CN109930238A - A kind of the styrene block copolymer mixture elastomer and its manufacturing method of crosslinking - Google Patents
A kind of the styrene block copolymer mixture elastomer and its manufacturing method of crosslinking Download PDFInfo
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Abstract
The present invention relates to a kind of manufacturing methods of the styrene block copolymer mixture elastomer of crosslinking, it comprises the following steps: a kind of styrene block copolymer mixture a) is provided by being blended, it includes at least one styrene block copolymer A and at least one ethylene copolymer B；B) melt spinning is carried out to obtain elastomer to the styrene block copolymer mixture；C) cross-linking radiation is carried out to obtained elastomer；Wherein, the styrene block copolymer A is unsaturated styrene block copolymer, its styrene/rubber ratio is between 10: 90 to 45: 55, and (200 DEG C/5.0kg) of melt index are 1~50g/10min, and the density of the ethylene copolymer B is 0.855~0.890g/cm3, (190 DEG C/2.16kg) of the melt index ratios for 0.5~10g/10min, the styrene block copolymer A and the ethylene copolymer B are between 85: 15~15: 85.
Description
Technical field
The present invention relates to a kind of manufacturing methods of the styrene block copolymer mixture elastomer of crosslinking；And it is a kind of
Use styrene block copolymer mixture elastomer made of the manufacturing method；And the elastomer is in all kinds of spinnings
Application in the fields such as knitted fabric or elastic cotton rope.
Background technique
Comfortably, zoarium, guarantor's type, crease-resistant, fitting movement needs, are the important categories that elastomer pays fabric or clothes
Property and clothes or fabric development direction, future can be described as " no cloth not bullet ", and elastic in elasticised garment or fabric
Source be mainly that elastomer is added in garment material to realize.
Spandex in existing elastomer (scientific name " polyurethane elastomeric fiber ", including dry method spandex, Wet-process Spandex and molten
Spin spandex) account for the market share close to 90% and occupy the dominant position of weaving or elastic cotton rope field, but spandex exist it is easy
Degradation with aging, easy fracture relaxation, containing hazardous solvent, it is not alkaline-resisting, chlorine-resistant drift, be not easy the defects of contaminating dark color.
In elastic cotton rope field, causes elastic cotton rope lasting, ageing-resistant using conventional spandex fiber, especially exist
Apparent defect is embodied in the elastic cotton rope of professional domain, needs a kind of elastomer that stability and durability is anti-aging instead.
The polyolefin elastic fiber of traditional crosslinking is that the Dow Chemical Company (Dow Chemical) released in 2002 or so
New elastic fiber product, such elastomer are resistant to up to 220 DEG C of setting temperature, chlorine-resistant drift, strong acid-base, uvioresistant drop
Solution, flexible and can be with the performances such as low-temperature shaped, the usage and dosage in textile is also suitable with spandex, overcomes spandex not
It is ageing-resistant, chlorine-resistant floats not alkaline-resisting disadvantage, be preferably a kind of elastomer of comprehensive performance.But Dow Chemical's production
There are three major defects for traditional polyolefin elastic fiber product:
1, intensity is low, breaking strength between 0.50~0.80cN/dtex, far below common dry method spandex 1.0~
The breaking strength of 1.7cN/dtex, thus it is smaller using the elastic fabric elasticity that the Dow Chemical Company's polyolefin elastic fiber produces, only
Fabric in being suitable for producing low elasticity fabric and can not produce；
2, elastic recovery rate is poor, and the elastic recovery rate after the polyolefin elastic fiber 300% of the Dow Chemical Company stretches is general
Not higher than 85%, lower than elastic recovery rate after 300% stretching of common dry method spandex nearly 10% is even more, so that nothing
Method is promoted the use of into many fabrics (such as underwear, swimming suit, jean, gym suit etc.) for needing normal rebound degree to require
It goes；
3, polyolefin elastic fiber processing technology complexity, the cost of the Dow Chemical Company's production can not be stood above any more, therefore are failed always
Into the mainstream market of elastomer.
Three above major defect causes the Dow Chemical Company to exit conventional polyolefins elastomer product in most finally 2010
Research and development and production field.
One well known fact is that styrene block copolymer (SBCs) compares traditional polyolefin elastic copolymer
(POE) there is better elastic recovery；And styrene block copolymer is also a kind of special polyolefin copolymers, it is resistance to
The acid characteristics such as alkaline-resisting are much stronger than polyurethane elastomer.But the use temperature of styrene block copolymer is lower, mainly due to benzene
The glass transition temperature of styrene hard block in ethylene block copolymer is at 95 DEG C or so, the mainstream of the different trades mark of different company
The normal use temperature that styrene block copolymer can be born is all at 60 DEG C~80 DEG C or less.So using produced in conventional processes
Styrene block copolymer elastomer can not bear dyeing, drying and the thermal finalization of textile fabric or elastic cotton rope
(the dyeing final finishing temperature of traditional textile fabric or elastic cotton rope is led at least at 100 DEG C or more for the requirement of equal normal process temperatures
Often between 120~150 DEG C, the temperature that part fabric processing technology requires is even up to 200 DEG C or so), therefore can not be direct
It applies in the market in textile fabric or elastic cotton rope field.
For the defect for overcoming styrene block copolymer non-refractory, one kind is disclosed in bibliography 1 and is included in inertia
Or under limited oxygen atmosphere (such as in nitrogen, argon, helium, carbon dioxide, under xenon and/or vacuum) cross-linking radiation (also referred to as " crosslinking with radiation ") system
The method of product, wherein the product includes at least one amine stabiliser and another optional stabilization additives.The elastic article packet
The block copolymerization that it is containing uniform branch ethenyl copolymer (preferably a kind of ethenyl copolymer of substantially straight chain), is substantially hydrogenated
Object or this two kinds combination.It must be noted that the limitation of the ambiance of cross-linking radiation is by the large-scale production to the elastomer
Big inconvenience is caused, production cost is improved and also reduces production efficiency simultaneously.The document thinks, unsaturated block copolymerization
Object is intended to show common thermal stability, especially such as styrene-fourth ethylene-stryene triblock copolymer (SBS)
Lower and undesirable UV stability in a molten state.Therefore hair of the block copolymer substantially hydrogenated more suitable for the document
It is bright.But it is understood that, relative to unsaturated block copolymer, substantially being hydrogenated under conditions of same cross-linking radiation
The cross-linking efficiency quantity of gel (inside generate) of block copolymer be much inferior.From the embodiment 14 in the document,
15,16 as can be seen that electron beam irradiation will reach the dosage of at least 22.4Mrad (or 224KGy) in a nitrogen environment, with basic
The fiber of the block copolymer production of upper hydrogenation just shows improved heat resistance, and passes through simulation dyeing and heat-setting process.
The irradiation of such high dose increases the production cost of fiber not only significantly, but also elastomer yellowing can significantly be caused to become
Color, elastomer spinning cake contraction distortion cause to significantly improve positioned at the elastomer adhesion of internal layer, end breakage rate, debatching difficulty etc.
Problem.
Bibliography 1:CN1505660
Summary of the invention
The purpose of the present invention is to provide with a kind of manufacture of the styrene block copolymer mixture elastomer of crosslinking
Method.There is provided a kind of novel polyolefin elastic fibers for the direct result of this invention, it has poly- with tradition crosslinking
Heat resistance that olefin elastic fibers compare favourably but present higher breaking strength and elastic recovery rate.Surprisingly exist
During making this new elastic fiber, unsaturated styrene block copolymer such as s-B-S
(SBS), styrene-isoprene-phenylethene (SIS) etc., by the way that suitable additive is mutually mixed and added with ethylene copolymer,
In the environment of high temperature process (265 DEG C), it is shown that the feasibility of lasting viscosity stability and large-scale production.It is same with this
When, which only needs less electron irradiation dosage to can produce enough gel contents and high heat resistance correspondingly
Property, production cost is reduced significantly and simplifies production procedure.
The present invention relates to a kind of manufacturing methods of styrene block copolymer mixture elastomer, comprise the following steps:
A) a kind of styrene block copolymer mixture is provided by being blended, it is total that it includes at least one styrene blocks
Polymers A and at least one ethylene copolymer B；
B) spinning is carried out to obtain elastomer to the styrene block copolymer mixture；
C) cross-linking radiation is carried out to obtained elastomer,
Wherein, the styrene block copolymer A is unsaturated styrene block copolymer, styrene/rubber ratio
Between 10: 90~45: 55, (200 DEG C/5.0kg) of melt index be 1~50g/10min；The density of the ethylene copolymer B
For 0.855~0.890g/cm3, (190 DEG C/2.16kg) of melt index be 0.5~10g/10min；The styrene
The ratio of object A and the ethylene copolymer B are between 85: 15~15: 85.
In the manufacturing method of the present invention, the preferably described ethylene copolymer B also includes olefin block copolymers (representative products
For the INFUSE of Dow ChemicalTM)。
In the manufacturing method of the present invention, the styrene block copolymer mixture may include crosslinking accelerator, described
Crosslinking accelerator includes copolymer ethylene propylene diene rubber (EPDM).
In the manufacturing method of the present invention, based on the styrene block copolymer mixture of 100 weight %, the friendship
The content of connection promotor is that the content of 0%-25%, styrene block copolymer A and ethylene copolymer B are 100%-75%.
In the manufacturing method of the present invention, the styrene block copolymer mixture may include plastic processing additives
(PPA) such as fluorochemical additive or super high molecular weight silicone oil master batch preferentially use fluorochemical additive
In the manufacturing method of the present invention, the manufacturing method further comprises that step c) is carried out after step b):
Electron Beam Irradiation or gamma-irradiation method can be used in step c), irradiated at room temperature, irradiation dose is 40~180KGy
(4~18Mrad).Radiation environment can be to carry out in air, or (such as in nitrogen, argon, helium, dioxy under inertia or limited oxygen atmosphere
Change carbon, under xenon and/or vacuum) it carries out.
In the manufacturing method of the present invention, in the step b) by the styrene block copolymer group mixture in spinning
Before, it is granulated again after being melted mixture using the pelletizer for being suitable for copolymer granulation, to further make the styrene
Block copolymer mixture each component uniformly mixes.
It can be long filament, thickness section using styrene block copolymer mixture elastomer made of above-mentioned manufacturing method
Silk, textured filament or profiled filament, fiber number are 10 denier~1000 denier.
In the manufacturing method of the present invention, the styrene block copolymer mixture elastomer of the crosslinking is being stretched to
In the case where 2.0~4.0 times of former length, 120 DEG C~200 DEG C of textile following process temperature can be resistant to.
Moreover, it relates to which a kind of be used for using the styrene block copolymer mixture elastomer of above-mentioned crosslinking
Mixed yarn or complex yarn made of together with other fibers or yarn (such as: covering yarn, wrap yarn or fasciated yarn etc.),
Other fibers or yarn include synthetic fibers, natural fiber and fiber class material etc..
Be directly added into the invention further relates to the styrene block copolymer mixture elastomer being crosslinked as described above or
Textile fabric is applied in the form of mixed yarn, complex yarn, and elastic textiles or elasticity perhaps is made in the production of cotton rope
Cotton rope product.
Specific embodiment
The present invention is described in detail below.
Term " styrene block copolymer " in the present invention refers to a kind of unique thermoplastic elastic material, it has
The polystyrene end blocks (i.e. " hard segment ", hereinafter referred to as " hard segment ") of hard and the rubber mid-block of softness are (i.e. " soft
Segment ", hereinafter referred to as " soft chain segment ") two phase structure.Polystyrene end blocks (hard segment) aggregation constitutes physics crosslinking points,
Polymer molecule can be fixed without vulcanization, so that good intensity is provided, and rubber mid-block (soft chain segment) provides bullet
Property performance.According to the difference of degree of hydrogenation, styrene block copolymer can be divided into unsaturated styrene block copolymer (USBS),
Such as SIS, SBS；Fractional saturation styrene block copolymer, such as SIBS；Hydrogenated styrene block copolymers (HSBC), such as
SEBS.Term " styrene block copolymer " in the present invention generally refers in particular to unsaturated styrene block copolymer.
Term " styrene block copolymer mixture " in the present invention refers to unsaturated styrene block copolymer and extremely
A kind of few ethylene copolymer, also may include copolymer ethylene propylene diene rubber (EPDM), is formed by mixture after evenly mixing.
Term " copolymer " in the present invention is also known as copolymer, refers to by two or more different monomers through being copolymerized
Copolymer obtained by reaction.Term " copolymer " include term " random copolymer ", " alternate copolymer ", " block copolymer ",
" graft copolymer ", " bipolymer " and " terpolymer " etc..Copolymer generally holds in a reactor or copolyreaction
It is prepared in device, but multiple reactors or the preparation of copolyreaction container also can be used.
Term " block copolymer " in the present invention refers to as two or more monomer through product made of block copolymer,
I.e. two or more monomer unit exists on copolymer main chain at section.
Term " heat resistance " in the present invention refers to that the styrene block copolymer mixture of the crosslinking of fibers form passes through
The ability of heretofore described high temperature baking test.
The term " tolerance " refers to that the styrene block copolymer mixture of the crosslinking of fibers form can be in certain temperature
Degree is lower not broken by required various procedure of processings.
Term " melt flow rate (MFR) " (also known as melt index) in the present invention is Copolymer Melts in predetermined temperature and
Under load (pressure) effect, pass through within 10 minutes the quality (g) of standard mouth mold, unit g/10min.
Term " irradiation " in the present invention refers to RADIATION PROCESSING, radiation treatment or irradiation processing, i.e., is issued by radiation source
Effects of ionizing radiation makes to be illuminated substance inside generation covalent cross-linking in something to make its quality or performance be improved
A kind of processing method.
The present invention relates to a kind of manufacturing methods of styrene block copolymer mixture elastomer, comprise the following steps:
A) a kind of styrene block copolymer mixture is provided by being blended, it is total that it includes at least one styrene blocks
Polymers A and at least one ethylene copolymer B；
B) spinning is carried out to obtain elastomer to the styrene block copolymer mixture；
C) cross-linking radiation is carried out to obtained elastomer,
Wherein, the styrene block copolymer A is unsaturated styrene block copolymer, styrene/rubber ratio
Between 10: 90~45: 55, (200 DEG C/5.0kg) of melt index be 1~50g/10min；The density of the ethylene copolymer B
For 0.855~0.890g/cm3, (190 DEG C/2.16kg) of melt index be 0.5~10g/10min；The styrene
The ratio of object A and the ethylene copolymer B are between 85: 15~15: 85.
Styrene block copolymer A
The unsaturation that the styrene block copolymer A can be any commercial available commodity or be prepared according to the prior art
Styrene block copolymer, as long as its styrene/rubber ratio is between 10: 90~45: 55, melt index (200 DEG C/5.0
It kg) is 1~50g/10min.
It is preferred that the not limiting example of the suitable commercial goods of the styrene block copolymer A includes: Taiwan rubber
The unsaturated styrene block copolymer (USBC) of limited liability company (TSRC Corp.) productionSeries
Product；Unsaturated styrene block copolymer (USBC) KRATON " D " series of Ke Teng copolymer company (KRATON) production produces
Product；The TUFPRENE of Japanese Asahi Kasei Corporation (Asahi Kasei Corp.)TMSeries of products；Global rubber company (the LCY in Taiwan
Grit Corp.) GLOBALPRENETMSeries of products etc. specifically include s-B-S (SBS), styrene-
Isoprene styrene (SIS), styrene-isoprene/butadiene-styrene (SIBS), etc..
Ethylene copolymer B
The ethylene copolymer that the ethylene copolymer B can be any commercial available commodity or be prepared according to the prior art,
As long as its density is 0.855~0.890g/cm3, (190 DEG C/2.16kg) of melt index be 0.5~10g/10min.
The ethylene copolymer is formed by ethylene and at least one C4~C20 olefin-copolymerization.C4~C20 olefinic monomer
Non-limitative example include: 'alpha '-olefin monomers, for example, 1- butylene, isobutene, 1- amylene, 1- hexene, 1- octene, its branch
Isomers, styrene, α-methylstyrene and their mixture.C4~C20 olefinic monomer and copolymerization conditions visually need
It is selected, as long as the density that can satisfy ethylene copolymer B is 0.855~0.890g/cm3, melt index (190 DEG C/
It 2.16kg) is 0.5~10g/10min, preferred molten index is 1~5g/10min.
The ethylene copolymer B includes ethylene-octene block copolymer.
It is preferred that the not limiting example of the suitable commercial goods of the ethylene copolymer B includes: Dow Chemical
The INFUSE of (Dow Chemical) productionTM、ENGAGETM、AFFINITYTM；Exxon Mobil Corporation (ExxonMobil) is raw
The EXACT of productionTM；The TAFMER of Mitsui Chemicals, Inc (Mitsui Chemicals) productionTMDeng.
The weight ratio of styrene block copolymer A and ethylene copolymer B are 85: 15~15: 85, preferred proportion 70: 30, more
Preferred proportion 50: 50.
The cross-linking efficiency of styrene block copolymer A and ethylene copolymer B under electron irradiation in order to further increase, institute
It states in styrene block copolymer mixture also optionally comprising the crosslinking accelerator of specific quantity.The crosslinking accelerator includes
Ethylene propylene diene rubber (EPDM).The non-limitative example of ethylene propylene diene rubber includes Dow Chemical (Dow Chemical)
The NORDEL of productionTM；The ROYALENE of lion chemical company (Lion Copolymer, LLC) productionTM；Exxon Mobil Corporation
(ExxonMobil) VISTALON producedTMEqual series of products.
Based on the styrene block copolymer mixture of 100 weight %, styrene block copolymer A and ethylene copolymer B
Total content be 75~100 weight %, preferably 80~98 weight %, more preferable 85~95 weight %；The content of crosslinking accelerator
Preferably 0~25 weight %, more preferable 2~20 weight %, more preferable 5~15 weight %.
In the case where styrene block copolymer mixture includes above-mentioned ethylene propylene diene rubber, needed for can further decreasing
The irradiation dose wanted promotes irradiation efficiency.
In the manufacturing method of the present invention, the styrene block copolymer mixture may include plastic processing additives
(PPA) such as fluorochemical additive or super high molecular weight silicone oil master batch preferentially use fluorochemical additive.
PPA auxiliary agent is the polymer processing aids by fluoro containing polymers polymer for basic structure, and PPA auxiliary agent is widely applied
In polyethylene (including LLDPE, mLLDPE, MDPE, HDPE, HMW-HDPE, LDPE, VLDPE etc.), ethylene-vinyl acetate
(EVA), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), nylon, the engineering plastics such as polyester PET and PC, ABS
The processing of material, main function of the PPA auxiliary agent in engineering plastics processing include:
1) apparent viscosity, extruder pressure and extrusion temperature are reduced.
2) melt fracture phenomena and die orifice buildup phenomenon are decreased or even eliminated.
3) cleaning capacity of reduction melt is shown in screw rod viscosity, lifting handle.
4) cross-linked gel and oxidation gel in extrusion process are reduced.
5) excellent high temperature resistant processing performance.
6) make final products that there is more preferably surface smoothness and appearance, not easy to break.
In the present embodiment using the main function of PPA auxiliary agent be improve resin processing performance, reduce melt pressure change
Kind fluidity of molten reduces processing torque energy consumption, increases product extrusion quality, improves and produces effect, improves product surface glossiness；Subtract
Cross-linked gel and oxidation gel in few extrusion process, while decreasing spinning nozzle buildup, reducing spinning crack conditions, and
Melt is reduced for the viscosity of spinning pipeline, promotes the service life of spinning equipment.
The non-limitative example of suitable fluorochemical additive commercial product includes: the DYNAMER of Minnesota Mining and Manufacturing CompanyTMSeries,
The DAI-EL of Daikin company (DAIKIN)TMSerial, ARKEMA company, France KYNARTMThe PPA product such as series.Suitable
The non-limitative example of super high molecular weight silicone oil master batch commercial product includes: the MB system of Dow Corning Corporation (Dow-Corning)
It arranges, the KJ series super high molecular weight silicone oil master batch of Hangzhou Kai Jie plastics Science and Technology Ltd..
Various conventional additives can be optionally further included in styrene block copolymer mixture of the invention,
Such as: antioxidant, plumper, antistatic agent, lubricant, nucleating agent, compatilizer, release agent, clarifying agent, is filled out at UV stabilizer
Material, colorant, water absorbing agent, cross-linked accelerating agent for irradiation etc..The weight of styrene-based block copolymer mixture, the additive
Content be 0.001~10 weight %, preferably up to 5.0 weight %, more preferably up to 2.0 weight %.
Above-mentioned additive can be added in styrene block copolymer mixture.These usual additives are squeezed in granulation
It is stirred evenly in advance with mixture before process out, or passes through individual weight-loss type feeder or screw rod in being granulated extrusion process
Feeder is added separately in the feed inlet of pelletizer by weight, with mixture.
For the mixing in step a) of the present invention, it can be used conventional vertical particle batch mixer, Horizontal type mixer, bipyramid mixed
Conjunction machine, trough type mixing machine etc..In order to obtain mixed effect more evenly, can after first mixing, using conventional kneading or
Mixing apparatus, such as banbury mixers, double roller rubber mills, Buss co-kneader or double screw extruder etc. carry out two
Secondary mixing carries out secondary mixing using rubber clearance mixing machine (Rubber Batch Mixer) superposition screw extruder pelletizer
It is granulated, thus to obtain uniformly mixed particulate material.
It, can be by the particle of styrene block copolymer mixture obtained in step a) in step b) of the invention
Raw material directly carries out spinning using melt spinning method, that is: by the particulate material of styrene block copolymer mixture in list
Melting, the pipeline by heated sealed, which input spinning manifold and then pumped by spinneret, in screw extruder is pressed into spinneret for melt
Head, melt are flowed out from spinning head to be formed filament, filament and through condensation forms fiber, and then coiled into silk by silk with spinning winding head again
The processes such as cake.
It can be used in the present invention and be suitable for spinning melting and spin spandex equipment or similar equipment to carry out spinning, usual spinning
Speed is 400~1000 ms/min, and spinning temperature can be optionally adjusted by those skilled in the art according to common sense.
It is 10 denier~1000 denier fiber that styrene block copolymer mixture of the invention, which can be made into fiber number,.It is sent out when by this
Fiber (in the present invention, fiber number fibre greater than 140 denier of the fiber number greater than 140 denier is made in bright styrene block copolymer mixture
Dimension is also known as thick fine) when, during spinning winding, it may be necessary to replace air cooling, using water cooling to prevent fiber viscous
Knot is on godet.
Term " denier " full name " danier ", English Denier in the present invention write a Chinese character in simplified form " D ", refer to 9000 meters of long fibers or
The grams of yarn weight in official regain, can pass through formula: (in formula: G is that fiber or yarn exist to D=(G/L) × 9000
Weight (gram) when official regain, L be the length (rice) of fiber or yarn) it is calculated.Grammes per square metre is bigger, that is, denier is got over
Height shows that fiber or yarn are thicker.
Term " tex " in the present invention refers to Tekes, and English TEX is referred to as special, refers to 1000 meters long of fiber or yarn
The grams of weight under official regain, can pass through formula: (wherein: G is fiber or yarn in public affairs to tex=(G/L) x1000
Determine the weight (gram) when regain, L is the length (rice) of fiber or yarn) it calculates.Grammes per square metre is bigger, that is, special number is higher, table
Bright yarn is thicker.
Term " dtex " in the present invention refers to dtex, refers to the long fiber of ten thousand metres or yarn under official regain
The grams of weight.It can pass through formula: (wherein: G is fiber or yarn in official regain to dtex=(G/L) x10000
Weight (gram), L be the length (rice) of fiber or yarn) it calculates.Grammes per square metre is bigger, that is, special number is higher, shows that yarn is thicker.
According to above-mentioned definition it is found that D can convert mutually with tex, dtex, 1tex=1/10dtex=1/9D.
Cross-linking radiation is carried out to styrene block copolymer mixture of fibers obtained.Irradiation is typically all in spinning coil
It is carried out after being coiled into spinning cake, and can use method known in the art under room temperature and air conditions or limited oxygen condition
Lower carry out cross-linking radiation, the method includes but be not limited to: Electron Beam Irradiation, corona irradiation method, gamma-irradiation method and UV spoke
According to method etc..In these methods, preferably Electron Beam Irradiation or gamma-irradiation method.
Irradiation dose can need the temperature born to determine according to the fiber, as long as guaranteeing that fibrous inside can generate enough
Curing gel to not broken under conditions of high-temperature process.Irradiation dose preferably 40~180K6y, more preferable 50~
150KGy, more preferable 60~120KGy.
Styrene block copolymer mixture of the invention can optionally carry out spinning to formed long filament, thickness section silk,
Textured filament or profiled filament, or composite fibre is formed with other copolymerization composition copolymers.
Term " long filament " refers to fiber of the length in terms of km in the present invention, can be divided into: monofilament, multifilament, cord silk.
Term " monofilament " refers to a continuous single fiber made of single hole spinning head spinning in the present invention.
Term " multifilament " refers to as two or two or more single fiber groups compound strand with made of in the present invention.
Term " thickness section silk " refers to and is shaped during the spinning process by technological means or special optional equipment in the present invention
Uneven thickness is alternately present slubbing and detail section, to reach the silk or yarn of Special use requirement.
Term " textured filament ", which refers to, in the present invention carries out deformation processing to fiber by technological means or special optional equipment
Treated silk or yarn.
Term " profiled filament " refers to special through having for certain geometrical shape (non-circular) spinneret orifice spinning in the present invention
The chemical fibre of cross sectional shape.
Term " composite fibre " refers to that there are two or more immiscible copolymers on section, cut in the present invention
Face can be divided into parallel type, core-skin type, split release, fabric of island-in-sea type etc..
The invention further relates to use styrene block copolymer mixture elastomer and other fibers or yarn of the invention
Perhaps complex yarn such as covering yarn, wrap yarn or fasciated yarn etc., " other fibers " wrap manufactured mixed yarn line together
Include synthetic fibers and natural fiber.
Term " mixed yarn " in the present invention refers to the scribbled being made of two or more fiber, such as wash/
Silk/cotton blended yarn, hair/wash mixed yarn, hair/nitrile mixed yarn is washed/glue/nitrile mixed yarn, real silk/cotton yarn twisted union yarn etc..
Term " natural fiber " in the present invention includes for example various wools, the rabbit hair, camel hair or other animal hairs, silkworm
Silk, cotton, fiber crops or other plant fibers and asbestos fibre etc..
Term " complex yarn " in the present invention refers to the yarn combined by two or more fiber, according to certain rules
Line.Preferred complex yarn includes: using styrene block copolymer mixture spandex filaments and other fibres of the invention
Covering yarn, wrap yarn or fasciated yarn is made in dimension together.
Term " covering yarn " in the present invention refers to by using strength or the preferable filament of synthetic fibre of elasticity as core filaments, outside
The weavings such as Bao Mian, hair, viscose rayon are twisted together with staple fiber and the complex yarn that is spun into.Covering yarn tool of the present invention
Body is coated on styrene block of the invention by core spinning equipment known in textile industry with staple fiber by other weavings
The covering yarn formed on copolymer mixture spandex filaments." weaving staple fiber " suitable for the present invention includes but not
It is limited to following three classes:
1) cotton fiber and the chemical fibre for being cut to 38mm or so are known as " cotton-type short fiber " in textile industry.
2) wool, the rabbit hair, camel-hair fiber and the chemical fibre for being cut to 70~85mm or so are known as " hair in textile industry
Type staple fiber ".
3) it is cut to the chemical fibre of 55mm or so, is known as " medium-length staple fiber " in textile industry.
Term " wrap yarn " of the present invention refers to using strength or the preferable filament of synthetic fibre of elasticity as core filaments, passes through
Air knot tying fashion envelopes core filaments and manufactured complex yarn.Wrap yarn of the present invention is specifically fine by other bicomponent filament yarns
Dimension is coated on styrene block copolymer mixture elasticity fibre of the invention by empty packet spinning equipment known in textile industry
The wrap yarn formed on dimension long filament.The outsourcing " composite long fiber " for being suitable for the upper wrap yarn includes but is not limited to: nylon
All kinds of chemical-fibres filaments such as long filament, polyester filament, viscose filament yarn, acrylic filaments, tencel long filament, polypropylene filament yarn preferably use Buddhist nun
The corresponding wrap yarn of the productions such as imperial long filament, polyester filament, viscose filament yarn, acrylic filaments.
Term " fasciated yarn " of the present invention refers to using strength or the preferable filament of synthetic fibre of elasticity as core filaments, uses
Other composite long fibers or yarn looping by way of around core filaments looping live core filaments and manufactured complex yarn.The present invention
The fasciated yarn specifically passes through wraping spinning equipment packet known in textile industry by other bicomponent filament yarn fibers or yarn
It twines in the fasciated yarn formed on styrene block copolymer mixture spandex filaments of the invention.It is suitable for the upper looping
The outsourcing " composite long fiber or yarn " of yarn include but is not limited to: Tynex, polyester filament, viscose filament yarn, acrylic filaments,
All kinds of chemical-fibres filaments such as tencel long filament, polypropylene filament yarn are and all kinds of cotton yarns, polyester, cotton acrylic fibers, Polyester Yarns, cotton glue yarn, cotton brocade
All kinds of yarns such as the viscous yarn of yarn, brocade, preferably use Tynex, polyester filament, viscose filament yarn, acrylic filaments, cotton yarn, polyester-cotton blend
The corresponding fasciated yarns of productions such as yarn, cotton nitrile yarn
The characteristics of each composition fiber is had concurrently using complex yarn product made from above-mentioned resultant yarn method, and can obtain as needed
Obtain special appearance.
Styrene block copolymer mixture spandex filaments and packet prepared by manufacturing method according to the invention
Complex yarn containing styrene block copolymer mixture elastomer prepared by manufacturing method according to the invention is (i.e. above-mentioned
The complex yarns such as covering yarn, wrap yarn, fasciated yarn) can be used for weft-knitted stretch knit fabric, warp knit stretch knit fabric, elasticity
The production of shuttle-woven fabric, elastic rope etc. has very extensive purposes in weaving or field of rope.
Embodiment
The present invention will be further elaborated by following embodiment.
Each component as shown in Table 1 is added in miniature high-speed blender and is mixed, is then transported to twin-screw again
Mixing granulation is carried out in extruder, thus 5~10 kilograms of styrene block copolymer compound particles of production.
Melt flow rate (MFR):
According to GB/T3682-2000 " measurement of thermoplastic melt flow rate (MFR) and melt volume-flow rate ",
The melt flow rate (MFR) of styrene block copolymer compound particles obtained is measured under 190 DEG C and 2.16kg loading condition.
The results are shown in Table 1.
The composition and content (weight %) of 1 styrene block copolymer mixture of table
Note:
1) ethylene-octene block copolymer, INFUSE-9107, supplier's DOW Chemical, melt index (190 DEG C/
2.16kg): 1.0, density: 0.866g/cm3；
2) ethylene-octene block copolymer, INFUSE-9507, supplier's DOW Chemical, melt index (190 DEG C/
2.16kg): 5.0, density: 0.866g/cm3；
3) styrene-isoprene-styrene copolymer (SIS): D1164, Ke Teng copolymer company, melt index
(200 DEG C/5kg): 12, density: 0.94g/cm3, styrene/rubber ratio: 29/71；
4) styrene-butadiene-styrene (SBS): 3527, Huizhou Li Changrong limited rubber company, melting refers to
Number (190 DEG C/5kg): 8, density: 0.94g/cm3, styrene/rubber ratio: 25/75；
5) ethylene propylene diene rubber (EPDM): Dow Chemical Nordel IP 4820P, melt index (190 DEG C/
2.16kg): 1.0, density 0.908g/cm3；
6) PPA (plastic processing additives): Dynamar 5924, the fluorine-containing auxiliary agent that Minnesota Mining and Manufacturing Company produces.
Then, the mixture obtained in comparative example and embodiment is enterprising in 25mm single screw rod single unit spinning machine respectively
Row spinning, the aperture of spinneret are 1.0mm, and spinning speed is set as 450m/min, and the fiber number of fiber is 111dtex (about 100
Denier).In embodiment and comparative example, the humidity province of screw extruder is set are as follows: 150 DEG C~235 DEG C~245 DEG C~255 DEG C~265
DEG C, and the temperature of spinneret (including spinneret) is set as 265 DEG C.
Each fiber sample obtained stretches by force tester (Wenzhou border high detection Instrument Ltd.) in YG008E fiber type
On carried out following measurement.
The breaking strength and elongation of fiber:
It is surveyed according to FZ/T 50006-1994 (2007) " spandex thread breaking strength and elongation at tear tests method "
It is fixed.According to following setting testing equipment: sample clamp distance: 50mm；Tensile speed: 500mm/min；Test fixture: 100cN.
Carry out 3 efficiency tests.The average of 3 obtained data of test by measurement sample measurement result.As a result such as 2 institute of table
Show.
Fiber determines elongation (300%) elastic recovery rate:
It is surveyed according to FZ/T 50006-1994 (2007) " spandex thread breaking strength and elongation at tear tests method "
It is fixed.According to following setting testing equipment: sample clamp distance: 50mm；Tensile speed 500mm/min.In elongation strain 300%
When, 1 time circulation after stop 30 seconds；2nd time takes the fibre length of tensioned value that time when stretching be length after extension recovery
(L2).It is calculated by following formula:
In formula, L1It is herein 200mm for the length of the fiber after stretching 300%；L2For length after extension recovery；L0For fibre
Wella stretches front clamp length, is herein 50mm.The average of 3 obtained data of test by measurement sample measurement result.
The results are shown in Table 2.
Table 2
Result as shown in table 2 it is found that the breaking strength of the made elastomer of embodiment to be apparently higher than comparative example elasticity fine
The breaking strength of dimension, the promotion of breaking strength is clearly (ratio that promoted in sample reaches 28.8%~75%)；And 300%
Surely the promotion of the elastic recovery rate extended is also clearly (the promotion ratio in embodiment reaches 9.4%~14.9%)；And it is real
Declined although applying the average elongation at break in example and being compared with comparative example, has also reached 500% or more, it completely can be with
Meet the requirement that downstream uses.
From result shown in table 2 it is found that the styrene block copolymer mixture bullet that the method manufactures according to the present invention
Property fiber has higher breaking strength and higher elastic recovery rate.
" breaking strength enhancing rate " (T) is calculated by following equation in table 2:
In formula, T is breaking strength enhancing rate；N1For embodiment breaking strength values；N0For comparative example breaking strength values.
" elastic recovery rate enhancing rate " (X) is calculated by following equation in table 2:
In formula, X is elastic recovery rate enhancing rate；H1For " 300% elasticity of elongation response rate of embodiment "；H0For " comparative example
300% elasticity of elongation response rate ".
Comparative example and the elastomer sample further progress electron irradiation of Examples 1 to 3 are crosslinked, irradiation dose difference
For 60KGy and 120KGy.All irradiation all carry out in air.It is carried out according to the following method by the fiber sample of cross-linking radiation
High temperature bakes and banks up with earth test, with the heat-resisting quantity of testing fiber.
High temperature baking test:
Fiber sample obtained carries out high temperature according to the following method and bakes and banks up with earth test with the heat-resisting quantity of testing fiber:
1) Constant Temp. Oven (Suzhou character baking oven electric furnace Manufacturing Co., Ltd, P688-1 type) is previously heated to set
Determine temperature, the set temperature is as shown in table 3；
2) by two carbon paste band (also known as high temperature gummed tape) glue surfaces upward, be parallel to each other, be fixed on the table at a distance of 60mm, from
5 sections are taken out in the sample fiber that spinning obtains, are placed in parallel on already fixed two sections of carbon paste bands at a distance of 10mm or so, institute
It is the length of 60mm with the original length of test silk.
3) separately take one section of carbon paste band to cling the carbon paste bands of the 5 sections of sample fibers to be tested placed, make 5 sections it is to be tested
Between the carbon paste band that fiber clamp is mutually clung at 2；This process is repeated, another carbon paste band is clung.
4) it after folding the double-layer carbon adhesive tape for clinging sample fiber, is clamped with clip and fixes one；This process is repeated with separately
One clip clamps other end.
5) clip for clamping carbon paste band is fixed on the homemade prefabricated fixture that bakes (homemade prefabricated bakes
Fixture is shown in Figure of description [Fig. 1]) one；Another clip is fixed on other end.
6) the prefabricated fixture suit that bakes according to designing in this way: after being fixed to two clips to bake on fixture,
The distance between two clips are 210mm, if above-mentioned [0132] 2) the original length of testing silk be 60mm, are stretched now
To 210mm, that is, it has been stretched 3.5 times.
7) fixture that bakes produced above is put into warmed-up electric heating constant temperature drying together with fiber to be tested after stretching
Then start timing in case, bake and bank up with earth and take out after ten minutes；
8) fiber broken end is checked whether there is, all fibres sample is all broken labeled as " X ", 2 fiber sample fractures and 3
The not broken label of root fiber sample is X (1) ", 3 fiber samples are broken and the not broken label of 2 fiber samples is X (2) ",
There is no fiber sample fracture labeled as " √ ".
It should be pointed out that above-mentioned [0135] 5) described in the homemade fixture that bakes show in the Figure of description [Fig. 1],
Only to facilitate illustrating the method and used tool for carrying out heat resistant test to sample fiber, the homemade fixture that bakes of institute is not
One of innovative point of the invention.
According to [0131] 1~[0138] 8 step as above, fiber made by same group of embodiment or comparative example is same
At a temperature of carry out 3 replications, the record data in test recording table 3 be 3 times test average values.
It should be noted that testing used fiber each time is all according to above-mentioned 1~8 under each set temperature
The fiber sample that step prepares again.
Measurement result is as shown in table 3.
Table 3
The heatproof test result shown in the table 3 shows that the fiber of embodiment is by the lower irradiation dose irradiation of 60KGy
It can be resistant to 110 DEG C~160 DEG C of Temperature Treatment afterwards, than the temperature tolerance of the comparative sample by the processing of identical irradiation dose
It can be promoted obvious；And embodiment fiber can be resistant to 110 DEG C~180 after the processing of the higher irradiation dose of 120KGy
DEG C high-temperature process, and the comparative example fiber for passing through the processing of identical irradiation dose cannot still be resistant to 180 DEG C or so of high temperature completely.
It can be by suitably mentioning if necessary to further promote heat resistance according to disclosed irradiance method
Rising the appropriate heat resistance for promoting irradiated fiber of irradiation dose can will irradiate under extreme case as described in [0076]
Dosage mentions 180KGy, to guarantee that the fiber after irradiating is resistant to 200 DEG C of limiting temperature.
Detailed description of the invention
[Fig. 1] is to bake fixture schematic diagram.
Conclusion
The purpose of the present invention is to provide a kind of manufacturers of the styrene block copolymer mixture elastomer of crosslinking
Method.There is provided a kind of novel polyolefins elastomers for the direct result of this invention, it has poly- with tradition crosslinking
The high-fire resistance that olefin elastic fibers compare favourably, but present higher breaking strength and elastic recovery rate.What the present invention illustrated
Styrene block copolymer mixture (265 DEG C) in the environment of high temperature process, it is shown that lasting viscosity stability and big rule
The feasibility of mould production.At the same time, the fiber only need less electron irradiation dosage can produce enough gel contents and
High-fire resistance correspondingly, reduces production cost significantly.
Industrial applicability
The present invention provides a kind of manufacturing method of new type polyolefin class elastomer, there is the polyolefin with tradition crosslinking
The similar high-fire resistance of elastomer, but present higher breaking strength and elastic recovery rate, it at the same reduce to spoke
According to requirement, simplify production procedure simultaneously save production cost.Styrene block prepared by manufacturing method according to the invention is total
It is very extensive that copolymer mixture elastomer can be used for making fields, the purposes such as all kinds of textile fabrics or elastic cotton rope.
Claims (11)
1. a kind of manufacturing method of the styrene block copolymer mixture elastomer of crosslinking, comprises the following steps:
A) a kind of styrene block copolymer mixture is provided by being blended, it includes at least one styrene block copolymers
And at least one ethylene copolymer B A,；
B) melt spinning is carried out to obtain elastomer to the styrene block copolymer mixture；
C) cross-linking radiation is carried out to obtained elastomer,
Wherein, the styrene block copolymer A is unsaturated styrene block copolymer, and styrene/rubber ratio is 10:
Between 90 to 45: 55, (200 DEG C/5.0kg) of melt index be 1~50g/10min；The density of the ethylene copolymer B is
0.855~0.890g/cm3, (190 DEG C/2.16kg) of melt index be 0.5~10g/10min；The styrene block copolymer
The ratio of A and the ethylene copolymer B are between 85: 15~15: 85.
2. manufacturing method as described in claim 1, which is characterized in that the ethylene copolymer B also includes olefin block copolymers
Object.
3. manufacturing method as described in claim 1, which is characterized in that the styrene block copolymer mixture is optionally
Also include ethylene propylene diene rubber (EPDM).
4. manufacturing method as claimed in claim 3, which is characterized in that the styrene based on 100 weight %
Object mixture, the content of the ethylene propylene diene rubber are 0%~25%.
5. manufacturing method as described in claim 1, which is characterized in that the styrene block copolymer mixture is optionally
It also include PPA (plastic processing additives), preferably fluorine-containing auxiliary agent that content is 100ppm~3000ppm.
6. manufacturing method as described in claim 1, which is characterized in that in step c), use electron irradiation method or gamma-irradiation
Method is irradiated at room temperature, and irradiation dose is 40~180KGy.
7. manufacturing method as described in claim 1, which is characterized in that by the styrene block copolymer in the step b)
Mixture carries out melting mixing using pelletizer before spinning and is granulated again, to further make the styrene block copolymer
Each component in mixture uniformly mixes.
8. a kind of styrene block copolymer mixture of crosslinking made of manufacturing method using as described in claim 1~7
Elastomer, the elastomer can be long filament, thickness section silk, textured filament or profiled filament, and fiber number is 10 denier~1000
Denier.
9. the styrene block copolymer mixture elastomer being crosslinked as claimed in claim 8, which is characterized in that the bullet
Property fiber be stretched to 2.0~4.0 times it is former long in the case where, 120 DEG C~200 DEG C of downstream textile industry can be resistant to processing
Temperature requirement.
10. the styrene block copolymer mixture elastomer being crosslinked as claimed in claim 8 be used for other fibers or
Yarn together made of in mixed yarn or complex yarn (such as: covering yarn, wrap yarn or fasciated yarn etc., other fibres
Dimension or yarn include synthetic fibers, natural fiber and fiber class material etc.), the mixed yarn or complex yarn can be into
Production of one step for all kinds of textile fabrics or elastic cotton rope etc..
11. the styrene block copolymer mixture elastomer being crosslinked as claimed in claim 8 is used in all kinds of woven faces
The fields such as material or elastic cotton rope.
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