CN107674166A - Hydrogenation type styrene analog thermoplastic elastomer and its synthetic method and application - Google Patents
Hydrogenation type styrene analog thermoplastic elastomer and its synthetic method and application Download PDFInfo
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Abstract
The present invention relates to a kind of hydrogenation type styrene analog thermoplastic elastomer and its production and use, the material is hydrogenated with to obtain by styrene-isoprene-styrene triblock copolymer.The present invention hydrogenation type styrene analog thermoplastic elastomer isoprene soft segment in combine styrene, can improve product melt index and product viscosity to the sensitiveness of temperature, be advantageous to be blended to use with polystyrene.The elastomer is suitable for the fields such as the anti-piping compound of binding agent, sealant, coating, class rubber compound (can replace vulcanization rubber), plastic modifier, compatilizer, thermosetting resin modifying agent and unsaturated polyester (UP) asphalt modifier.
Description
Technical field
The invention belongs to thermoplastic elastic material, more particularly to hydrogenation type styrene analog thermoplastic elastomer and its conjunction
Into methods and applications.
Background technology
Thermoplastic elastomer (TPE) (Thermoplastic elastomers, TPEs) is to pass through Physical Network between a kind of macromolecule
The material that shape is cross-linked to form, be characterized under high temperature can as plastics processing plasticizing, and finished product can be made at normal temperatures
Used for rubber elastomer.Styrene analog thermoplastic elastomer is found earliest and by industrialized thermoplastic elastomer (TPE),
It is one of current most widely used elastomer product, the main block copolymer for including synthesizing with styrene and isoprene
(SIS, abbreviation SIS), the block copolymer synthesized with styrene and butadiene
(SBS, abbreviation SBS) and their hydrogenated products SEPS, SEBS etc..20th century
The eighties, Kuraray companies carry out hydrotreating to SIS first, develop SIS series hydrogenated products (containing SEPS and SEP etc. six
Kind), the trade mark isSIS is greatly improved its heat-resisting, antioxygen or ozone, UV resistant irradiation after selection is hydrogenated with
Deng the performance of oxidation or cross-linking reaction degraded, while the temperature in use of product is improved, improve the chemistry such as weather resistance, acid and alkali-resistance
Performance and wearability and pliability.The thermoplasticity of the SIS existing non-hydrogenated product of hydride material, there is the height of rubber under normal temperature again
Elasticity, the mobility of resin is shown at high temperature, can direct machine-shaping.The above-mentioned performance of the hydride material makes it
It is significantly larger than common line style and star-like SIS in actual applications.SIS hydrogenated products SEPS commodity mainly have at present
Shell companies Kraton G series of products and the SEPTON series of products of Japanese Kuraray companies.Hydrogenation type phenylethylene thermoplastic
Property elastomeric material be mainly used in binding agent, sealant, coating, class rubber compound (can replace vulcanization rubber), plastics and change
Property agent, compatilizer, thermosetting resin modifying agent and unsaturated polyester (UP) asphalt modifier the field such as anti-piping compound in.
In styrene analog thermoplastic elastomer series, SEBS and SEPS are the hydrogenation that two kinds functional, cost is cheap
Type styrene analog thermoplastic elastomer, the both ends of its structure are usually that polystyrene, interlude that molecular weight is 1-2 ten thousand are usually
The copolymer of ethylene/butylene -1 that molecular weight is 3-10 ten thousand or the ethylene/propene copolymer that molecular weight is 3-10 ten thousand.Due to polyphenyl second
The solubility parameter difference of alkene and olefin copolymer is bigger, therefore the generally melt index of hydrogenation type styrene analog thermoplastic elastomer
It is smaller, processing difficulties.In order to adapt to different purposes, the design to polymer molecular structure is necessary.For SEBS systems
Row, Shell chemical companies from macromolecular design angle, with anionic polymerization in SEBS elastomeric networks with chemical bond
Two polyisoprene (PI) chains are connected, and this new product SEBIS is named as Kraton GRP-6919.In SEBIS,
SEBS accounts for molecular weight 64%, and PI accounts for 36%.For SEPS series, the report on its modification is also less at present.
The content of the invention
An object of the present invention be to provide a kind of isoprene styrene atactic polymer, styrene-isoprene-
(SIS hydrogenation products are a kind of hydrogenation type styrene analog thermoplastic for styrene block copolymer (SIS) and their hydrogenation products
Elastomer).
The second object of the present invention is to provide above-mentioned hydrogenation type process for preparing thermoplastic phenylethylene elastomer.
The third object of the present invention is to provide the application of above-mentioned hydrogenation type styrene analog thermoplastic elastomer.
To achieve these goals, the present invention provides a kind of isoprene styrene atactic polymer, is designated as P1, and it is wrapped
Include the repeat unit shown in formula (I), formula (II) and formula (III)：
Wherein, the repeat unit shown in formula (I) accounts for the 5-75mol% of repeat unit summation shown in formula (I) and formula (II)；
In formula (III), R is aryl, preferably phenyl.
According to the present invention, the repeat unit shown in formula (I) accounts for the 6- of repeat unit summation shown in formula (I) and formula (II)
70mol%, further preferred 6.5-65mol%.
According to the present invention, it is total that the repeat unit shown in formula (III) accounts for formula (I), formula (II) and repeat unit shown in formula (III)
The 1-25mol% of sum, preferably 2-20mol%.
According to the present invention, the isoprene styrene atactic polymer uses the number-average molecular weight that GPC is determined as 2-25
Ten thousand.
The present invention further provides a kind of polymer, P2 is designated as, is adding for above-mentioned isoprene styrene atactic polymer
Hydrogen product.
According to the present invention, in the hydrogenation products, the degree of hydrogenation of double bond is more than 98mol% in non-phenyl ring, double bond in phenyl ring
Degree of hydrogenation be less than 2mol%.
According to the present invention, in the hydrogenation products, the degree of hydrogenation of double bond is 50-98mol% (preferably 50- in non-phenyl ring
90mol%), the degree of hydrogenation of double bond is less than 2mol% in phenyl ring.
The present invention furthermore provides a kind of SIS, is designated as BP1, and it is tied
Structure formula is such as shown in (IV)：
In formula (IV), the both ends of the triblock copolymer are polystyrene hard section, and centre is polyisoprene soft segment；It is described
Polyisoprene soft segment includes the repeat unit shown in formula (I), formula (II) and formula (III)：
Wherein, the repeat unit shown in formula (I) accounts for the 5-75mol% of repeat unit summation shown in formula (I) and formula (II)；
In formula (III), R is aryl, preferably phenyl.
According to the present invention, the repeat unit shown in formula (I) accounts for the 6- of repeat unit summation shown in formula (I) and formula (II)
70mol%, further preferred 6.5-65mol%.
According to the present invention, it is total that the repeat unit shown in formula (III) accounts for formula (I), formula (II) and repeat unit shown in formula (III)
The 1-25mol% of sum, preferably 2-20mol%.
According to the present invention, wherein polystyrene hard section accounts for the 15-50wt% of three block quality.
The present invention also provides a kind of hydrogenation type styrene analog thermoplastic elastomer, is designated as BP2, and it is above-mentioned styrene-different
Isoprene-styrene triblock copolymer BP1 hydrogenation products.
According to the present invention, in above-mentioned thermoplastic elastomer (TPE), the degree of hydrogenation of the double bond in non-phenyl ring is more than 98mol% (preferably
98.1-99.9mol%), the degree of hydrogenation of double bond is less than 2mol% in phenyl ring.
According to the present invention, in above-mentioned thermoplastic elastomer (TPE), the degree of hydrogenation of the double bond in non-phenyl ring for 50-98mol% (preferably
50-90mol%), the degree of hydrogenation of double bond is less than 2mol% in phenyl ring.
According to the present invention, described thermoplastic elastomer (TPE) uses the number-average molecular weight that GPC is determined as 4-30 ten thousand, preferably 5-25
Ten thousand；Molecular weight distribution is 1.05 or so.Melt index of the described thermoplastic elastomer (TPE) under 230 DEG C, 2.16kg test conditions
For 0.05-20g/10min.
The present invention also provides a kind of hydrogenation type process for preparing thermoplastic phenylethylene elastomer, and it comprises the following steps：
(1) anionic polymerization is used, the benzene using styrene and isoprene as Material synthesis with structural formula shown in formula (IV)
Ethene-isoprene styrene triblock copolymer；(2) triblock copolymer Hydrogenation under catalyst action obtains institute
The hydrogenation type styrene analog thermoplastic elastomer stated；
In formula (IV), the both ends of the triblock copolymer are polystyrene hard section, and centre is polyisoprene soft segment；It is described
Polyisoprene soft segment includes the repeat unit shown in formula (I), formula (II) and formula (III)：
Wherein, the repeat unit shown in formula (I) accounts for the 5-75mol% of repeat unit summation shown in formula (I) and formula (II)；
In formula (III), R is aryl, preferably phenyl.
According to the present invention, the repeat unit shown in formula (I) accounts for the 6- of repeat unit summation shown in formula (I) and formula (II)
70mol%, further preferred 6.5-65mol%.
According to the present invention, it is total that the repeat unit shown in formula (III) accounts for formula (I), formula (II) and repeat unit shown in formula (III)
The 1-25mol% of sum, preferably 2-20mol%.
According to the present invention, wherein polystyrene hard section accounts for the 15-50wt% of three block quality.
According to the present invention, in the polymerization process of polyisoprene soft segment, micmstructure of polymer conditioning agent is added to control
The content of repeat unit shown in formula (I) processed.
According to the present invention, above-mentioned steps (1) specifically include：
Using styrene and isoprene as raw material, butyl lithium be initiator in non-polar organic solvent, synthesize benzene second
Alkene-isoprene styrene triblock copolymer；Weight shown in formula (I) and formula (II) is accounted for for the repeat unit shown in control formula (I)
The 5-75mol% of multiple unit summation, in polyisoprene soft segment polymerization process, introduce micmstructure of polymer conditioning agent.
According to the present invention, the micmstructure of polymer conditioning agent is selected from tetrahydrofuran, tetrahydrofurfuryl alcohol ethylether or N, N-
Dimethyl tetrahydro chaff amine.
According to the present invention, the dosage of the micmstructure of polymer conditioning agent is：0<r<100.Preferably, 0.01<r<10,
It is highly preferred that 0.05<r<2.The r represents the mol ratio of micmstructure of polymer conditioning agent and initiator.
According to the present invention, described preparation method preferably includes：(1) styrene polymerization, polymerization are triggered with initiator first
Time is 30-60min, 40-70 DEG C of polymerization temperature；Then isoprene and styrene mixture are added, in the microcosmic knot of polymer
It polymerize in the presence of structure conditioning agent, reaction time 60-90min, reaction temperature is 40-80 DEG C；Finally add remaining benzene second
Alkene carries out polymerisation, polymerization time 30-60min, 40-70 DEG C of polymerization temperature, obtains triblock polymer；(2) in gained
To triblock polymer in add non-polar organic solvent wiring solution-forming, addition be selected from organic nickel/aluminum alkyl catalyst or cyclopentadienyl
The hydrogenation catalyst of titanium catalyst, reaction 1-5 is small under conditions of temperature is 60-90 DEG C, Hydrogen Vapor Pressure keeps 1.5-2.5MPa
When, described hydrogenation type styrene analog thermoplastic elastomer is obtained after hydrogenation.
According to the present invention, in step (2), hydrogenation catalyst is selected from organic nickel/aluminum alkyl catalyst or metallocene-titanium catalyst.
According to the present invention, when using organic nickel/alkyl aluminum as hydrogenation catalyst, in the thermoplastic elastomer (TPE) of gained, non-benzene
The degree of hydrogenation of double bond in ring is more than 98mol% (preferably 98.1-99.9mol%), and the degree of hydrogenation of double bond is less than in phenyl ring
2mol%.
According to the present invention, when using metallocene-titanium catalyst as hydrogenation catalyst, in the thermoplastic elastomer (TPE) of gained, in non-phenyl ring
The degree of hydrogenation of double bond be 50-98mol% (preferably 50-90mol%), the degree of hydrogenation of double bond is less than 2mol% in phenyl ring.
According to the present invention, described butyl lithium is selected from n-BuLi, s-butyl lithium, tert-butyl lithium.
According to the present invention, described non-polar organic solvent is selected from cycloalkane.Preferably, the cycloalkane be hexamethylene or
Pentamethylene.It is further preferred that the hexamethylene is the hexamethylene containing less than 30% hexane.
According to the present invention, in the polymerization process of polystyrene hard section, the monomer concentration of styrene is (excellent for 0.1-20wt%
Select 0.5-2.5wt%)；In the polymerization process of polyisoprene soft segment, the monomer of the mixture of isoprene and styrene is dense
Spend for 5-20wt% (preferably 6-10wt%), wherein, content of the styrene in the mixture is 1-25wt%, preferably 2-
20wt%.
According to the present invention, described organic nickel is selected from nickel naphthenate, alkyl nickel etc..
The hydrogenation type styrene analog thermoplastic elastomer of the present invention can be used for binding agent, sealant, coating, class rubber chemical combination
Thing (vulcanization rubber can be replaced), plastic modifier, compatilizer, thermosetting resin modifying agent and unsaturated polyester (UP) asphalt modifier
The field such as anti-piping compound in.
The beneficial effects of the invention are as follows：
Hydrogenation type styrene analog thermoplastic elastomer provided by the invention, have and list is repeated shown in the formula (I) of certain content
Structure after the hydrogenation of member, such elastomer have good compatibility with polypropylene.Further, benzene second is introduced in soft segment
The repeat unit of alkene, it is possible to increase sensitiveness of the product viscosity to temperature is improved while the melt index of the elastomer, favorably
It is blended to use in the elastomer with polystyrene.
Present invention also offers a kind of side for simply and efficiently preparing above-mentioned hydrogenation type styrene analog thermoplastic elastomer
Method, and prepare by the selections of different catalysts the product of different degrees of hydrogenation, suitable for different application fields, greatly
Extend the use range of the thermoplastic elastomer (TPE) of the present invention.
Embodiment
The present invention core purpose be to provide it is a kind of can both improve product melt index, product viscosity pair can be improved again
The hydrogenation type styrene analog thermoplastic elastomer of temperature sensitivity.The present invention is using styrene, isoprene as Material synthesis benzene second
Alkene-isoprene styrene triblock copolymer, hydrogenation section is realized based on the design to polyisoprene soft segment structure and control
All or part of hydrogenation of polyisoprene so that repeat unit shown in formula (I) in the triblock copolymer prepared by the present invention
Content significantly improve, the product after hydrogenation and polypropylene have good compatibility.Further, the hydrogenation prepared by the present invention
Type styrene analog thermoplastic elastomer, repeating styrene units are combined in its soft segment, can improve melt index and the production of product
The sensitiveness of product viscosity temperature, be advantageous to the elastomer and be blended to use with polystyrene.Specifically, the present invention closes
Into SIS in, by controlling polystyrene hard section and polyisoprene soft segment
Molecular weight, the weight/mass percentage composition of polystyrene hard section, the molar content of repeat unit shown in formula (I), formula (III) institute
Show molar content, degree of hydrogenation of repeat unit etc. to change and adjust the performance of this kind of polymer, prepare a series of productions
Thing is to meet the needs of different application field.
For the object, technical solutions and advantages of the present invention are more clearly understood, below in conjunction with specific embodiment, to this hair
Bright further description.But those skilled in the art know, the invention is not limited in following examples.
Embodiment 1
In the reactor, adding styrene, solvent pentamethylene and initiator n-BuLi, the concentration of styrene is
0.9wt%, the concentration of initiator is 1.5M, polymerize 40min at 50 DEG C；Then tetrahydrofuran, isoprene and benzene second are added
Alkene, the concentration of tetrahydrofuran are 0.48M, and for 8.2wt%, (wherein, the concentration of styrene is the concentration of isoprene and styrene
0.26wt%), it polymerize 80min at 60 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%, is polymerize at 50 DEG C
40min, obtain SIS；
Nickel naphthenate/aluminum alkyl catalyst 120ml is added in above-mentioned system, Hydrogen Vapor Pressure keeps 1.9MPa, at 65 DEG C
Lower hydrogenation reaction 2h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 6.4 ten thousand, molecular weight distribution 1.02；230℃、
Under 2.16kg test conditions, melt index 4.35g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II) weight
The 6.98mol% of multiple unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 99.1mol% in soft segment after hydrogenation.
Embodiment 2
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 1.5M, polymerize 40min at 50 DEG C；Then tetrahydrofuran, isoprene and styrene, tetrahydrofuran are added
Concentration be 2.4M, the concentration of isoprene and styrene is 8.2wt% (wherein, the concentration of styrene is 0.26wt%),
Polymerase 17 0min at 60 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%, polymerize 40min at 50 DEG C, obtains benzene
Ethene-isoprene styrene triblock copolymer；
Nickel naphthenate/aluminum alkyl catalyst 120ml is added in above-mentioned system, Hydrogen Vapor Pressure keeps 1.9MPa, at 65 DEG C
Lower hydrogenation reaction 2h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 6.3 ten thousand, molecular weight distribution 1.01；230℃、
Under 2.16kg test conditions, melt index 4.54g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II) weight
The 11.33mol% of multiple unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 99.3mol% in soft segment after hydrogenation.
Embodiment 3
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 1.2M, polymerize 40min at 50 DEG C；Then tetrahydrofuran, isoprene and styrene, tetrahydrofuran are added
Concentration be 1.8M, the concentration of isoprene and styrene is 8.2wt% (wherein, the concentration of styrene is 0.26wt%),
Polymerase 17 0min at 60 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%, polymerize 40min at 50 DEG C, obtains benzene
Ethene-isoprene styrene triblock copolymer；
Nickel naphthenate/aluminum alkyl catalyst 120ml is added in above-mentioned system, Hydrogen Vapor Pressure keeps 1.9MPa, at 65 DEG C
Lower hydrogenation reaction 2h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, gained hydrogenated polymers molecular weight is 8.1 ten thousand, molecular weight distribution 1.03；230 DEG C, 2.16kg test-strips
Under part, melt index 0.53g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II) repeat unit summation
10.56mol%；The degree of hydrogenation of non-phenyl ring repeat unit is 98.9mol% in soft segment after hydrogenation.
Embodiment 4
In reactor, styrene, solvent pentamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 0.9M, polymerize 40min at 50 DEG C；Then N, N- dimethyl tetrahydro chaffs amine, isoprene and benzene second are added
Alkene, N, the concentration of N- dimethyl tetrahydro chaff amine are 0.36M, and the concentration of isoprene and styrene is 8.2wt% (wherein, benzene second
The concentration of alkene is 0.26wt%), the polymerase 17 0min at 50 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%,
It polymerize 40min at 70 DEG C, obtains SIS；
Nickel naphthenate/aluminum alkyl catalyst 200ml is added in above-mentioned system, Hydrogen Vapor Pressure keeps 1.8MPa, at 75 DEG C
Lower hydrogenation reaction 2.5h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 11.2 ten thousand, molecular weight distribution 1.04；230
DEG C, under 2.16kg test conditions, melt index is less than 0.1g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula
(II) 31.02mol% of repeat unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 98.3mol% in soft segment after hydrogenation.
Embodiment 5
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 0.9M, polymerize 40min at 50 DEG C；Then N, N- dimethyl tetrahydro chaffs amine, isoprene and benzene second are added
Alkene, N, the concentration of N- dimethyl tetrahydro chaff amine are 0.54M, and the concentration of isoprene and styrene is 8.2wt% (wherein, benzene second
The concentration of alkene is 0.26wt%), the polymerase 17 0min at 50 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%,
It polymerize 40min at 70 DEG C, obtains SIS；
Nickel naphthenate/aluminum alkyl catalyst 220ml is added in above-mentioned system, Hydrogen Vapor Pressure keeps 1.8MPa, at 75 DEG C
Lower hydrogenation reaction 2h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 10.8 ten thousand, molecular weight distribution 1.03；230
DEG C, under 2.16kg test conditions, melt index is less than 0.1g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula
(II) 45.17mol% of repeat unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 98.6mol% in soft segment after hydrogenation
Embodiment 6
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 0.9M, polymerize 40min at 50 DEG C；Then N, N- dimethyl tetrahydro chaffs amine, isoprene and benzene second are added
Alkene, N, the concentration of N- dimethyl tetrahydro chaff amine are 0.54M, and the concentration of isoprene and styrene is 8.2wt% (wherein, benzene second
The concentration of alkene is 0.65wt%), the polymerase 17 0min at 50 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%,
It polymerize 40min at 70 DEG C, obtains SIS；
Nickel naphthenate/aluminum alkyl catalyst 240ml is added in above-mentioned system, Hydrogen Vapor Pressure keeps 1.9MPa, at 80 DEG C
Lower hydrogenation reaction 2.5h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 11.7 ten thousand, molecular weight distribution 1.04；230
DEG C, under 2.16kg test conditions, melt index 0.21g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II)
The 44.57mol% of repeat unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 99.0mol% in soft segment after hydrogenation.
Embodiment 7
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 0.9M, polymerize 40min at 50 DEG C；Then N, N- dimethyl tetrahydro chaffs amine, isoprene and benzene second are added
Alkene, N, the concentration of N- dimethyl tetrahydro chaff amine are 0.54M, and the concentration of isoprene and styrene is 8.2wt% (wherein, benzene second
The concentration of alkene is 1.0wt%), the polymerase 17 0min at 50 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%,
It polymerize 40min at 70 DEG C, obtains SIS；
Nickel naphthenate/aluminum alkyl catalyst 240ml is added in above-mentioned system, Hydrogen Vapor Pressure keeps 1.8MPa, at 65 DEG C
Lower hydrogenation reaction 2.5h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 10.5 ten thousand, molecular weight distribution 1.02；230
DEG C, under 2.16kg test conditions, melt index 0.87g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II)
The 45.12mol% of repeat unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 98.7mol% in soft segment after hydrogenation.
Embodiment 8
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 0.9M, polymerize 40min at 50 DEG C；Then N, N- dimethyl tetrahydro chaffs amine, isoprene and benzene second are added
Alkene, N, the concentration of N- dimethyl tetrahydro chaff amine are 0.54M, and the concentration of isoprene and styrene is 8.2wt% (wherein, benzene second
The concentration of alkene is 1.5wt%), the polymerase 17 0min at 50 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%,
It polymerize 40min at 70 DEG C, obtains SIS；
Nickel naphthenate/aluminum alkyl catalyst 240ml is added in above-mentioned system, Hydrogen Vapor Pressure keeps 1.9MPa, at 65 DEG C
Lower hydrogenation reaction 2.5h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 10.8 ten thousand, molecular weight distribution 1.03；230
DEG C, under 2.16kg test conditions, melt index 2.43g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II)
The 45.35mol% of repeat unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 98.9mol% in soft segment after hydrogenation.
Embodiment 9
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 1.5M, polymerize 40min at 50 DEG C；Then N, N- dimethyl tetrahydro chaffs amine, isoprene and benzene second are added
Alkene, N, the concentration of N- dimethyl tetrahydro chaff amine are 1.5M, and the concentration of isoprene and styrene is 8.2wt% (wherein, styrene
Concentration be 1.0wt%), the polymerase 17 0min at 50 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%, 75
It polymerize 40min at DEG C, obtains SIS；
Nickel naphthenate/aluminum alkyl catalyst 240ml is added in above-mentioned system, Hydrogen Vapor Pressure keeps 1.9MPa, at 70 DEG C
Lower hydrogenation reaction 2.5h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 6.6 ten thousand, molecular weight distribution 1.02；230℃、
Under 2.16kg test conditions, melt index 7.78g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II) weight
The 63.71mol% of multiple unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 98.1mol% in soft segment after hydrogenation.
Embodiment 10
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 1.5M, polymerize 40min at 50 DEG C；Then N, N- dimethyl tetrahydro chaffs amine, isoprene and benzene second are added
Alkene, N, the concentration of N- dimethyl tetrahydro chaff amine are 1.5M, and the concentration of isoprene and styrene is 8.2wt% (wherein, styrene
Concentration be 1.5wt%), the polymerase 17 0min at 50 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%, 75
It polymerize 40min at DEG C, obtains SIS；
Nickel iso-caprylate/aluminum alkyl catalyst 240ml is added in above-mentioned system, Hydrogen Vapor Pressure keeps 1.9MPa, at 70 DEG C
Lower hydrogenation reaction 2.5h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 6.5 ten thousand, molecular weight distribution 1.02；230℃、
Under 2.16kg test conditions, melt index 12.01g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II) weight
The 61.58mol% of multiple unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 98.9mol% in soft segment after hydrogenation.
Embodiment 11
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 1.5M, polymerize 40min at 50 DEG C；Then addition tetrahydrofurfuryl alcohol ethylether, isoprene and styrene, four
The concentration of hydrogen furfuryl alcohol ethylether is 0.6M, and for 8.2wt%, (wherein, the concentration of styrene is the concentration of isoprene and styrene
0.65wt%), the polymerase 17 0min at 50 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%, is polymerize at 70 DEG C
40min, obtain SIS；
Nickel naphthenate/aluminum alkyl catalyst 240ml is added in above-mentioned system, Hydrogen Vapor Pressure keeps 1.9MPa, at 65 DEG C
Lower hydrogenation reaction 2.5h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 6.6 ten thousand, molecular weight distribution 1.02；230℃、
Under 2.16kg test conditions, melt index 5.01g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II) weight
The 30.89mol% of multiple unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 99.5mol% in soft segment after hydrogenation.
Embodiment 12
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 1.3wt%,
Initiator concentration is 1.5M, polymerize 40min at 50 DEG C；Then addition tetrahydrofurfuryl alcohol ethylether, isoprene and styrene, four
The concentration of hydrogen furfuryl alcohol ethylether is 0.9M, and for 7.4wt%, (wherein, the concentration of styrene is the concentration of isoprene and styrene
0.59wt%), the polymerase 17 0min at 50 DEG C；Styrene is eventually adding, the concentration of styrene is 1.3wt%, is polymerize at 70 DEG C
40min, obtain SIS；
Neodecanoic acid nickel/aluminum alkyl catalyst 200ml is added in above-mentioned system, Hydrogen Vapor Pressure keeps 1.9MPa, at 65 DEG C
Lower hydrogenation reaction 2.5h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 6.7 ten thousand, molecular weight distribution 1.03；230℃、
Under 2.16kg test conditions, melt index 5.65g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II) weight
The 43.60mol% of multiple unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 99.0mol% in soft segment after hydrogenation.
Embodiment 13
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 1.6wt%,
Initiator concentration is 1.5M, polymerize 40min at 50 DEG C；Then addition tetrahydrofurfuryl alcohol ethylether, isoprene and styrene, four
The concentration of hydrogen furfuryl alcohol ethylether is 0.9M, and for 6.8wt%, (wherein, the concentration of styrene is the concentration of isoprene and styrene
0.54wt%), the polymerase 17 0min at 50 DEG C；Styrene is eventually adding, the concentration of styrene is 1.6wt%, is polymerize at 70 DEG C
40min, obtain SIS；
Nickel naphthenate/aluminum alkyl catalyst 240ml is added in above-mentioned system, Hydrogen Vapor Pressure keeps 1.9MPa, at 75 DEG C
Lower hydrogenation reaction 2.5h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 6.6 ten thousand, molecular weight distribution 1.01；230℃、
Under 2.16kg test conditions, melt index 4.79g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II) weight
The 42.11mol% of multiple unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 98.4mol% in soft segment after hydrogenation
Embodiment 14
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 0.9M, polymerize 40min at 50 DEG C；Then addition tetrahydrofurfuryl alcohol ethylether, isoprene and styrene, four
The concentration of hydrogen furfuryl alcohol ethylether is 0.9M, and for 8.2wt%, (wherein, the concentration of styrene is the concentration of isoprene and styrene
1.0wt%), the polymerase 17 0min at 50 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%, is polymerize at 75 DEG C
40min, obtain SIS；
Nickel naphthenate/aluminum alkyl catalyst 240ml is added in above-mentioned system, Hydrogen Vapor Pressure keeps 2.0MPa, at 65 DEG C
Lower hydrogenation reaction 2.5h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 11.5 ten thousand, molecular weight distribution 1.03；230
DEG C, under 2.16kg test conditions, melt index 0.62g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II)
The 60.30mol% of repeat unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 98.9mol% in soft segment after hydrogenation.
Embodiment 15
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 0.45M, polymerize 40min at 50 DEG C；Then tetrahydrofurfuryl alcohol ethylether, isoprene and styrene are added,
The concentration of tetrahydrofurfuryl alcohol ethylether is 0.45M, and the concentration of isoprene and styrene is 8.2wt% (wherein, the concentration of styrene
For 0.54wt%), the polymerase 17 0min at 50 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%, is gathered at 75 DEG C
40min is closed, obtains SIS；
Nickel naphthenate/aluminum alkyl catalyst 240ml is added in above-mentioned system, Hydrogen Vapor Pressure keeps 2.1MPa, at 65 DEG C
Lower hydrogenation reaction 2.5h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 24.3 ten thousand, molecular weight distribution 1.02；230
DEG C, under 2.16kg test conditions, melt index is less than 0.1g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula
(II) 55.38mol% of repeat unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 98.0mol% in soft segment after hydrogenation.
Embodiment 16
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 1.5M, polymerize 40min at 50 DEG C；Then tetrahydrofuran, isoprene and styrene, tetrahydrofuran are added
Concentration be 2.4M, the concentration of isoprene and styrene is 8.2wt% (wherein, the concentration of styrene is 0.26wt%),
Polymerase 17 0min at 60 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%, polymerize 40min at 50 DEG C, obtains benzene
Ethene-isoprene styrene triblock copolymer；
Metallocene-titanium catalyst 0.29g is added in above-mentioned system, Hydrogen Vapor Pressure keeps 1.9MPa, the hydrogenation reaction at 65 DEG C
2h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 6.5 ten thousand, molecular weight distribution 1.02；230℃、
Under 2.16kg test conditions, melt index 4.33g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II) weight
The 12.02mol% of multiple unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 67.5mol% in soft segment after hydrogenation.
Embodiment 17
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 1.5M, polymerize 40min at 50 DEG C；Then tetrahydrofuran, isoprene and styrene, tetrahydrofuran are added
Concentration be 2.4M, the concentration of isoprene and styrene is 8.2wt% (wherein, the concentration of styrene is 0.26wt%),
Polymerase 17 0min at 60 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%, polymerize 40min at 50 DEG C, obtains benzene
Ethene-isoprene styrene triblock copolymer；
Metallocene-titanium catalyst 0.14g is added in above-mentioned system, Hydrogen Vapor Pressure keeps 1.9MPa, the hydrogenation reaction at 65 DEG C
2h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 6.4 ten thousand, molecular weight distribution 1.02；230℃、
Under 2.16kg test conditions, melt index 4.59g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II) weight
The 11.87mol% of multiple unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 52.3mol% in soft segment after hydrogenation.
Embodiment 18
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 1.2M, polymerize 40min at 50 DEG C；Then tetrahydrofuran, isoprene and styrene, tetrahydrofuran are added
Concentration be 0.4M, the concentration of isoprene and styrene is 8.2wt% (wherein, the concentration of styrene is 0.26wt%),
Polymerase 17 0min at 60 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%, polymerize 40min at 50 DEG C, obtains benzene
Ethene-isoprene styrene triblock copolymer；
Metallocene-titanium catalyst 0.26g is added in above-mentioned system, Hydrogen Vapor Pressure keeps 1.9MPa, the hydrogenation reaction at 68 DEG C
2h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 8.2 ten thousand, molecular weight distribution 1.03；230℃、
Under 2.16kg test conditions, melt index 2.14g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II) weight
The 7.56mol% of multiple unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 88.9mol% in soft segment after hydrogenation.
Embodiment 19
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 1.5M, polymerize 40min at 50 DEG C；Then N, N- dimethyl tetrahydro chaffs amine, isoprene and benzene second are added
Alkene, N, the concentration of N- dimethyl tetrahydro chaff amine are 0.6M, and the concentration of isoprene and styrene is 8.2wt% (wherein, styrene
Concentration be 0.26wt%), the polymerase 17 0min at 60 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%, 70
It polymerize 40min at DEG C, obtains SIS；
Metallocene-titanium catalyst 0.31g is added in above-mentioned system, Hydrogen Vapor Pressure keeps 2.0MPa, the hydrogenation reaction at 71 DEG C
2.5h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 6.6 ten thousand, molecular weight distribution 1.03；230℃、
Under 2.16kg test conditions, melt index 4.17g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II) weight
The 29.74mol% of multiple unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 71.8mol% in soft segment after hydrogenation.
Embodiment 20
In reactor, styrene, solvent hexamethylene and initiator n-BuLi are added, the concentration of styrene is 0.9wt%,
Initiator concentration is 1.5M, polymerize 40min at 50 DEG C；Then addition tetrahydrofurfuryl alcohol ethylether, isoprene and styrene, four
The concentration of hydrogen furfuryl alcohol ethylether is 0.9M, and for 8.2wt%, (wherein, the concentration of styrene is the concentration of isoprene and styrene
0.26wt%), the polymerase 17 0min at 60 DEG C；Styrene is eventually adding, the concentration of styrene is 0.9wt%, is polymerize at 75 DEG C
40min, obtain SIS；
Metallocene-titanium catalyst 0.19g is added in above-mentioned system, Hydrogen Vapor Pressure keeps 2.0MPa, the hydrogenation reaction at 75 DEG C
2.5h, obtain the hydrogenation type styrene analog thermoplastic elastomer of the present invention.
After testing, the number-average molecular weight of gained hydrogenated polymers GPC measure is 6.5 ten thousand, molecular weight distribution 1.01；230℃、
Under 2.16kg test conditions, melt index 5.13g/10min；In soft segment, formula (I) repeat unit accounts for formula (I) and formula (II) weight
The 43.75mol% of multiple unit summation；The degree of hydrogenation of non-phenyl ring repeat unit is 63.8mol% in soft segment after hydrogenation.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above-mentioned embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., it should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. a kind of isoprene styrene atactic polymer, is designated as P1, it is characterised in that the polymer includes formula (I), formula
And the repeat unit shown in formula (III) (II)：
Wherein, the repeat unit shown in formula (I) accounts for the 5-75mol% of repeat unit summation shown in formula (I) and formula (II)；
In formula (III), R is aryl, preferably phenyl.
Preferably, the repeat unit shown in formula (I) accounts for the 6-70mol% of repeat unit summation shown in formula (I) and formula (II), enters one
Walk preferred 6.5-65mol%.
It is further preferred that the repeat unit shown in formula (III) accounts for the 1- of formula (I), formula (II) and repeat unit summation shown in formula (III)
25mol%, preferably 2-20mol%.
It is further preferred that the isoprene styrene atactic polymer uses the number-average molecular weight that GPC is determined as 2-25 ten thousand.
2. a kind of polymer, is designated as P2, it is characterised in that the polymer is the isoprene styrene described in claim 1
The hydrogenation products of atactic polymer.
3. polymer according to claim 2, it is characterised in that in the hydrogenation products, the hydrogenation of double bond in non-phenyl ring
Spend and be more than 98mol%, the degree of hydrogenation of double bond is less than 2mol% in phenyl ring；
Or
In the hydrogenation products, the degree of hydrogenation of double bond is 50-98mol% (preferably 50-90mol%) in non-phenyl ring, double in phenyl ring
The degree of hydrogenation of key is less than 2mol%.
4. a kind of SIS, is designated as BP1, it is characterised in that the copolymer
Structural formula is such as shown in (IV)：
In formula (IV), the both ends of the triblock copolymer are polystyrene hard section, and centre is polyisoprene soft segment；It is described poly- different
Pentadiene soft segment includes the repeat unit shown in formula (I), formula (II) and formula (III)：
Wherein, the repeat unit shown in formula (I) accounts for the 5-75mol% of repeat unit summation shown in formula (I) and formula (II)；
In formula (III), R is aryl, preferably phenyl.
Preferably, the repeat unit shown in formula (I) accounts for the 6-70mol% of repeat unit summation shown in formula (I) and formula (II), enters one
Walk preferred 6.5-65mol%.
It is further preferred that the repeat unit shown in formula (III) accounts for the 1- of formula (I), formula (II) and repeat unit summation shown in formula (III)
25mol%, preferably 2-20mol%.
It is further preferred that wherein polystyrene hard section accounts for the 15-50wt% of three block quality.
5. a kind of hydrogenation type styrene analog thermoplastic elastomer, is designated as BP2, it is characterised in that the elastomer is claim 4
Described SIS BP1 hydrogenation products.
Preferably, in above-mentioned thermoplastic elastomer (TPE), the degree of hydrogenation of the double bond in non-phenyl ring is more than 98mol% (preferably 98.1-
99.9mol%), the degree of hydrogenation of double bond is less than 2mol% in phenyl ring；Or
In above-mentioned thermoplastic elastomer (TPE), the degree of hydrogenation of the double bond in non-phenyl ring is 50-98mol% (preferably 50-90mol%), benzene
The degree of hydrogenation of double bond is less than 2mol% in ring.
Preferably, described thermoplastic elastomer (TPE) uses the number-average molecular weight that GPC is determined as 4-30 ten thousand, preferably 5-25 ten thousand；Molecule
Amount is distributed as 1.05 or so.Preferably, melt index of the described thermoplastic elastomer (TPE) under 230 DEG C, 2.16kg test conditions
For 0.05-20g/10min.
6. the hydrogenation type process for preparing thermoplastic phenylethylene elastomer described in claim 5, it is characterised in that methods described
Comprise the following steps：(1) anionic polymerization is used, has using styrene and isoprene as Material synthesis and is tied shown in formula (IV)
The SIS of structure formula；(2) triblock copolymer is in catalyst action
Lower Hydrogenation obtains described hydrogenation type styrene analog thermoplastic elastomer；
In formula (IV), the both ends of the triblock copolymer are polystyrene hard section, and centre is polyisoprene soft segment；It is described poly- different
Pentadiene soft segment includes the repeat unit shown in formula (I), formula (II) and formula (III)：
Wherein, the repeat unit shown in formula (I) accounts for the 5-75mol% of repeat unit summation shown in formula (I) and formula (II)；
In formula (III), R is aryl, preferably phenyl.
Preferably, the repeat unit shown in formula (I) accounts for the 6-70mol% of repeat unit summation shown in formula (I) and formula (II), enters one
Walk preferred 6.5-65mol%.
It is further preferred that the repeat unit shown in formula (III) accounts for the 1- of formula (I), formula (II) and repeat unit summation shown in formula (III)
25mol%, preferably 2-20mol%.
It is further preferred that wherein polystyrene hard section accounts for the 15-50wt% of three block quality.
It is further preferred that in the polymerization process of polyisoprene soft segment, micmstructure of polymer conditioning agent is added to control formula (I)
The content of shown repeat unit.
7. preparation method according to claim 6, it is characterised in that above-mentioned steps (1) specifically include：
Using styrene and isoprene as raw material, butyl lithium be initiator in non-polar organic solvent, synthesize styrene-different
Isoprene-styrene triblock copolymer；Accounted for for the repeat unit shown in control formula (I) and list is repeated shown in formula (I) and formula (II)
The 5-75mol% of first summation, in polyisoprene soft segment polymerization process, introduce micmstructure of polymer conditioning agent.
It is further preferred that described preparation method includes：(1) styrene polymerization, polymerization time 30- are triggered with initiator first
60min, 40-70 DEG C of polymerization temperature；Then isoprene and styrene mixture are added, is deposited in micmstructure of polymer conditioning agent
In lower polymerization, reaction time 60-90min, reaction temperature is 40-80 DEG C；Remaining styrene is finally added to be polymerize
Reaction, polymerization time 30-60min, 40-70 DEG C of polymerization temperature, obtains triblock polymer；(2) in resulting three block
Non-polar organic solvent wiring solution-forming is added in polymer, is added selected from organic nickel/aluminum alkyl catalyst or metallocene-titanium catalyst
Hydrogenation catalyst, it is 60-90 DEG C, is reacted 1-5 hours under conditions of Hydrogen Vapor Pressure holding 1.5-2.5MPa in temperature, after hydrogenation
To described hydrogenation type styrene analog thermoplastic elastomer.
8. the preparation method according to claim 6 or 7, it is characterised in that the micmstructure of polymer conditioning agent is selected from
Tetrahydrofuran, tetrahydrofurfuryl alcohol ethylether or N, N- dimethyl tetrahydro chaff amine.
Preferably, the dosage of the micmstructure of polymer conditioning agent is：0<r<100.Preferably, 0.01<r<10, more preferably
Ground, 0.05<r<2.The r represents the mol ratio of micmstructure of polymer conditioning agent and initiator.
Preferably, in step (2), hydrogenation catalyst is selected from organic nickel/aluminum alkyl catalyst or metallocene-titanium catalyst.
It is further preferred that when using organic nickel/alkyl aluminum as hydrogenation catalyst, in the thermoplastic elastomer (TPE) of gained, in non-phenyl ring
The degree of hydrogenation of double bond is more than 98mol% (preferably 98.1-99.9mol%), and the degree of hydrogenation of double bond is less than 2mol% in phenyl ring.
It is further preferred that when using metallocene-titanium catalyst as hydrogenation catalyst, in the thermoplastic elastomer (TPE) of gained, the double bond in non-phenyl ring
Degree of hydrogenation be 50-98mol% (preferably 50-90mol%), the degree of hydrogenation of double bond is less than 2mol% in phenyl ring.
9. according to the preparation method described in claim any one of 6-8, it is characterised in that described butyl lithium is selected from normal-butyl
Lithium, s-butyl lithium, tert-butyl lithium.
Preferably, described non-polar organic solvent is selected from cycloalkane.Preferably, the cycloalkane is hexamethylene or pentamethylene.
It is further preferred that the hexamethylene is the hexamethylene containing less than 30% hexane.
It is further preferred that in the polymerization process of polystyrene hard section, the monomer concentration of styrene is 0.1-20wt% (preferably 0.5-
2.5wt%)；In the polymerization process of polyisoprene soft segment, the monomer concentration of the mixture of isoprene and styrene is 5-
20wt% (preferably 6-10wt%), wherein, content of the styrene in the mixture is 1-25wt%, preferably 2-20wt%.
It is further preferred that described organic nickel is selected from nickel naphthenate, alkyl nickel etc..
10. the purposes of the hydrogenation type styrene analog thermoplastic elastomer described in claim 5, it is characterised in that the elastomer
Available for binding agent, sealant, coating, class rubber compound (vulcanization rubber can be replaced), plastic modifier, compatilizer, thermosetting
In the fields such as the anti-piping compound of property modifier and unsaturated polyester (UP) asphalt modifier.
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