CN107540799A - Hydrogenated styrene-b- phenylethylene/butadiene-b- styrol copolymers and elastomer silk material and preparation method and application - Google Patents
Hydrogenated styrene-b- phenylethylene/butadiene-b- styrol copolymers and elastomer silk material and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of hydrogenated styrene b phenylethylene/butadiene b styrol copolymers and elastomer silk material and preparation method and application；The random copolymerization section that copolymer both ends are polystyrene block, centre is styrene and butadiene, and butadiene unit hydrogenation degree, more than 96%, its preparation method is：S (SB) S triblock copolymers are first prepared using anionic polymerisation, hydrogenated to obtain S (SEB) S elastomers again, the elastomer obtains elastomer silk material by single screw extrusion machine expressing technique, the elastomer silk material is highly suitable for desktop level fusion sediment pattern 3D printer, printing has good stability, the product surface printed by the elastomer silk material is smooth, elasticity is moderate, rubber sense is full, adhesive strength is big between layers, product comprehensive mechanical property is excellent, it can be applied to toy for children, the field such as consumer electronicses and automotive upholstery, with wide market prospects.
Description
Technical field
The present invention relates to a kind of hydrogenated styrene-b- phenylethylene/butadiene-b- styrol copolymers and elastomer yarn
Material and preparation method and application, more particularly to a kind of hydrogenated styrene suitable for 3D printing fusion sediment pattern
The preparation method and applications of-b- phenylethylene/butadiene-b- styrol copolymer silk materials, category 3D printing consumptive material are opened
Hair field.
Background technology
3D printing, it is according to designed 3D models, material is successively increased by 3D printing equipment to manufacture
The technology of three-dimensional objects.This successively stack shaping technology is also referred to as increasing material manufacturing.3D printing combines number
The cutting edge technology of the numerous areas such as word modeling technique, Electromechanical Control technology, information technology, material science and chemistry,
It is one kind of rapid shaping technique, is described as the core technology of " the third time industrial revolution ".
3D printing technique mainly includes selective laser sintering (SLS), Stereo Lithography (SLA), melts and sink
Product shaping (FDM) etc., wherein FDM is a kind of the most frequently used technical matters, and principle is to utilize thermoplasticity
Polymeric material in the molten state, squeezes out at shower nozzle, and solidification forms the thin layer of contour shape, further
It is layering and ultimately forms product.Polymeric material in the market for FDM forming techniques is of less types,
Import is relied primarily on, conventional has acrylonitrile-butadiene-styrene terpolymer (ABS), PLA (PLA)
With nylon (PA) etc., these are mostly rigid plastics, and hardness is higher, it is impossible to are met higher to toughness reguirements
The demand of occasion.
3D printing material is the important substance basis of 3D printing technique development, to a certain extent, material
Development decides that can 3D printing have wider application.In recent years, 3D printing technique has obtained quickly
Development, its practical application area gradually increase.But the Supply situation of 3D printing material is simultaneously pessimistic, turns into
Restrict the bottleneck of 3D printing industry development.3D printing material mainly includes engineering plastics, photosensitive resin, rubber
Glue class material, metal material and ceramic material etc., in addition, coloured plaster material, artificial bone meal, cell
The food material such as biological raw material and granulated sugar is also applied in 3D printing field.Wherein, rubber type of material
Possesses the feature of a variety of rank elastomeric materials, these material possessed hardness, elongation at break, tear-proof are strong
Degree and tensile strength, being very suitable for it, requirement is anti-skidding or the application field of soft-surface.According to report system in the industry
Meter, 3D printing consumptive material has exceeded 200 kinds at present.From the point of view of Direct Digital manufactures (DDM) angle, this
200 multiple materials are very limited amount of, and the species of especially flexible consumptive material is very few.
The exploitation of 3D printing elastomeric material is referred to as " class rubber also in starting stage, foreign countries' exploitation
Material, existing patent, the elastomeric material of document report are acrylic polymer, polyurethane elastomer
Material.
It is reported that the flexible silk material of overseas market mainly have Fenner Drives companies NinjaFlex,
The FilaFlex of Recreus companies, but either NinjaFlex either SemiFlex all containing BPA or its
His toxic gas, it is impossible to be used in make the equipment related to food tableware.In addition, the Tango of Objet companies exploitation
Series of elastic body, is suitable for Stereolithography pattern (SLA), and these materials are mainly used in consumer electronics
The fields such as product, Medical Devices and automotive trim, but the problem of generally existing intensity and relatively low elongation.China
In 3D printing flexible material development field close to blank.Styrene analog thermoplastic elastomer (SBC) is current
Maximum, the with fastest developing speed a kind of thermoplastic elastomer (TPE) of yield in the world.By its high intensity, softness, there is rubber
The characteristics of glue elasticity, small permanent deformation, styrene analog thermoplastic elastomer is in shoe industry, modifying plastics, pitch
Modification, water-repellent paint, liquid sealant, electric wire, cable, automobile component, medical device element, household electrical appliance,
Office automation and adhesive etc. have a wide range of applications.
The content of the invention
For existing fusion sediment pattern (FDM) 3D printing consumptive material it is flexible not good enough the problem of, of the invention the
One purpose is to be to provide a kind of comprehensive mechanical property excellent flexible hydrogenated styrene-b- phenylethylene/butadienes
- b- styrol copolymers.
Second object of the present invention be to provide it is a kind of it is simple to operate, cost is low, the preparation of mild condition institute
The method for stating hydrogenated styrene-b- phenylethylene/butadiene-b- styrol copolymers.
Third object of the present invention is to be to provide that a kind of melt viscosity is low, die swell ratio is low, melt-flow
Property it is good, comprehensive mechanical property is excellent, especially suitable for fusion sediment pattern 3D printer SBC elastomers
Silk material.
Fourth object of the present invention is to be to provide a kind of application of SBC elastomers silk material, the elastomer yarn
Material combination property meets requirement of the FDM patterns 3D printer to silk material, and is not in print procedure
Disconnected or gambling material phenomenon, printing have good stability.
In order to realize above-mentioned technical purpose, the invention provides a kind of hydrogenated styrene-b- phenylethylene/butadienes-b-
Styrol copolymer, there is the structure of formula 1：
Wherein,
N is 42~78；X is 85~156；Y is 292~367；Z is 125~244；M is 42~78.
Preferable scheme, obtained by styrene-b- phenylethylene/butadiene-b- polystyrene copolymers by hydrogenation modification
Arrive.
The present invention styrene-b- phenylethylene/butadiene-b- polystyrene copolymers both ends for polystyrene block,
Centre is styrene and the random copolymerization block of butadiene.The random copolymerization block of styrene and butadiene it is random
Change degree is very high, and substantially close to full disordered structure, its randomization degree is carried out with the proton nmr spectra of polymer
Characterize, the contraposition hydrogen that characterizing method is the ortho-hydrogens that chemical shift δ values are 6.56 on phenyl ring and δ values are 7.12
The ratio between absorption peak.
More preferably scheme, the polystyrene-b- styrene/butadiene random copolymers-b- polystyrene three are embedding
Butadiene unit degree of hydrogenation >=96% in section copolymer, and styrene units degree of hydrogenation≤5%.Butadiene unit
Selective hydrogenation degree it is higher, it is preferably flexible to assign polymer, makes its processing characteristics preferable.
More preferably scheme, styrene-b- phenylethylene/butadiene-b- styrol copolymer number-average molecular weights are
4.5~5.5 ten thousand, molecular weight distributing index≤1.04.
Present invention also offers the hydrogenated styrene-b- phenylethylene/butadiene-b- styrene described in a kind of prepare to be total to
The method of polymers, this method be maintain polymeric kettle in pressure be 0.1MPa~0.5MPa under conditions of, to institute
State in the anionic polymerisation system in polymeric kettle, first add styrene monomer, at 60 DEG C~70 DEG C, carry out one
Duan Juhe；Butadiene and styrene mix monomer are added, at 60~80 DEG C, carries out two sections of polymerizations；Again plus
Enter styrene monomer, at 60 DEG C~70 DEG C, carry out three stage polymerization；After the completion of polymerization, glue is transferred to hydriding reactor
In, it is 70~75 DEG C in temperature, and under conditions of hydrogenation catalyst being present, be passed through hydrogen, hydrogenate anti-
Should, produce.
After preferable scheme, divinylic monomer and styrene monomer are well mixed, anionic polymer is then added to
Two sections of polymerizations are carried out in system.
More preferably scheme, divinylic monomer and styrene monomer are well mixed by the following method：1) will be close
Negative pressure is pumped into sealed cans I, styrene monomer is squeezed into the hermetically sealed can I；2) will be pumped into hermetically sealed can II
Negative pressure, divinylic monomer is squeezed into the hermetically sealed can II；3) with nitrogen by the styrene list in hermetically sealed can I
Body is pressed into the hermetically sealed can II, makes styrene monomer and fourth two using the nitrogen pressure effect in hermetically sealed can II
Alkene monomer is sufficiently mixed uniformly, or, the divinylic monomer in hermetically sealed can II is pressed into the sealing with nitrogen
In tank I, divinylic monomer is set to be sufficiently mixed with styrene monomer using the nitrogen pressure effect in hermetically sealed can I
It is even.
Further preferred scheme, hermetically sealed can I or hermetically sealed can II nitrogen pressure maintain 0.4~0.6MPa.
The feed postition of preferable scheme, butadiene and styrene mix monomer is disposably to add, be added portionwise
Or it is continuously added to.
Preferable scheme, anionic polymerisation system include non-polar alkane class solvent, initiator and randomization reagent.
More preferably scheme, non-polar alkane class solvent are hexamethylene, and the hexamethylene dosage maintains anion to gather
The mass percent concentration of polymerized monomer is in the range of 5~15% in compound system.
More preferably scheme, initiator are n-BuLi, and the dosage of n-BuLi is according to the polymer molecule of design
Measure to determine, this is well known to this technology personnel.
More preferably scheme, randomization reagent are double tetrahydrochysene chaff propane, tetramethylethylenediamine, tetrahydrofurfuryl alcohol ethyl
At least one of ether, tetrahydrofuran；Dosage in described randomization reagent relative non-polarity alkane solvents
For 70~110mg/kg.
Preferable scheme, one-step polymerization time are 25~35min.
Preferable scheme, two sections of polymerization times are >=50min.
Preferable scheme, three stage polymerization time are 25~35min.
Preferable scheme, Hydrogen Vapor Pressure is 1.0~2MPa in hydriding process, and the hydrogenation time is
1.5~2.5h.
Preferable scheme, described hydrogenation catalyst are dicyclopentadiene titanium chloride/repefral
Combined hydrogenation catalyst.
Dicyclopentadiene titanium chloride/repefral combination catalyst that the present invention uses, with adjacent benzene
Dicarboxylic acid dimethyl ester is co-catalyst, using dicyclopentadiene titanium chloride as major catalyst.In hydriding process,
Glue is pressed into the hydrogenation kettle through nitrogen displacement, is warming up to 70~75 DEG C, first adds co-catalyst neighbour benzene two
Formic acid dimethyl ester 5~15min of passivation reaction, adds major catalyst dicyclopentadiene titanium chloride,
Hydrogenation reaction, hydrogenation reaction 1.5~2.5 hours, polymer poly butadiene are carried out under 1.0~2.0MPa Hydrogen Vapor Pressures
Section degree of hydrogenation >=98%, benzene ring hydrogenation degree≤5%.
Hydrogenated styrene-phenylethylene/butadiene-styrol copolymer (S (SEB) S) prepared by the present invention need to take off
Except metal ion, main technique is：Glue terminating reaction 15min first will be hydrogenated with a small amount of soft water, then with tertiary certain herbaceous plants with big flowers
Acid acidifying 30min, it is eventually adding after volume compares the soft water emulsification and extraction 15min that glue volume is 10% and centrifuges
Separation, stand, separate aqueous phase, β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid is added into remaining glue
The mixture of positive octadecanol ester (1076) or itself and three [2.4- di-tert-butyl-phenyls] phosphite esters (168) is made
For antioxidant.Condensed through steam, be placed in air dry oven drying 8h and produce.
The invention provides a kind of SBC elastomers silk material, and the SBC elastomers silk material is by described hydrogenation of benzene second
Alkene-b- phenylethylene/butadiene-b- styrol copolymers are obtained by double screw extruder expressing technique.
Preferable scheme, the technological parameter of single screw extrusion machine is in expressing technique：The mouth mold of single screw extrusion machine
For diameter between 1.5~1.7mm, screw speed is 120~150 rpms；Cavity is by feeding end to discharging
End includes five regions successively, and the temperature and pressure condition in each region is followed successively by, an area：175~185 DEG C, 14~16
bar；2nd area：185~195 DEG C；12~14bar；3rd area：195~205 DEG C；11~13bar；4th area：195~205 DEG C；
11~13bar；5th area：195~205 DEG C；11~13bar.Further preferably, each region of double screw extruder
Temperature and pressure condition be followed successively by, an area：180 DEG C, 15bar；2nd area：190℃；13bar；3rd area：
200℃；12bar；4th area：200℃；12bar；5th area：200℃；12bar.
Present invention also offers the application of described SBC elastomer silk materials, the application is by SBC elastomer yarns
Material prepares device as 3D printing materials application in 3D printing.
Preferable scheme, 3D printing use desktop level fusion sediment pattern 3D printer.
Compared with the prior art, the beneficial effect that technical scheme is brought：
1st, hydrogenated styrene-b- phenylethylene/butadienes-b- styrol copolymers provided by the invention have special
Molecular structure, its both ends is styrene block, and centre is styrene butadiene block, and butadiene block
1 containing higher proportion, 2 structures, and butadiene unit obtains highly hydrogenated, this special molecular structure
The good comprehensive mechanical property of polymer is imparted, particularly it is flexible preferably, and processing characteristics is preferable, is applied to
FDM pattern 3D printing consumptive materials.
2nd, SBC prepared by flexible hydrogenated styrene-b- phenylethylene/butadiene-b- styrol copolymers of the invention
Elastomer silk material has three outstanding advantages：One of advantage is that S (SEB) S interludes are styrene and fourth two
The special construction of alkene random copolymerization section assigns elastomer relatively low melt viscosity, silk material die swelling prepared therefrom
Rate is low, die swelling coefficient≤1.05.Second, silk material melt fluidity is splendid, at 200 DEG C, 5Kg loads
Under the conditions of melt index be：15~20g/10min.Third, silk material Shao A hardness is at 78~82 degree, bullet
Property is moderate, can meet some application scenarios higher to flexibility requirements.Therefore, S (SEB) S elasticity developed
Body silk material can meet requirement of the FDM patterns 3D printer to silk material completely.
3rd, elastomer yarn timber-used provided by the invention is printing in the 3D printing of desktop level FDM printing devices
During be not in that the printing of most of commercialization flexible wires is interrupted or the phenomenon of gambling material, printing stability are good
It is good.In addition, the elastomer silk material good thermal stability, whole printing process does not smell a strange smell, compared to ABS
With PLA silk materials more safety and environmental protection.Printed article surface is bright and clean, good physical properties, and rubber sense is full,
It is highly suitable for the fields such as toy for children, consumer electronicses and automotive upholstery, there are wide market prospects.
The exploitation of the elastomer silk material, the species of FDM pattern 3D printing consumptive materials is not only enriched, will also promote China
Phenylethylene (SBC) thermoplastic elastomer (TPE) develops to higher extreme direction.
4th, hydrogenated styrene-b- phenylethylene/butadiene-b- styrol copolymers preparation method of the invention it is simple,
Cost is low, process conditions are gentle, meets industrial production application requirement.
Brief description of the drawings
【Fig. 1】S (SB) the S bases glue nucleus magnetic hydrogen spectrum figure prepared for embodiment 1.
Embodiment
Following examples are intended to further illustrate present invention, rather than the protection of limitation the claims in the present invention
Scope.
Embodiment 1
In the 5 liters of polymeric kettles replaced with high pure nitrogen add 3000 milliliters of pure hexamethylenes (water number ＜ 20ppm),
The double tetrahydrochysene chaff propane of 2.0mL (are configured to 0.5mol/L cyclohexane solution, dosage is molten equivalent to 80mg/kg
Agent), stirring is opened, is warming up to 60 DEG C, then be separately added into 49mL styrene monomers and 6.0mmol normal-butyls
Lithium, polymerisation 30 minutes, the mix monomer of 242mL butadiene and 65mL styrene is then added, is mixed
Closing monomer takes the mode disposably added to add in polymeric kettle, and controlling reaction temperature is below 80 DEG C, reaction
49mL styrene monomers are added after 50 minutes, are reacted 30 minutes under 60~65 DEG C of temperature conditionss.Polymerization
Glue is introduced into 10L hydrogenation kettles after the completion of reaction, 70 DEG C is warming up to, adds 8mmol n-BuLis, use hydrogen
Gas terminating reaction 10 minutes.Add co-catalyst dibutyl phthalate 4mL (0.2mol/L) and sponsor
Agent dicyclopentadiene titanium chloride 0.2g, hydrogenation pressure control are two small in 1.0~1.5Mpa, hydrogenation reaction
When, co-catalyst is added 2~3 times in centre, is 2mL per secondary amounts.After hydrogenation reaction, hydrogenation glue turns
Washing kettle is moved to, is warming up to 60~65 DEG C, glue terminating reaction 15min will be hydrogenated with 10mL soft water, then use
The tertiary certain herbaceous plants with big flowers of 2mL sour (being dissolved in 200mL hexamethylenes) acidifying 30min, last 300mL soft water emulsification and extraction
Centrifuge, stand after 15min, separate aqueous phase, remaining glue is condensed through steam, is dried to obtain hydrogenation of benzene
Ethylene-stryene/BS.
In high-speed mixer by hydrogenated styrene-phenylethylene/butadiene-styrol copolymer and β-
The positive octadecanol ester (1076) of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid or itself and three [2.4- di-t-butyls
Phenyl] the mixing antioxygen of phosphite ester (168) is well mixed for 99.7 ﹕ 0.3 ratio in mass ratio.Will
Compound melting extrusion on small-sized single-screw machine, expressing technique are：Screw speed is 270~350 revolutions per minute
Clock；Each area's temperature of screw in injection molding machine is respectively：One area：180℃；2nd area：190℃；3rd area：200℃；
4th area：200℃；5th area：200℃；Each area's relevant pressure is：One area：15bar；2nd area：13bar；Three
Area：12bar；4th area：12bar；5th area：12bar.
Select printer model, by prepared elastomer silk material model makerbot replicator 2 desktop
Printed on printer, software print temperature is arranged to 230 DEG C.
Corresponding performance test is carried out respectively.Each test result is as follows：
Gpc analysis result：Basic glue number-average molecular weight is 5.1 ten thousand, molecular weight distribution 1.03, and testing standard is pressed
ISO16014-1:2003 perform；
HNMR analysis results：S (SB) S bases glue PB sections 1,2- structural contents are 35.4%, styrene
Be 99.5 with the degree of randomness of the random copolymerization section of butadiene, its nucleus magnetic hydrogen spectrum figure as shown in Figure 1, testing standard
Performed by JJF 1448-2014；
Iodine number analysis result：Degree of hydrogenation is 98.2%；
S (SEB) S elastomer performance test results are shown in Table 1, and testing standard is performed by GB/T3354-1999：
1 embodiment of table 1 gained S (SEB) S elastomer performance test results
Note：Die swelling coefficient=silk material diameter ÷ port mould diameters
Printing situation describes：Do not block silk, printing has good stability.Product surface is smooth, elasticity preferably, layer with
Adhesive strength is high between layer, and comprehensive mechanical property is excellent.
Embodiment 2
For preparation process with embodiment 1, addition (6.6mmol) synthesis for changing initiator n-BuLi is basic
Xanthan molecule amount is 4.6 ten thousand hydrogenated styrene-phenylethylene/butadiene-styrol copolymer.Experimental result is shown in Table
2：
Gained S (SEB) the S elastomer structures of 2 embodiment of table 2 and the performance test results
Printing situation describes：Do not block silk, printing has good stability；Product apparent mass is excellent.
Embodiment 3
Preparation process changes one, three section of styrene addition (39mL) and three sections of benzene respectively with embodiment 1
It is 12%, random section styrene-content that ethene addition (85mL), which synthesizes one, three section of styrene block content,
For 26% hydrogenated styrene-phenylethylene/butadiene-styrol copolymer.Experimental result is shown in Table 3：
Gained S (SEB) the S elastomer structures of 3 embodiment of table 3 and the performance test results
Printing situation describes：Do not block silk, printing has good stability；Product apparent mass is excellent.
Embodiment 4
Randomization reagent is changed into tetrahydrofurfuryl alcohol ethylether, its addition is with double four by preparation process with embodiment 1
Hydrogen health propane.Experimental result is shown in Table 4：
4 embodiment of table 4 gained S (SEB) S elastomer performance test results
Upper table illustrates that the more double tetrahydrochysene chaff propane of randomization effect of tetrahydrofurfuryl alcohol ethylether are slightly worse.
Printing situation describes：Do not block silk, printing has good stability；Product apparent mass is excellent.
Embodiment 5
Preparation process with embodiment 1, change double tetrahydrochysene chaff propane additions (2.6mL, dosage equivalent to
100mg/kg solvents) synthesis 1,2- structural contents and the higher hydrogenated styrene-styrene/fourth of randomization degree
Diene-styrene copolymer, experimental result are shown in Table 5：
Gained S (SEB) the S elastomer structures of 5 embodiment of table 5 and the performance test results
Printing situation describes：Do not block silk, printing has good stability；Product apparent mass is excellent.
Embodiment 6
The feed postition of mix monomer in embodiment 1 is added in ten times by being once changed to, synthesizes randomization journey
Du Genggao hydrogenated styrene-phenylethylene/butadiene-styrol copolymer, experimental result are shown in Table 6：
Gained S (SEB) the S elastomer structures of 6 embodiment of table 6 and the performance test results
Thus it is not very obvious to randomization degree improvement to illustrate that mix monomer adds in ten times.
Printing situation describes：Do not block silk, printing has good stability；Product apparent mass is excellent.
Embodiment 7
The feed postition of mix monomer in embodiment 1 is added in ten times by being once changed to, synthesizes randomization journey
Du Genggao hydrogenated styrene-phenylethylene/butadiene-styrol copolymer, experimental result are shown in Table 7：
Gained S (SEB) the S elastomer structures of 7 embodiment of table 7 and the performance test results
Mix monomer can obtain the hydrogenated styrene-benzene being basically completed close to randomization by the way of being continuously added to
Ethene/BS.
Printing situation describes：Do not block silk, printing has good stability；Product apparent mass is excellent.
Claims (20)
- A kind of 1. hydrogenated styrene-b- phenylethylene/butadienes-b- styrol copolymers, it is characterised in that：With formula 1 Structure：Wherein,N is 42~78；X is 85~156；Y is 292~367；Z is 125~244；M is 42~78.
- 2. hydrogenated styrene-b- phenylethylene/butadienes-b- styrol copolymers according to claim 1, it is special Sign is：Obtained by styrene-b- phenylethylene/butadiene-b- styrol copolymers by hydrogenation modification.
- 3. hydrogenated styrene-b- phenylethylene/butadienes-b- styrol copolymers according to claim 2, it is special Sign is：Butadiene unit degree of hydrogenation in the styrene-b- phenylethylene/butadienes-b- styrol copolymers >=96%, and styrene units degree of hydrogenation≤5%.
- 4. hydrogenated styrene-b- phenylethylene/butadienes-b- styrol copolymers according to claim 2, it is special Sign is：Described styrene-b- phenylethylene/butadiene-b- styrol copolymers number-average molecular weight is 4.5~5.5 Ten thousand, molecular weight distributing index≤1.04.
- 5. hydrogenated styrene-b- phenylethylene/butadienes-the b- prepared described in any one of Claims 1 to 4 is styrene copolymerized The method of thing, it is characterised in that：Under conditions of pressure is 0.1MPa~0.5MPa in maintenance polymeric kettle, to In anionic polymerisation system in the polymeric kettle, styrene monomer is first added, at 60 DEG C~70 DEG C, is carried out One-step polymerization；Butadiene and styrene mix monomer are added, at 60~80 DEG C, carries out two sections of polymerizations；Again Styrene monomer is added, at 60 DEG C~70 DEG C, carries out three stage polymerization；After the completion of polymerization, glue is transferred to hydrogenation It it is 70~75 DEG C in temperature, and under conditions of hydrogenation catalyst being present, be passed through hydrogen, hydrogenated in kettle Reaction, is produced.
- 6. hydrogenated styrene-b- phenylethylene/butadiene-b- the styrol copolymers according to claim 5 of preparing Method, it is characterised in that：After divinylic monomer and styrene monomer are well mixed, anionic polymerisation is then added to Two sections of polymerizations are carried out in system.
- 7. hydrogenated styrene-b- phenylethylene/butadiene-b- the styrol copolymers according to claim 6 of preparing Method, it is characterised in that：Divinylic monomer and styrene monomer are well mixed by the following method：1) will be close Negative pressure is pumped into sealed cans I, styrene monomer is squeezed into the hermetically sealed can I；2) will be pumped into hermetically sealed can II Negative pressure, divinylic monomer is squeezed into the hermetically sealed can II；3) with nitrogen by the styrene list in hermetically sealed can I Body is pressed into the hermetically sealed can II, makes styrene monomer and fourth two using the nitrogen pressure effect in hermetically sealed can II Alkene monomer is sufficiently mixed uniformly；Or the divinylic monomer in hermetically sealed can II is pressed into the sealing with nitrogen In tank I, divinylic monomer is set to be sufficiently mixed with styrene monomer using the nitrogen pressure effect in hermetically sealed can I It is even.
- 8. hydrogenated styrene-b- phenylethylene/butadiene-b- the styrol copolymers according to claim 7 of preparing Method, it is characterised in that：Described hermetically sealed can I or hermetically sealed can II nitrogen pressure maintain 0.4~0.6MPa.
- 9. hydrogenated styrene-b- phenylethylene/butadiene-b- the styrol copolymers according to claim 5 of preparing Method, it is characterised in that：The feed postition of butadiene and styrene mix monomer is disposable addition, added in batches Enter or be continuously added to.
- 10. hydrogenated styrene-b- phenylethylene/butadiene-b- the styrol copolymers according to claim 1 of preparing Method, it is characterised in that：Described anionic polymerisation system includes non-polar alkane class solvent, initiator and nothing Ruleization reagent.
- 11. hydrogenated styrene-b- phenylethylene/butadiene-b- the styrol copolymers according to claim 10 of preparing Method, it is characterised in that：Described non-polar alkane class solvent is hexamethylene, and the hexamethylene dosage remains cloudy The mass percent concentration of polymerized monomer is in the range of 5~15% in ionomer systems.
- 12. according to claim 10 prepare hydrogenated styrene-b- phenylethylene/butadiene-b- styrol copolymers Method, it is characterised in that：Described initiator is n-BuLi.
- 13. according to claim 10 prepare hydrogenated styrene-b- phenylethylene/butadiene-b- styrol copolymers Method, it is characterised in that：Described randomization reagent is double tetrahydrochysene chaff propane, tetramethylethylenediamine, tetrahydrochysene At least one of furfuryl alcohol ethylether, tetrahydrofuran；Described randomization reagent relative non-polarity alkane solvents In dosage be 70~110mg/kg.
- 14. hydrogenated styrene-b- phenylethylene/butadiene-b- the styrol copolymers according to claim 5 of preparing Method, it is characterised in that：The one-step polymerization time is 25~35min, and two sections of polymerization times are >=50min, three sections Polymerization time is 25~35min.
- 15. hydrogenated styrene-b- phenylethylene/butadiene-b- the styrol copolymers according to claim 5 of preparing Method, it is characterised in that：Hydrogen Vapor Pressure is 1.0~2MPa in described hydriding process, during hydrogenation Between be 1.5~2.5h.
- 16. hydrogenated styrene-b- phenylethylene/butadiene-b- the styrol copolymers according to claim 5 of preparing Method, it is characterised in that：Described hydrogenation catalyst is dicyclopentadiene titanium chloride/phthalic acid diformazan Ester combined hydrogenation catalyst.
- A kind of 17. SBC elastomers silk material, it is characterised in that：As the hydrogenation of benzene described in any one of Claims 1 to 4 Ethene-b- phenylethylene/butadiene-b- styrol copolymers are obtained by double screw extruder expressing technique.
- 18. SBC elastomers silk material according to claim 17, it is characterised in that：In described expressing technique The technological parameter of single screw extrusion machine is：The port mould diameter of single screw extrusion machine is between 1.5~1.7mm, spiral shell Bar rotating speed is 120~150 rpms；Cavity includes five regions, each area successively by feeding end to discharge end The temperature and pressure condition in domain is followed successively by, an area：175~185 DEG C, 14~16bar；2nd area：185~195 DEG C； 12~14bar；3rd area：195~205 DEG C；11~13bar；4th area：195~205 DEG C；11~13bar；5th area： 195~205 DEG C；11~13bar.
- 19. the application of the SBC elastomer silk materials described in claim 18, it is characterised in that：As 3D printing material Material prepares device applied to 3D printing.
- 20. the application of SBC elastomers silk material according to claim 19, it is characterised in that：Described 3D Printing uses desktop level fusion sediment pattern 3D printer.
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