easy breakage and relaxation, harmful solvent content, no alkali resistance, no chlorine bleaching resistance, no dark color dyeing and the like.
In the field of elastic cords, the conventional spandex fiber is used, so that the elastic cord cannot be durable and ageing-resistant, and particularly, the elastic cord in the professional field has obvious defects, and a stable, durable and ageing-resistant elastic fiber is needed to replace the conventional spandex fiber.
The traditional cross-linked polyolefin elastic fiber is a novel elastic fiber product which is released by Dow Chemical company (Dow Chemical) in 2002, the elastic fiber can resist the setting temperature of 220 ℃, resist chlorine bleaching, strong acid and alkali, resist ultraviolet degradation, have soft elasticity, can be set at low temperature and the like, the usage amount in the textile is also equivalent to that of spandex, the defects that the spandex is not aging-resistant, chlorine bleaching-resistant and alkali-resistant are overcome, and the elastic fiber is excellent in comprehensive performance. However, conventional polyolefin elastic fiber products produced by the dow chemical company suffer from three important drawbacks:
1. the strength is low, the breaking strength is between 0.50 and 0.80cN/dtex, and is far lower than the breaking strength of common dry method spandex 1.0 to 1.7cN/dtex, so that the elasticity of the elastic fabric produced by adopting polyolefin elastic fiber of the Dow company is smaller, and the elastic fabric is only suitable for producing low-elasticity fabric but not medium-high elasticity fabric;
2. the elastic recovery rate is poor, the elastic recovery rate of the polyolefin elastic fiber of the dow company after being stretched by 300 percent is generally not higher than 85 percent, and is lower than that of the polyolefin elastic fiber of the ordinary dry-process spandex by nearly 10 percent or more after being stretched by 300 percent, so that the polyolefin elastic fiber can not be popularized and used in a plurality of fabrics (such as underwear, swimwear, jeans, sportswear and the like) which need the normal recovery rate requirement;
3. polyolefin elastic fibers produced by the Dow company have a complex processing technology and high cost, so that the polyolefin elastic fibers cannot enter the mainstream market of the elastic fibers all the time.
The above three important defects lead the dow company to finally quit the research and development and production fields of the traditional polyolefin elastic fiber products in 2010.
It is a well-known fact that Styrene Block Copolymers (SBCs) have better elastic recovery than conventional polyolefin elastomeric copolymers (POE); the styrene block copolymer is also a special polyolefin copolymer, and the acid resistance, alkali resistance and other properties of the styrene block copolymer are far stronger than those of a polyurethane elastomer. However, the use temperature of the styrene block copolymer is low, mainly because the glass transition temperature of the styrene hard block in the styrene block copolymer is about 95 ℃, and the normal use temperature which can be born by different grades of main-stream styrene block copolymers of different companies is below 60-80 ℃. Therefore, the styrene block copolymer elastic fiber produced by the traditional method can not bear the requirements of normal process temperature of dyeing, drying, heat setting and the like of textile fabrics or elastic cords (the finishing temperature after dyeing of the traditional textile fabrics or elastic cords is at least above 100 ℃, usually between 120 and 150 ℃, and the temperature required by part of fabric processing processes even reaches about 200 ℃), so that the styrene block copolymer elastic fiber cannot be directly applied to the market in the field of textile fabrics or elastic cords.
To overcome the drawback of styrene block copolymers not being resistant to high temperatures, reference 1 discloses a process comprising radiation crosslinking (also called "radiation crosslinking") of an article under an inert or oxygen-limited atmosphere (e.g. under nitrogen, argon, helium, carbon dioxide, xenon and/or vacuum), wherein the article comprises at least one amine stabilizer and another optional stabilizing additive. The elastic article comprises a homogeneously branched ethylene interpolymer (preferably a substantially linear ethylene interpolymer), a substantially hydrogenated block copolymer, or a combination of the two. It must be pointed out that the limitation of the atmosphere of the irradiation for crosslinking would cause great inconvenience to the mass production of the elastic fiber, increasing the production cost while also reducing the production efficiency. It is believed that unsaturated block copolymers, such as styrene-butadiene-styrene triblock copolymers (SBS), tend to exhibit ordinary thermal stability, particularly in the molten state and poor UV stability. Thus, substantially hydrogenated block copolymers are more suitable for the invention of this document. It is understood, however, that the crosslinking efficiency (the amount of gel produced internally) of the substantially hydrogenated block copolymer is far inferior to that of the unsaturated block copolymer under equivalent irradiation crosslinking conditions. It can be seen from examples 14,15 and 16 of this document that to achieve a dose of at least 22.4Mrad (or 224KGy) of electron beam irradiation in a nitrogen environment, fibers made with substantially hydrogenated block copolymers exhibit improved heat resistance and pass through simulated dyeing and heat setting processes. Such high dose irradiation not only significantly increases the production cost of the fiber, but also can significantly cause yellowing and discoloration of the elastic fiber, shrinkage and deformation of the elastic fiber cake, and causes the problems of adhesion of the elastic fiber positioned in the inner layer, significant increase of the end breakage rate, difficult unwinding and the like.
Reference 1: CN1505660
Disclosure of Invention
The invention aims to provide a method for manufacturing an elastic fiber by using a crosslinked styrene block copolymer mixture. The direct result of this invention is to provide a novel polyolefin elastic fiber which has heat resistance comparable to that of conventional crosslinked polyolefin elastic fibers, but exhibits higher breaking strength and elastic recovery. Surprisingly, unsaturated styrene block copolymers such as styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), etc., exhibit sustained viscosity stability and feasibility of mass production in a high temperature processing environment (265 ℃) by blending with ethylene copolymers and adding appropriate amounts of additives during the manufacture of the novel elastic fibers. Meanwhile, the elastic fiber can generate enough gel content and high heat resistance corresponding to the gel content only by using less electron irradiation dose, thereby remarkably reducing the production cost and simplifying the production flow.
The invention relates to a method for manufacturing an elastic fiber of a styrene block copolymer mixture, which comprises the following steps:
a) providing a styrenic block copolymer mixture comprising at least one styrenic block copolymer a, and at least one ethylene copolymer B by blending;
b) spinning the styrene block copolymer mixture to obtain an elastic fiber;
c) the obtained elastic fiber is subjected to irradiation crosslinking,
wherein the styrene block copolymer A is an unsaturated styrene block copolymer, the styrene/rubber ratio is 10: 90-45: 55, and the melt index (200 ℃/5.0kg) is 1-50 g/10 min; the density of the ethylene copolymer B is 0.855-0.890 g/cm3The melt index (190 ℃/2.16kg) is 0.5-10 g/10 min; the styrene block copolymer A is co-polymerized with the ethyleneThe proportion of the polymer B is 85: 15-15: 85.
In the production process of the present invention, it is preferable that the ethylene copolymer B further contains an olefin block copolymer (representative product is INFUSE available from the Dow chemical Co., Ltd.)TM)。
In the manufacturing method of the present invention, the styrene block copolymer mixture may contain a crosslinking accelerator including a copolymer Ethylene Propylene Diene Monomer (EPDM).
In the manufacturing method of the present invention, the content of the crosslinking accelerator is 0% to 25% and the contents of the styrene block copolymer a and the ethylene copolymer B are 100% to 75% based on 100% by weight of the styrene block copolymer mixture.
In the manufacturing method of the present invention, the styrene block copolymer mixture may contain a Plastic Processing Aid (PPA) such as a fluorine-containing additive or ultra-high molecular weight silicon kerogen, preferably a fluorine-containing additive
In the manufacturing method of the present invention, the manufacturing method further includes performing step c) after step b): in step c), an electron beam irradiation method or a gamma-irradiation method can be used for irradiation at room temperature, and the irradiation dose is 40-180 KGy (4-18 Mrad). The irradiation environment may be in air or under an inert or oxygen-limited atmosphere (e.g., under nitrogen, argon, helium, carbon dioxide, xenon, and/or vacuum).
In the manufacturing method of the present invention, in the step b), the styrene block copolymer group mixture is melted and re-granulated using a granulator suitable for copolymer granulation before spinning, thereby further uniformly mixing the components of the styrene block copolymer mixture.
The elastic fiber of the styrene block copolymer mixture produced by the above production method may be a filament, a thick and thin yarn, a textured yarn, or a profiled fiber, and has a fineness of 10 to 1000 denier.
In the manufacturing method, the crosslinked styrene block copolymer mixture elastic fiber can resist the subsequent processing temperature of the textile of 120-200 ℃ under the condition of stretching to 2.0-4.0 times of the original length.
In addition, the invention also relates to a blended yarn or composite yarn (such as covering yarn, covering yarn or wrapping yarn and the like) which is made by using the crosslinked styrene block copolymer mixture elastic fiber and other fibers or yarns, wherein the other fibers or yarns comprise synthetic fibers, natural fibers, fiber-like materials and the like.
The invention also relates to the crosslinked styrene block copolymer mixture elastic fiber which is directly added or applied to the manufacturing of textile fabrics or ropes in the form of blended yarns or composite yarns to manufacture elastic textiles or elastic rope products.
Detailed Description
Hereinafter, the present invention will be described in detail.
The term "styrenic block copolymer" as used herein refers to a unique thermoplastic elastomeric material having a two-phase structure of hard polystyrene endblocks (i.e., "hard segments", hereinafter "hard segments") and soft rubber midblocks (i.e., "soft segments", hereinafter "soft segments"). The polystyrene end blocks (hard segments) aggregate to form physical crosslinks that anchor the polymer molecules without vulcanization, providing good strength, while the rubber midblocks (soft segments) provide elastomeric properties. Depending on the degree of hydrogenation, styrenic block copolymers can be classified as unsaturated styrenic block copolymers (USBS), such as SIS, SBS; partially saturated styrene block copolymers, such as SIBS; hydrogenated Styrene Block Copolymers (HSBC), such as SEBS. The term "styrenic block copolymer" in the present invention generally refers to unsaturated styrenic block copolymers.
The term "styrenic block copolymer blend" as used herein refers to a blend of an unsaturated styrenic block copolymer and at least one ethylene copolymer, and may also include the copolymer Ethylene Propylene Diene Monomer (EPDM), which is homogeneously mixed.
The term "copolymer" in the present invention is also referred to as an interpolymer, and refers to a copolymer obtained by copolymerizing two or more different monomers. The term "copolymer" includes the terms "random copolymer", "alternating copolymer", "block copolymer", "graft copolymer", "bipolymer", and "terpolymer", and the like. The copolymer is generally prepared in one reactor or copolymerization reactor, but may be prepared using a plurality of reactors or copolymerization reactors.
The term "block copolymer" in the present invention means a product of block copolymerization of two or more monomers, i.e., two or more monomer units are present in segments on the main chain of the copolymer.
The term "heat resistance" in the present invention means the ability of the crosslinked styrenic block copolymer mixture in the form of fibers to pass the high-temperature baking test described in the present invention.
The term "resistant" means that the crosslinked styrenic block copolymer mixture in fiber form is capable of undergoing the various processing steps required at a certain temperature without breaking.
The term "melt flow rate" (also known as melt index) in the context of the present invention is the mass (g) of the copolymer melt in g/10min at a specified temperature and load (pressure) for 10 minutes through a standard die.
The term "irradiation" in the present invention refers to radiation processing, radiation treatment or radiation processing, i.e., a processing mode in which ionizing radiation emitted from a radiation source acts on a substance to cause covalent crosslinking in the irradiated substance, thereby improving the quality or performance thereof.
The invention relates to a method for manufacturing an elastic fiber of a styrene block copolymer mixture, which comprises the following steps:
a) providing a styrenic block copolymer mixture comprising at least one styrenic block copolymer a, and at least one ethylene copolymer B by blending;
b) spinning the styrene block copolymer mixture to obtain an elastic fiber;
c) the obtained elastic fiber is subjected to irradiation crosslinking,
wherein the styrene block copolymer A is an unsaturated styrene block copolymer of styrene/rubberThe glue ratio is 10: 90-45: 55, and the melt index (200 ℃/5.0kg) is 1-50 g/10 min; the density of the ethylene copolymer B is 0.855-0.890 g/cm3The melt index (190 ℃/2.16kg) is 0.5-10 g/10 min; the ratio of the styrene block copolymer A to the ethylene copolymer B is 85: 15-15: 85.
Styrene Block copolymer A
The styrene block copolymer A can be any commercially available product or unsaturated styrene block copolymer prepared according to the prior art, as long as the styrene/rubber ratio is between 10:90 and 45:55, and the melt index (200 ℃/5.0kg) is 1 to 50g/10 min.
Non-limiting examples of suitable commercially available commercial products for the styrene block copolymer a include: unsaturated Styrene Block Copolymer (USBC) produced by Taiwan rubber company Limited (TSRC Corp.)
A series of products; unsaturated Styrene Block Copolymer (USBC) KRATON "D" series products from Keteng copolymer company (KRATON); TUFPRENE of Asahi Kasei Corp, Asahi Kasei CorpTMA series of products; GLOBALPRENE, TOUCH GRIT Corp, Taiwan, ChinaTMThe series of products and the like specifically include styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-isoprene/butadiene-styrene (SIBS), and the like.
Ethylene copolymer B
The ethylene copolymer B can be any commercially available product or an ethylene copolymer prepared according to the prior art as long as the density is 0.855-0.890 g/cm3And the melt index (190 ℃/2.16kg) is 0.5-10 g/10 min.
The ethylene copolymer is formed by copolymerizing ethylene and at least one C4-C20 olefin. Non-limiting examples of the C4 to C20 olefin monomers include: alpha-olefin monomers such as 1-butene, isobutylene, 1-pentene, 1-hexene, 1-octene, branched isomers thereof, styrene, alpha-methylstyrene and mixtures thereof. The C4-C20 olefinThe monomer and copolymerization conditions can be selected as required, as long as the density of the ethylene copolymer B is 0.855-0.890 g/cm3The melt index (190 ℃/2.16kg) is 0.5 to 10g/10min, preferably 1 to 5g/10 min.
The ethylene copolymer B comprises an ethylene-octene block copolymer.
Non-limiting examples of suitable commercially available products for which ethylene copolymer B is preferred include: INFUSE manufactured by Dow ChemicalTM、ENGAGETM、AFFINITYTM(ii) a EXACT manufactured by ExxonmobilTM(ii) a TAFMER, manufactured by Mitsui Chemicals, IncTMAnd the like.
The weight ratio of the styrene block copolymer A to the ethylene copolymer B is 85: 15-15: 85, preferably 70:30, and more preferably 50: 50.
In order to further increase the crosslinking efficiency of the styrene block copolymer a and the ethylene copolymer B under electron irradiation, the styrene block copolymer mixture may optionally further contain a specific amount of a crosslinking accelerator. The crosslinking accelerator comprises Ethylene Propylene Diene Monomer (EPDM). Non-limiting examples of ethylene propylene diene monomer rubber include NORDEL manufactured by Dow ChemicalTM(ii) a ROYALENE, PRODUCED BY LION COPER (LLC)TM(ii) a VISTALON manufactured by ExxonMobil, Inc. (ExxonMobil)TMAnd the like.
The total content of the styrene block copolymer A and the ethylene copolymer B is 75 to 100% by weight, preferably 80 to 98% by weight, more preferably 85 to 95% by weight, based on 100% by weight of the styrene block copolymer mixture; the content of the crosslinking accelerator is preferably 0 to 25% by weight, more preferably 2 to 20% by weight, and still more preferably 5 to 15% by weight.
Under the condition that the styrene block copolymer mixture contains the ethylene propylene diene monomer, the required irradiation dose can be further reduced, and the irradiation efficiency is improved.
In the manufacturing method of the present invention, the styrene block copolymer mixture may contain a Plastic Processing Aid (PPA) such as a fluorine-containing additive or ultra-high molecular weight silicon kerogen particles, preferably a fluorine-containing additive.
The PPA auxiliary agent is a polymer processing auxiliary agent taking a fluorine-containing high molecular polymer as a basic structure, and is widely applied to processing of engineering plastics such as polyethylene (including LLDPE, mLLDPE, MDPE, HDPE, HMW-HDPE, LDPE, VLDPE and the like), ethylene-vinyl acetate (EVA), polypropylene (PP), polyvinyl chloride (PVC), Polystyrene (PS), nylon, polyester PET, PC, ABS and the like, and the PPA auxiliary agent has the main functions in the engineering plastics processing:
1) the apparent viscosity, extruder pressure and extrusion temperature were reduced.
2) The melt fracture phenomenon and the die orifice material accumulation phenomenon are reduced or even eliminated.
3) Reduce the viscosity of the melt on the screw and improve the cleaning capability of the screw.
4) Reducing cross-linked gels and oxidized gels during extrusion.
5) Excellent high temperature processing resistance.
6) The final product has better surface finish and appearance and is not easy to break.
In the embodiment, the PPA additive is mainly used for improving the processability of resin, reducing the melt pressure, improving the melt flowability, reducing the processing torque energy consumption, increasing the extrusion quality of products, improving the production efficiency and improving the surface gloss of the products; the cross-linked gel and the oxidized gel in the extrusion process are reduced, the accumulated material of a spinning nozzle is reduced, the spinning fracture condition is reduced, the viscosity of the melt to a spinning pipeline is reduced, and the service life of spinning equipment is prolonged.
Non-limiting examples of suitable commercial products of fluorine-containing additives include: DYNAMER of 3M corporation, USATMDAI-EL of DAIKIN (DAIKIN) seriesTMKYNAR of ARKEMA, France seriesTMSeries and the like PPA products. Non-limiting examples of suitable commercial products of ultra-high molecular weight silica kerogen particles include: MB series of Dow Corning company (Dow-Corning), KJ series of ultrahigh molecular weight silicone oil master pellets of Kyozhou Qianji plastics science and technology Co.
The styrenic block copolymer mixture of the present invention may further comprise various conventional additives as required, for example: antioxidants, UV stabilizers, acid scavengers, antistatic agents, lubricants, nucleating agents, compatibilizers, mold release agents, clarifying agents, fillers, colorants, water absorbers, radiation crosslinking promoters, and the like. The additive is contained in an amount of 0.001 to 10 wt%, preferably at most 5.0 wt%, more preferably at most 2.0 wt%, based on the weight of the styrene block copolymer mixture.
The above additives may be added to the styrene block copolymer mixture. Usually, these additives are stirred with the mixture before the pelletizing and extruding process, or added separately from the mixture in the feed port of the pelletizer by a separate weight loss feeder or screw feeder during the pelletizing and extruding process.
For the mixing in step a) of the present invention, a conventional vertical pellet mixer, horizontal mixer, double cone mixer, trough mixer, etc. may be used. In order to obtain a more uniform mixing effect, secondary mixing may be performed after the primary mixing using a conventional kneading or mixing apparatus such as a banbury Mixer, a two-roll Rubber roll mill, a Buss co-kneader, or a twin-screw extruder, or secondary mixing granulation may be performed using a Rubber gap Mixer (Rubber Batch Mixer) superimposed screw extrusion granulator, thereby obtaining uniformly mixed granular raw materials.
In step b) of the present invention, the particulate raw material of the styrene block copolymer mixture obtained in step a) may be directly spun using a melt spinning method, that is: melting the granular raw material of the styrene block copolymer mixture in a single screw extruder, inputting the molten material into a spinning box through a sealed and heated pipeline, pressing the molten material into a spinning nozzle through a spinning pump, enabling the molten material to flow out of the spinning nozzle to form filaments, condensing the filaments to form fibers, receiving the filaments by a spinning winding head, winding the filaments into cakes and the like.
The invention can use equipment suitable for spinning melt spinning spandex or similar equipment to spin, the spinning speed is 400-1000 m/min, and the spinning temperature can be adjusted by the technicians in the field according to common knowledge.
The styrene block copolymer mixture of the present invention can be made into fibers having a fineness of 10 to 1000 denier. When the styrenic block copolymer blends of the present invention are made into fibers having a denier of greater than 140 (in the present invention, fibers having a denier of greater than 140 are also referred to as macrofibers), it may be necessary to use water cooling instead of air cooling during the spin-winding process to prevent the fibers from sticking to the godet.
The term "Denier" in the present invention, abbreviated as "D" in the english Denier, refers to the grams of weight of a 9000 meter length of a fiber or yarn at a given moisture regain, which can be expressed by the formula: d is (G/L) × 9000 (where G is the weight (G) of the fiber or yarn at the official moisture regain and L is the length (m) of the fiber or yarn). A larger grammage, i.e. a higher denier, indicates a thicker fiber or yarn.
The term "TEX" in the present invention refers to TEX, english TEX, abbreviated TEX, and refers to the grams of weight of a 1000 meter length of fiber or yarn at a given moisture regain, which can be expressed by the formula: tex is calculated as (G/L) x1000 (where G is the weight of the fiber or yarn in grams at official moisture regain and L is the length of the fiber or yarn in meters). A higher grammage, i.e. higher tex, indicates a thicker yarn.
The term "dtex" in the present invention refers to decitex, which refers to the grams of weight of a 10000 meter length of fiber or yarn at a official moisture regain. It can be represented by the formula: dtex is calculated as (G/L) x10000 (where G is the weight of the fiber or yarn in grams at the official moisture regain and L is the length of the fiber or yarn in meters). A higher grammage, i.e. higher tex, indicates a thicker yarn.
As can be seen from the above definitions, D is equivalent to tex and dtex, and 1tex is 1/10dtex is 1/9D.
The obtained styrene block copolymer mixture fiber was subjected to irradiation crosslinking. Irradiation is generally performed after spinning to wind a cake, and may be performed at room temperature and air conditions or under limited oxygen conditions using methods known in the art, including but not limited to: electron beam irradiation, corona irradiation, gamma irradiation, UV irradiation, and the like. Among these methods, electron beam irradiation or γ -irradiation is preferable.
The irradiation dose may be determined according to the temperature to which the fiber is subjected, provided that sufficient cured gel is generated inside the fiber so as not to break under the high temperature treatment conditions. The irradiation dose is preferably 40-180 KGy, more preferably 50-150 KGy, and more preferably 60-120 KGy.
The styrenic block copolymer blends of the present invention may be spun as desired to form filaments, macrofilaments, textured filaments, or shaped fibers, or to form composite fibers with other copolymer copolymers.
The term "filament" in the present invention means a fiber having a length of kilometers, which can be classified as: monofilament, multifilament, cord yarn. The term "monofilament" as used herein refers to a single continuous filament spun from a single-hole spinneret.
The term "multifilament" in the present invention means a composite yarn composed of two or more filaments.
The term "thick and thin yarn" in the present invention refers to a yarn or thread which is formed into uneven thickness, alternatively thick and thin portions by technical means or special additional equipment during the spinning process to meet the special use requirements.
The term "textured yarn" as used herein refers to a yarn or filament obtained by texturing a fiber by technical means or by special additional equipment.
The term "shaped fiber" as used herein refers to a chemical fiber having a particular cross-sectional shape that is spun through a geometric (non-circular) spinneret orifice.
The term "composite fiber" in the present invention means that two or more immiscible copolymers exist in the cross section, and the cross section can be classified into a side-by-side type, a sheath-core type, a split type, a sea-island type, and the like.
The present invention also relates to blended or composite yarns, such as core, covered or wrapped yarns and the like, made using the styrenic block copolymer blends of the present invention with other fibers or yarns, including synthetic and natural fibers.
The term "blended yarn" in the present invention means a blended yarn composed of two or more kinds of fibers, such as a polyester/cotton blended yarn, a wool/polyester blended yarn, a wool/nitrile blended yarn, a polyester/viscose/nitrile blended yarn, a real silk/cotton yarn twisted yarn, etc.
The term "natural fibers" in the present invention includes, for example, various kinds of wool, rabbit hair, camel hair or other animal hair, silk, cotton, hemp or other plant fibers, asbestos fibers, and the like.
The term "composite yarn" in the present invention means a yarn composed of two or more kinds of fibers in a regular combination. Preferred composite yarns include: the styrene block copolymer mixture elastic fiber filament of the present invention is used together with other fibers to make a core spun yarn, a covering yarn or a wrapping yarn.
The term "core spun yarn" in the present invention means a composite yarn spun by twisting together short fibers for textile such as cotton, wool, viscose and the like, which are wrapped with synthetic fiber filaments having a high tenacity or a high elasticity as core filaments. The core-spun yarn of the present invention is particularly a core-spun yarn formed by covering the styrene block copolymer mixture elastic fiber filament of the present invention with other textile staple fibers by a core-spinning apparatus well known in the textile industry. "textile staple fibers" suitable for use in the present invention include, but are not limited to, the following three types:
1) cotton fibers and chemical fibers cut to about 38mm are referred to in the textile industry as "cotton staple fibers".
2) Wool, rabbit hair, camel hair fiber and chemical fiber cut into about 70-85 mm are called 'hair type short fiber' in the textile industry.
3) The cut pieces are chemical fibers of about 55mm, and are referred to in the textile industry as "medium-long staple fibers".
The term "covered yarn" in the invention refers to a composite yarn which is made by using a strong or elastic synthetic fiber filament as a core filament and covering the core filament by air knotting. The covered yarn of the present invention is specifically a covered yarn formed by covering other composite filament fibers on the elastic fiber filament of the styrene block copolymer mixture of the present invention by a blank spinning device well known in the textile industry. Suitable overwrap "composite long fibers" for the covering yarns described above include, but are not limited to: the coating yarn is prepared from various chemical fiber filaments such as nylon filaments, polyester filaments, viscose filaments, acrylic filaments, tencel filaments and polypropylene filaments, and the corresponding coating yarn is preferably produced by using the nylon filaments, the polyester filaments, the viscose filaments, the acrylic filaments and the like.
The term "wrapped yarn" as used herein refers to a composite yarn produced by wrapping a synthetic filament having a high tenacity or elasticity as a core filament with another composite filament or yarn by wrapping the core filament around the core filament. The wrapped yarn of the present invention is specifically a wrapped yarn formed by wrapping other composite filament fibers or yarns on the elastic fiber filaments of the styrene block copolymer blend of the present invention by a wrapping spinning apparatus well known in the textile industry. Suitable "composite long fibers or yarns" for the wrapping of the above-described wrapped yarns include, but are not limited to: various chemical fiber filaments such as nylon filament, polyester filament, viscose filament, acrylic filament, tencel filament, polypropylene filament and the like, various cotton yarns, polyester cotton yarns, cotton acrylic fibers, polyester yarns, cotton viscose yarns, cotton brocade yarns, brocade viscose yarns and the like, and the nylon filament, the polyester filament, the viscose filament, the acrylic filament, the cotton yarns, the polyester cotton yarns, the cotton nitrile yarns and the like are preferably used for producing corresponding wrapped yarn winding yarns
The composite yarn product prepared by the yarn forming method has the characteristics of all the component fibers, and can obtain special appearance effect according to the requirement.
The styrene block copolymer mixture elastic fiber filament prepared according to the manufacturing method of the present invention and the composite yarn comprising the styrene block copolymer mixture elastic fiber prepared according to the manufacturing method of the present invention (i.e., the composite yarn of the above-mentioned covering yarn, wrapping yarn, etc.) can be used for the manufacture of weft-knitted elastic knit fabrics, warp-knitted elastic knit fabrics, elastic woven fabrics, elastic ropes, etc., and have very wide uses in the textile or rope field.
Examples
The present invention will be further illustrated by the following examples.
The components shown in Table 1 were added to a small high-speed mixer to be mixed, and then conveyed to a twin-screw extruder to be mixed and granulated, thereby producing 5 to 10 kg of styrene block copolymer mixture pellets.
Melt flow rate:
the melt flow rate of the obtained styrene block copolymer mixture pellets was measured under the conditions of 190 ℃ and 2.16kg load according to GB/T3682-2000 "determination of melt flow rate and melt volume flow rate of thermoplastic plastics". The results are shown in Table 1.
TABLE 1 composition and content (wt%) of styrene block copolymer mixture
Note:
1) ethylene-octene block copolymer, INFUSE-9107, supplier Dow chemical, melt index (190 ℃/2.16 kg): 1.0, density: 0.866g/cm3；
2) Ethylene-octene block copolymer, INFUSE-9507, supplier Dow chemical, melt index (190 ℃/2.16 kg): 5.0, density: 0.866g/cm3；
3) Styrene-isoprene-styrene copolymer (SIS): d1164, Koteng copolymer, melt index (200 ℃/5 kg): 12, density: 0.94g/cm3Styrene/rubber ratio: 29/71, respectively;
4) styrene-butadiene-styrene copolymer (SBS): 3527, hey li chang rubber ltd, melt index (190 ℃/5 kg): 8, density: 0.94g/cm3Styrene/rubber ratio: 25/75, respectively;
5) ethylene Propylene Diene Monomer (EPDM): nordel IP 4820P Dow chemical company, melt index (190 ℃/2.16 kg): 1.0, density 0.908g/cm3；
6) PPA (plastic processing aid): dynamar 5924, a fluorochemical adjuvant manufactured by 3M company, USA.
Subsequently, the mixtures obtained in comparative examples and examples were each spun on a 25mm single-screw single-head spinning machine, the orifice diameter of the spinneret being 1.0mm, the spinning speed being set at 450m/min, and the fineness of the fibers being 111dtex (about 100 denier). In examples and comparative examples, the temperature zones of the screw extruders were set to: 150 ℃ to 235 ℃ to 245 ℃ to 255 ℃ to 265 ℃, and the temperature of the spinning head (including the spinneret) is set to 265 ℃.
Each of the obtained fiber samples was measured as follows on a type YG008E fiber tensile tester (wechhou international high detection instrument limited).
Breaking strength and elongation of fiber:
the determination was carried out in accordance with FZ/T50006-1994 (2007) test method for breaking strength and breaking elongation of spandex filaments. The test apparatus was set up as follows: sample holding distance: 50 mm; stretching speed: 500 mm/min; test fixture: 100 cN. 3 validation tests were performed. The average of the data obtained from the 3 tests is the result of the measurement of the sample being measured. The results are shown in Table 2.
Constant elongation (300%) elastic recovery of the fiber:
the determination was carried out in accordance with FZ/T50006-1994 (2007) test method for breaking strength and breaking elongation of spandex filaments. The test apparatus was set up as follows: sample holding distance: 50 mm; the drawing speed was 500 mm/min. When the tensile strain is 300%, the tensile strain stays for 30 seconds after 1 cycle; the length of the fiber at the moment of tension value in the 2 nd stretching is taken as the length (L) after stretching recovery2). The calculation is made by the following formula:
in the formula, L1Is the length of the fiber after drawing 300%, here 200 mm; l is2Is the stretched recovered length; l is0The clamping length before fiber drawing is here 50 mm. The average of the data obtained from the 3 tests is the result of the measurement of the sample being measured. The results are shown in Table 2.
TABLE 2
As shown in the results of table 2, the breaking strength of the elastic fiber prepared in the example is obviously higher than that of the elastic fiber prepared in the comparative example, and the improvement of the breaking strength is very obvious (the improvement ratio in the sample reaches 28.8% -75%); the improvement of the elastic recovery rate of the fixed elongation of 300 percent is very obvious (the improvement proportion in the embodiment reaches 9.4 to 14.9 percent); the average elongation at break in the examples is reduced to some extent compared with the comparative examples, but is also more than 500%, and can completely meet the requirements of downstream use.
As is apparent from the results shown in Table 2, the elastic fiber of the styrene block copolymer mixture produced according to the method of the present invention has higher breaking strength and higher elastic recovery.
The "breaking strength increasing rate" (T) in table 2 was calculated by the following formula:
in the formula, T is the breaking strength increasing rate; n is a radical of1Example breaking strength values; n is a radical of0The breaking strength values of the comparative examples are shown.
The "elastic recovery improvement rate" (X) in Table 2 was calculated by the following formula:
wherein X is the elastic recovery rate; h1Is "example 300% elongation elastic recovery"; h0Is "comparative example 300% elongation elastic recovery".
The elastic fiber samples of comparative example and examples 1 to 3 were further subjected to electron irradiation crosslinking at irradiation doses of 60KGy and 120KGy, respectively. All irradiation was carried out in air. The radiation crosslinked fiber samples were subjected to a high temperature bake test according to the following method to examine the high temperature resistance of the fibers.
High temperature baking test:
the fiber samples obtained were subjected to a high temperature baking test to examine the high temperature resistance of the fibers according to the following method:
1) an electric heating constant temperature drying oven (suzhou pin oven electric furnace manufacturing ltd., model P688-1) was previously heated to a set temperature, which is shown in table 3;
2) two carbon adhesive tapes (also called high-temperature adhesive tapes) are fixed on a table top with the adhesive surfaces facing upwards, parallel to each other and 60mm apart, 5 sections of the carbon adhesive tapes are taken out from sample fibers obtained by spinning and are placed on the two fixed carbon adhesive tapes in parallel with each other with the distance of about 10mm, and therefore the original length of the test filament is 60 mm.
3) Another section of the carbon adhesive tape is stuck to 5 sections of the placed carbon adhesive tape of the sample fiber to be tested, and the 5 sections of the fiber to be tested are clamped between 2 carbon adhesive tapes which are stuck to each other; this process was repeated to stick another piece of carbon tape.
4) Folding the double-layer carbon adhesive tape stuck with the sample fiber, and clamping and fixing one end by a clamp; this process is repeated with another clip gripping the other end.
5) Fixing a clamp for clamping the carbon adhesive tape at one end of a self-made prefabricated baking clamp (the self-made prefabricated baking clamp is shown in the attached drawing of the specification (figure 1)); the other clip is fixed at the other end.
6) The prefabricated baking clamp set is designed as follows: when the two clamps were secured to the bake fixture, the distance between the two clamps was 210mm, as described in [0132]2) above, the original test wire was 60mm in length and was now stretched to 210mm, i.e., 3.5 times.
7) Putting the baking clamp prepared in the above way and the stretched fiber to be tested into a preheated electrothermal constant-temperature drying oven, starting timing, baking for 10 minutes, and taking out;
8) checking whether there is fiber breakage, all fiber samples are marked as "X", 2 fiber samples are broken and 3 fiber samples are not broken are marked as "X (1)", 3 fiber samples are broken and 2 fiber samples are not broken are marked as "X (2)", and no fiber sample is broken is marked as "v (square)".
It should be noted that the homemade baking jig described in [0135]5) is shown in the accompanying drawing [ fig. 1] of the specification, and the homemade baking jig is not one of the innovative points of the present invention, only for convenience of explaining the method and the tools for performing the heat resistance test on the sample fiber.
The fibers produced in the same group of examples or comparative examples were subjected to 3 repeated measurements at the same temperature according to the above [0131]1 to [0138]8 procedures, and the data recorded in the test record table 3 is an average value of the 3 measurements.
It should be noted that at each set temperature, the fibers used in each test were fiber samples prepared according to the above 1-8 steps.
The measurement results are shown in Table 3.
TABLE 3
The temperature resistance test results shown in table 3 show that the fiber of the embodiment can withstand temperature treatment at 110-160 ℃ after being irradiated by lower irradiation dose of 60KGy, and the temperature resistance of the fiber is obviously improved compared with that of a comparative sample treated by the same irradiation dose; the fiber of the embodiment can endure the high temperature treatment of 110-180 ℃ after the fiber of the embodiment is treated by the higher irradiation dose of 120KGy, and the fiber of the comparative embodiment which is treated by the same irradiation dose can not endure the high temperature of about 180 ℃ completely.
According to the irradiation method disclosed by the invention, if the temperature resistance is required to be further improved, the temperature resistance of the irradiated fiber can be properly improved by properly improving the irradiation dose, as described in [0076], the irradiation dose can be increased to 180KGy under extreme conditions, so that the irradiated fiber can be ensured to be capable of resisting the limit temperature of 200 ℃.
Drawings
Fig. 1 is a schematic view of a baking jig.
Conclusion
The invention aims to provide a method for manufacturing a crosslinked styrene block copolymer mixture elastic fiber. The direct result of this invention is to provide a novel polyolefin-based elastic fiber having high heat resistance comparable to that of the conventional crosslinked polyolefin elastic fiber, but exhibiting higher breaking strength and elastic recovery. The styrenic block copolymer blends described herein exhibit sustained viscosity stability and feasibility of large scale production in a high temperature processing environment (265 ℃). Meanwhile, the fiber can generate enough gel content and high heat resistance corresponding to the gel content only by using less electron irradiation dose, thereby remarkably reducing the production cost.
Industrial applicability
The invention provides a method for manufacturing novel polyolefin elastic fiber, which has high heat resistance similar to that of the traditional crosslinked polyolefin elastic fiber, but shows higher breaking strength and elastic recovery rate, simultaneously reduces the requirement on irradiation, simplifies the production flow and saves the production cost. The styrene block copolymer mixture elastic fiber prepared by the preparation method can be used for manufacturing various textile fabrics or elastic cords and other fields, and has very wide application.
Claims (11)
1. A method for producing a crosslinked styrene block copolymer mixture elastic fiber, comprising the steps of:
a) providing a styrenic block copolymer mixture comprising at least one styrenic block copolymer a, and at least one ethylene copolymer B by blending;
b) melt spinning the styrenic block copolymer mixture to obtain an elastic fiber;
c) the obtained elastic fiber is subjected to irradiation crosslinking,
wherein the styrene block copolymer A is an unsaturated styrene block copolymer, which isThe ratio of styrene to rubber is between 10:90 and 45:55, the melt index is 200 ℃/5.0kg, and the ratio is 1-50 g/10 min; the density of the ethylene copolymer B is 0.855-0.890 g/cm3The melt index is 0.5-10 g/10min at 190 ℃/2.16 kg; the ratio of the styrene block copolymer A to the ethylene copolymer B is 85: 15-15: 85.
2. The method of claim 1, wherein the ethylene copolymer B further comprises an olefin block copolymer.
3. The method of claim 1, wherein the styrenic block copolymer mixture optionally further comprises Ethylene Propylene Diene Monomer (EPDM).
4. The method of claim 3, wherein the ethylene-propylene-diene monomer rubber is contained in an amount of 0 to 25% based on 100% by weight of the styrene block copolymer mixture.
5. The method of claim 1, wherein the styrenic block copolymer mixture optionally further comprises PPA in an amount of 100ppm to 3000 ppm.
6. The method according to claim 1, wherein in step c), the irradiation is performed at room temperature using electron irradiation or γ -irradiation at a dose of 40 to 180 KGy.
7. The method of claim 1, wherein in step b), the styrenic block copolymer mixture is melt mixed using a pelletizer prior to spinning and re-pelletized, thereby further uniformly mixing the components of the styrenic block copolymer mixture.
8. An elastic fiber of a crosslinked styrene block copolymer mixture, which is produced by the production method according to any one of claims 1 to 7, and which can be a thick and thin yarn, a textured yarn, or a profiled fiber, and has a fineness of 10 to 1000 denier.
9. The crosslinked styrenic block copolymer blend elastic fiber of claim 8 wherein the elastic fiber is capable of withstanding the processing temperature requirements of the downstream textile industry of 120 ℃ to 200 ℃ when stretched to 2.0 to 4.0 times its original length.
10. The crosslinked styrenic block copolymer blend elastic fiber of claim 8 is used in a blended or composite yarn with other fibers or yarns, which can be further used in the production of textile fabrics or elastic cords.
11. The crosslinked styrenic block copolymer blend elastic fiber of claim 8 used in the field of textile fabrics or elastic cords.
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Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304436A (en) * | 1998-06-01 | 2001-07-18 | 陶氏化学公司 | Method of making washable, dryable elastic erticles |
| CN1306556A (en) * | 1998-05-18 | 2001-08-01 | 陶氏化学公司 | Articles having elevated temp. elasticity made from irradiated and crosslinked ethylene polymers and method for making same |
| CN1382187A (en) * | 1999-09-17 | 2002-11-27 | 宝洁公司 | Radiation crosslinked elastomeric materials |
| CN1505660A (en) * | 2000-05-11 | 2004-06-16 | 陶氏化学公司 | Method of making elastic articles having improved heat-resistance |
| JP2004307843A (en) * | 2003-03-27 | 2004-11-04 | Jsr Corp | Molded resin product and processed product thereof |
| CN1701089A (en) * | 2003-03-27 | 2005-11-23 | Jsr株式会社 | Molded resin product and processed product thereof |
| CN101253046A (en) * | 2005-09-01 | 2008-08-27 | 金伯利-克拉克环球有限公司 | Apparatus and methods for making crosslinked elastic laminates |
| CN101313094A (en) * | 2005-10-21 | 2008-11-26 | 陶氏环球技术公司 | Flame and heat resistant stretch fabrics with improved chemical resistance and durability |
| CN101432356A (en) * | 2004-08-13 | 2009-05-13 | 埃克森美孚化学专利公司 | Polymeric compositions including their uses and methods of production |
| CN102016149A (en) * | 2008-02-29 | 2011-04-13 | 陶氏环球技术公司 | Fibers and fabrics made from ethylene/ alpha-olefin interpolymers |
| CN102272223A (en) * | 2008-12-30 | 2011-12-07 | 巴斯夫欧洲公司 | Elastic particle foam based on polyolefin/styrene polymer mixtures |
| CN102762782A (en) * | 2009-12-23 | 2012-10-31 | 英威达技术有限公司 | Elastic fiber containing an anti-tack additive |
| CN102770590A (en) * | 2009-12-23 | 2012-11-07 | 英威达技术有限公司 | Fabric including polylefin elastic fiber |
| CN103668550A (en) * | 2013-11-08 | 2014-03-26 | 江苏纺科新复合材料有限公司 | Preparation method of composite elastic fiber |
| CN104619731A (en) * | 2012-09-19 | 2015-05-13 | 科腾聚合物美国有限责任公司 | Paramethylstyrene block copolymers and their use |
| CN105040147A (en) * | 2015-07-06 | 2015-11-11 | 陈援朝 | Preparation method and preparation system of elastic fiber which can be used for replacing low temperature spandex |
| CN107057618A (en) * | 2017-06-05 | 2017-08-18 | 湖北大学 | A kind of medical pressure sensitive adhesive of novel radiation crosslinking and preparation method thereof |
| CN107057334A (en) * | 2017-05-12 | 2017-08-18 | 四川恒领皓睿塑胶科技有限公司 | Toughness reinforcing strengthens the preparation method of polymer composites |
| CN108699311A (en) * | 2016-02-19 | 2018-10-23 | 特诺尔艾佩斯公司 | Fiber forms composition, fiber and manufacturing method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150328347A1 (en) * | 2005-03-24 | 2015-11-19 | Xyleco, Inc. | Fibrous materials and composites |
-
2019
- 2019-02-26 CN CN201910143596.3A patent/CN109930238B/en active Active
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1306556A (en) * | 1998-05-18 | 2001-08-01 | 陶氏化学公司 | Articles having elevated temp. elasticity made from irradiated and crosslinked ethylene polymers and method for making same |
| CN1304436A (en) * | 1998-06-01 | 2001-07-18 | 陶氏化学公司 | Method of making washable, dryable elastic erticles |
| CN1382187A (en) * | 1999-09-17 | 2002-11-27 | 宝洁公司 | Radiation crosslinked elastomeric materials |
| CN1505660A (en) * | 2000-05-11 | 2004-06-16 | 陶氏化学公司 | Method of making elastic articles having improved heat-resistance |
| JP2004307843A (en) * | 2003-03-27 | 2004-11-04 | Jsr Corp | Molded resin product and processed product thereof |
| CN1701089A (en) * | 2003-03-27 | 2005-11-23 | Jsr株式会社 | Molded resin product and processed product thereof |
| CN101432356A (en) * | 2004-08-13 | 2009-05-13 | 埃克森美孚化学专利公司 | Polymeric compositions including their uses and methods of production |
| CN101253046A (en) * | 2005-09-01 | 2008-08-27 | 金伯利-克拉克环球有限公司 | Apparatus and methods for making crosslinked elastic laminates |
| CN101313094A (en) * | 2005-10-21 | 2008-11-26 | 陶氏环球技术公司 | Flame and heat resistant stretch fabrics with improved chemical resistance and durability |
| CN102016149A (en) * | 2008-02-29 | 2011-04-13 | 陶氏环球技术公司 | Fibers and fabrics made from ethylene/ alpha-olefin interpolymers |
| CN102272223A (en) * | 2008-12-30 | 2011-12-07 | 巴斯夫欧洲公司 | Elastic particle foam based on polyolefin/styrene polymer mixtures |
| CN102762782A (en) * | 2009-12-23 | 2012-10-31 | 英威达技术有限公司 | Elastic fiber containing an anti-tack additive |
| CN102770590A (en) * | 2009-12-23 | 2012-11-07 | 英威达技术有限公司 | Fabric including polylefin elastic fiber |
| CN104619731A (en) * | 2012-09-19 | 2015-05-13 | 科腾聚合物美国有限责任公司 | Paramethylstyrene block copolymers and their use |
| CN103668550A (en) * | 2013-11-08 | 2014-03-26 | 江苏纺科新复合材料有限公司 | Preparation method of composite elastic fiber |
| CN105040147A (en) * | 2015-07-06 | 2015-11-11 | 陈援朝 | Preparation method and preparation system of elastic fiber which can be used for replacing low temperature spandex |
| CN108699311A (en) * | 2016-02-19 | 2018-10-23 | 特诺尔艾佩斯公司 | Fiber forms composition, fiber and manufacturing method |
| CN107057334A (en) * | 2017-05-12 | 2017-08-18 | 四川恒领皓睿塑胶科技有限公司 | Toughness reinforcing strengthens the preparation method of polymer composites |
| CN107057618A (en) * | 2017-06-05 | 2017-08-18 | 湖北大学 | A kind of medical pressure sensitive adhesive of novel radiation crosslinking and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 功能弹性体;金鹰泰;《弹性体》;19931231(第01期);第44-51页 * |
| 钢丝绳涂塑材料HDPE的研究进展;梅文杰等;《塑料工业》;20130720(第07期);第7-12页 * |
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