CN105175659B - A kind of transparent type hydrogenated polystyrene b random copolymerizations conjugated diene/styrene resin and preparation method thereof - Google Patents
A kind of transparent type hydrogenated polystyrene b random copolymerizations conjugated diene/styrene resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of transparent type hydrogenated polystyrene b random copolymerizations conjugated diene/styrene resin and preparation method thereof, the transparent type resin is made up of the random copolymerization block of styrene block and styrene, conjugated diene and divinylbenzene, and the double bond hydrogenation ratio in block copolymer in conjugated diene unit reaches more than 98%；Its preparation method is that styrene monomer is first carried out into homopolymerization under lithium alkylide initiation, then carries out random copolymerization with styrene, conjugated diene and divinylbenzene mix monomer, and copolymerization product carries out hydrogenation reaction, produced；The preparation method is simple, and obtained hydrogenated polystyrene b random copolymerizations conjugated diene/styrol copolymer intensity is high, and with the features such as preferable processing characteristics and ageing-resistant performance, turbidity are low, transparency is high, can be molded and be molded with membrane, and application field is extensive.
Description
Technical field
The present invention relates to a kind of transparent type hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene resin and its system
Preparation Method；Belong to modified butadiene styrene resin Material Field.
Background technology
Styrene polymerize synthesis random copolymer or block with orientable under the initiation of lithium alkylide in a solvent with butadiene
Block ratio S/B=(20-40)/(80-60) in copolymer, such as SBS, usually triblock copolymer；S/B=in SBR molecules
(20-40)/(80-60), usually random copolymer；SEBS is SBS hydrogenated products；SEPS is SIS hydrogenated products.These
Material is applied to manufacture elastomeric material such as footwear material, adhesive, handle for tool, tire, medical material etc..Commercially available KR-03, KR-
01 is styrene-butadiene transparent resin, and wherein S/B=(70-80)/(30-20), molecular structure is line style and the molecule composition of coupling chain, is put down
Average molecular weight is Mn=80000-100000, and styrene-butadiene transparent resin is to be made to draw in a solvent with lithium alkylide by styrene and butadiene
Agent is sent out, stereospecfic polymerization synthesis finally carries out coupling with epoxidised soybean oil and form branch with random copolymer and block copolymerization section
The polymer of chain, this polymer is eventually passed after dry method desolventizing, is formed through pelletizing, belongs to non-hydrogenated styrene-butadiene polymer, its
Contain substantial amounts of unsaturated double-bond in polybutadiene section in molecular structure.Its key property is to have high transparency and good concurrently to resist
Impact, density are small, strong coloring force, processing characteristics are excellent, nontoxicity, are widely used in refrigerator manufacture, shoemaking, toy, food and hold
Device, packaging, medicine equipment, daily product, electrical instrumentation disk and mixed with other materials (such as GPPS, SAN, SMA, PP, HIPS)
The fields such as mixed modification.That density is low the characteristics of K- resin copolymers compared with other transparent polymers, economically on see
More attractive, meets the clauses of the U.S. 21 CFR of food and medicine management FDA 177 1640 and Europe EEC guides 90/128/EEC
The regulation of revised provision, can be used as the packaging of food.Butadiene styrene resin is partially crystalline polymer, good fluidity, the production processed
Product surface is smooth, good luster, transparency are high, can be processed using traditional processing mode, such as injection, extrude, it is blown film and curtain coating, hollow
The processing method such as blowing, thermoforming is although after styrene-butadiene transparent resin injection molding, mist degree is low, transparent height, but is used as outdoor use
The shortcomings of not ageing-resistant, the easy yellowing and cracking such as equipment panel and packaging equipment, usage cycles short life.
In existing styrene-butadiene transparent resin technology, (Wang Xingya etc., the synthesis of transparent butadiene-styrene impact resin and performance [J] are closed
Synthetic rubber industry, 1995) describe using styrene, butadiene as monomer in a text, s-BuLi is initiator, and hexamethylene is molten
Agent, alkoxy silane is coupling agent, by anionic polymerization and coupling reaction, then chemically treated and be made embedding with star
Two trade mark transparent butadiene-styrene impact resins of segment structure, experiment investigation influence of the polymerization temperature to reaction rate, monomer ratio,
The relation of copolymer structure and resin property.In addition, (Qi Jun, Study on structure and properties of
star-type transparent impact styrene butadiene resin[J].China synthetic resin
And plastics, 2011.05.) it have studied in a text and make monomer with styrene and butadiene, make initiator with n-BuLi,
Make coupling agent with epoxidised soybean oil, the styrene-butadiene transparent resin synthesized by anionic polymerisation have studied polymerization
The molecular mass control of thing and random block control method, examine shock strength and fluidity of molten and relative molecular mass
Relation；And polymerization finish after with carbonated water or oil-soluble organic acids be de- lithium agent so that the resin being made reach it is transparent
Purpose.
(Zambelli A, Binary copolymerizations of styrene and conjugated
diolefins in the presence of cyclopentadienyltitanium trichloride-
Methylaluminoxane [J], Macromol Chem Phys, 1994.) conventional styrene-ethene/fourth is described in a text
The preparation of alkene-styrene triblock polymer (SEBS) is that in thiacyclohexane solvent, it is raw material, cyclopentadienyl to have butadiene, styrene
Metal is catalyst, and n-BuLi is initiator, and polar solvent tetrahydrofuran is polymerize for control contents of ethylene.
At present, researcher be to cyclopentadienyl titanium dichloride/butyl lithium bi-component catalyst system and catalyzing Hydrogenated SBS prepare SEBS research compared with
It is many, such as USA 4501875, USA 3595942, CN 1166498A.
The hydrogenation of block type styrene-conjugated diene lithium series of polymer adds usually using cyclopentadienyl-titanium system catalysis and the catalysis of nickel system
Hydrogen, wherein cyclopentadienyl-titanium catalyst system can all hydrogenate polybutadiene section in SBS.As Chinese patent ZL97108078.4, the U.S. are special
Sharp USP4980421 (1990), European patent EP 0471415 (1991) etc. provide a kind of method for hydrogenation to styrene-butadiene polymer,
Its degree of hydrogenation is up to 99.5%.United States Patent (USP) USP5132372 (1992), United States Patent (USP) USP5206307 (1993) etc. provide one
Particularly polyisoprene section can whole hydrogen in the method for planting nickel system catalytic hydrogenation styrene-conjugated diene polymer, polymer
Change.Above-mentioned block type polymers embody the behavior of thermoplastic elastomer (TPE).
In addition, SSBR be by butadiene, styrene be raw material, n-BuLi is initiator, and lewis base is conditioning agent, control
In polymerisation processed during polymerizing butadiene contents of ethylene and obtain random copolymer, do not have to be hydrogenated with SSBR preparation process
Processing, is mainly used as tire.The product that SSBR has been commercialized has Solprene1204, Y-031 and HPR-850 etc..
At present, the also no reported in literature of polymer hydrogenated as the butylbenzene copolymer of high styrenic percentage.
The content of the invention
For being deposited after styrene-butadiene transparent resin injection molding in the prior art as outdoor use equipment, panel and packaging equipment etc.
The shortcomings of not ageing-resistant, easy yellowing and cracking, usage cycles short life；The purpose of the present invention is to be to provide a kind of chemistry surely
Qualitative good, ultraviolet light, heat-resisting, weather-proof, resistance to ozone, and with higher elasticity, high-impact, high extension at break, high intensity it is saturating
Bright type hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene resin, the resin is adapted to prepare outdoor instrument, packing timber
Material, sheet material and instrument panel etc., can also be in preparing the medical devices such as woven hose, infusion bag, needle tubing.
Another object of the present invention is to be to provide a kind of simple to operate, reaction condition gently, prepares the transparent type
The method of hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene resin.
It is randomly common the invention provides a kind of transparent type hydrogenated polystyrene-b- in order to realize the technical purpose of the present invention
Polymerized conjugated diene/styrene resin, the resin is obtained by the block copolymer hydrogenation with the chemical expression of formula 1：
S1-B/S/D
Formula 1
Wherein,
S1The equal poly block being made up of styrene units for being number-average molecular weight in the range of 40000~45000；
B/S/D be number-average molecular weight in the range of 50000~55000 by styrene units, conjugated diene unit and two
The random copolymerization block that vinyl benzene unit is constituted；
Hydrogenation degree >=98% of conjugated diene unit in B/S/D random copolymerization blocks；
S1The ratio between styrene units gross mass and conjugated diene unit gross mass are 45~80 in-B/S/D block copolymers:
55~20.
It is preferred that transparent type hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene resin in, conjugated diene unit
It is made up of butadiene and/or isoprene.
More preferably in transparent type hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene resin, 1,2- structure
The quality of butadiene unit and/or the isoprene unit of 3,4- structures accounts for the 50%~68% of conjugated diene unit gross mass.
More preferably in transparent type hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene resin, conjugated diene list
Member is made up of butadiene.The quality of the butadiene unit of 1,2- structures accounts for the 50%~68% of conjugated diene unit gross mass.
More preferably in transparent type hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene resin, styrene units
Block ratio S/B with conjugated diene unit is 35~80:65~20.
It is preferred that transparent type hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene resin in, divinylbenzene list
The quality of member is S10.08 ‰~the 0.14 ‰ of-B/S/I/D block copolymerization amount of substance.The divinylbenzene list a small amount of by introducing
Member is by S1- B/S/D block copolymers carry out cladodification.
It is preferred that transparent type hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene copolymer resin in, S1Homopolymerization
The quality of styrene units is the 50~60% of total styrene units quality in block；Remaining styrene units are distributed in B/S/
In D random copolymerization blocks.Styrene units are in S1Distribution form in-B/S/I/D block copolymers, it is therefore prevented that S1-B/S/I/D
Polymer formation crystallization after block copolymer hydrogenation, increases the transparency and intensity of polymer.
Transparent type hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene resin is prepared present invention also offers one kind
The method of fat, this method be first by styrene monomer by anionic polymerisation system carry out homopolymerization, after the completion of homopolymerization, then the moon from
Styrene, conjugated diene and divinylbenzene mix monomer are added in subparadigm system and carries out random copolymerization, obtain polystyrene-
B- random copolymerizations conjugated diene/styrol copolymer, gained polystyrene-b- random copolymerizations conjugated diene/styrol copolymer
Hydrogenation reaction is carried out, is produced.
It is preferred that method in, homopolymerization temperature be 50 DEG C~60 DEG C, the homopolymerization time be 20min~25min.
It is preferred that method in, random copolymerization temperature be 50 DEG C~75 DEG C, the copolymerization time be 20min~25min.
It is preferred that method in, lewis base is added during random copolymerization and is used as structure regulator regulation polystyrene-b-
In random copolymerization conjugated diene/styrol copolymer in B/S/D random copolymerization blocks 1,2- structures butadiene unit and/or 3,
The isoprene unit quality of 4- structures accounts for the ratio 50%~68% of conjugated diene unit gross mass.Appropriate 1,2- structures
Butadiene unit or the isoprene unit of 3,4- structures can guarantee that the S that hydrogenation is closed1- B/S/D block copolymers have suitable
Elasticity and extension at break.
It is preferred that method in, structure regulator is at least one of tetrahydrofurfuryl alcohol ethylether, double tetrahydrochysene chaff propane.It is preferred that
Structure regulator be more beneficial for the accurate adjustment energy of the 1,2- structures of butadiene unit or the 3,4- structural contents of isoprene
Power.
It is preferred that method in, structure regulator consumption be total monomer quality 0.30~0.40%.
It is preferred that method in, hydrogenation reaction temperature be 70 DEG C~85 DEG C, hydrogenation reaction pressure be 1.2MPa~1.5MPa, plus
2 hours~2.5 hours hydrogen reaction time.
It is preferred that method in, hydrogenation reaction be under dicyclopentadiene titanium chloride catalytic condition carry out, dicyclopentadiene
The consumption of titanium chloride is 0.030~0.035g/100g polystyrene-b- random copolymerizations conjugated diene/styrol copolymer.
It is preferred that method in, the iodine number after polystyrene-b- random copolymerizations conjugated diene/styrol copolymer hydrogenation
＜ 4.5g iodine/100g hydrogenated copolymers.
It is preferred that preparation method in, after polystyrene-b- random copolymerizations conjugated diene/styrol copolymer hydrogenation
Iodine number ＜ 4.5g iodine/100g hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer；Hydrogenated polystyrene-b-
Random copolymerization conjugated diene/styrol copolymer hydrogenation degree >=98%.
It is preferred that preparation method in, in the glue of hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer
The cyclohexane solution of middle addition 4~5wt% isooctyl acids is terminated with active catalyst, decomposition reaction forms water miscible different pungent
Sour lithium, lithium chloride and water miscible titaniferous compound are simultaneously soluble in the aqueous phase.Wherein, isooctyl acid/butyl lithium (molecular proportion)=(1.1~
1.2):1。
The specific preparation side of transparent type hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene resin of the present invention
Method is as follows：
1st, thiacyclohexane and normal hexane mixed solvent are added in polymeric kettle, structure regulator is added, will after stirring
Styrene monomer is added in polymeric kettle after further stirring, with appropriate butyl lithium initiated polymerization, at 50~60 DEG C,
React after 20~25min；The mix monomer of styrene, butadiene and divinylbenzene is added, 20 are reacted at 50~75 DEG C
After~25min, polystyrene-block-random copolymerization conjugated diene/styrol copolymer is obtained, sampling does gpc analysis and surveys polymerization
The molecular weight and contents of ethylene of thing.
2nd, polystyrene-b- random copolymerizations conjugated diene/styrol copolymer is moved in hydriding reactor, and adds hydrogenation and urged
Agent dicyclopentadiene titanium chloride, the temperature of hydrogenation reaction is 70~85 DEG C, and hydrogen is passed through pressure for 1.2~1.5MPa, hydrogen
It is 2~2.5 hours to change the reaction time, after the completion of hydrogenation, adds the cyclohexane solution and hydrogenation activity catalyst of isooctyl acid
Terminated, decomposition reaction 15min, then add deionized water carry out washing stirring 10~15min, finally separate after aqueous phase,
Add total resin demand 0.25wt% antioxidant 1076 and stir 10~20min, glue discharges afterwards, condensed with ethanol
Glue simultaneously separates out resin, then resin is carried out into hot-air drying and obtained, and finally surveys the iodine number of hydropolymer.
Compared with the prior art, the beneficial effects of the invention are as follows：
The present invention obtains one end first has styrene block, and there is the other end side chain to be distributed or lightly crosslinked S/B/D
Hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer of block of random copolymer；Its special molecular structure
Impart the preferable heat resistance of block polymer, ageing resistance, weather-proof, resistance to ozone, uvioresistant, stretch breaking strength, shock resistance strong
Degree, the transparency, processability and film forming, hydrogenated polystyrene-block-random copolymerization conjugation of particularly high butadienyl content
Diene/styrol copolymer elasticity is good, elongation at break is high；The block polymer can with injection moulding and biaxial tension film forming,
Its product surface is clear, the low feature of product turbidity.
Transparent type hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene resin prepared by the present invention, styrene/
During block ratio S/B=(35~80)/(65~20) of butadiene, its elongation rate of tensile failure >=200%, hardness (Shore D)≤65,
Then it is applicable to transparent membrane material, such as packaging film, woven hose, infusion bag, electric wire foreskin, handle for tool.If S/B=(70-
80)/(30-20) elongation rate of tensile failure ＜ 150%, hardness (Shore D) ＞ 70, then be applicable to plastic material, such as clear sheet,
Instrument and meter panel, packing box etc..
Hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer mature preparation process of the present invention, raw material
Source is wide, meets demand of industrial production.
Embodiment
Following examples are intended to illustrate present invention, and the protection domain of the claims in the present invention is not implemented
The limitation of example.
The number-average molecular weight of polymer is determined in the following example with gel permeation chromatograph (GPC).
The microstructure content of quantitative determination polymer is composed using H-NMR.
The physical property of polymer is determined using INSTRON-5565 electronic tensile machines.
Embodiment 1
Cyclohexane solution of the mass fraction for 10% normal hexane is added in 5 liters of steel steel polymeric kettles under nitrogen protection
3500mL, then adds 1.36mL tetrahydrofurfuryl alcohol ethylethers, is warming up to hot water after 50~60 DEG C, 80g styrene is added poly-
Close in kettle and open stirring, the n-BuLi 12mL for then injecting 0.5mol/L with syringe enters in polymeric kettle, react 20~25min
Afterwards；The mix monomer of 292.5g butadiene and 77.5g styrene and 0.03mL divinylbenzene is added, it is anti-at 50~75 DEG C
Answer after 25min；Measure the vinyl mass content 50.6% of butadiene segment in polymer, polymer number-average molecular weight Mn=
82000。
Then, pump the polymer into after hydriding reactor, add the dicyclopentadiene titanium chloride 0.13g of mass fraction 99%,
Hydrogen Vapor Pressure 1.2MPa is controlled, hydrogenation glue is moved into after 2 hours and terminate kettle, now added by stirring reaction at 70~85 DEG C
The cyclohexane solution 25mL of 4.2wt% isooctyl acids is terminated with hydrogenation activity catalyst, decomposition reaction 15min, is then added
Deionized water 300mL is washed and is stirred 10-15min, is finally separated after aqueous phase, then adds in glue antioxidant
10761.2g simultaneously stirs 15min, and glue discharges afterwards, and glue is condensed with ethanol, and now resin is isolated, then resin is carried out into 70
DEG C hot-air is dried and obtained, and measures hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer hydrogenation degree
98.2%, melt flow rate (MFR) (MFR) is 10.43g/10min (being tested under the conditions of conventional criteria).
Embodiment 2
Cyclohexane solution of the mass fraction for 10% normal hexane is added in 5 liters of steel steel polymeric kettles under nitrogen protection
3500mL, then adds 1.54mL tetrahydrofurfuryl alcohol ethylethers, is warming up to hot water after 50~60 DEG C, 100g styrene is added poly-
Close in kettle and open stirring, the n-BuLi 11mL for then injecting 0.5mol/L with syringe enters in polymeric kettle, react 20~25min
Afterwards；The mix monomer of 247.5g butadiene and 102.5g styrene and 0.04mL divinylbenzene is added, at 50~75 DEG C
React after 25min；Measure the vinyl mass content 57.6% of butadiene segment in polymer, polymer number-average molecular weight Mn=
96000.
Then, pump the polymer into after hydriding reactor, add the dicyclopentadiene titanium chloride 0.14g of mass fraction 99%,
Hydrogen Vapor Pressure 1.3MPa is controlled, hydrogenation glue is moved into after 2 hours and terminate kettle, now added by stirring reaction at 70~85 DEG C
The cyclohexane solution 25mL of 4.2wt% isooctyl acids is terminated with hydrogenation activity catalyst, decomposition reaction 15min, is then added
Deionized water 300mL is washed and is stirred 10-15min, is finally separated after aqueous phase, then adds in glue antioxidant
10761.2g simultaneously stirs 15min, and glue discharges afterwards, and glue is condensed with ethanol, and now resin is isolated, then resin is carried out
70 DEG C of hot-air is dried and obtained, and measures hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer hydrogenation degree
99.1%, MFR are 9.47g/10min (being tested under the conditions of conventional criteria).
Embodiment 3
Cyclohexane solution of the mass fraction for 10% normal hexane is added in 5 liters of steel steel polymeric kettles under nitrogen protection
3500mL, then adds the double tetrahydrochysene chaff chaff propane of 1.60mL, is warming up to hot water after 50~60 DEG C, 140g styrene is added poly-
Close in kettle and open stirring, the n-BuLi 10mL for then injecting 0.5mol/L with syringe enters in polymeric kettle, react 20~25min
Afterwards；The mix monomer of 202.5g butadiene and 107.5g styrene and 0.06mL divinylbenzene is added, at 50~75 DEG C
React after 25min；Measure the vinyl mass content 62.5% of butadiene segment in polymer, polymer number-average molecular weight Mn=
104000.
Then, pump the polymer into after hydriding reactor, add the dicyclopentadiene titanium chloride 0.14g of mass fraction 99%,
Hydrogen Vapor Pressure 1.5MPa is controlled, hydrogenation glue is moved into after 2 hours and terminate kettle, now added by stirring reaction at 70~85 DEG C
The cyclohexane solution 25mL of 4.2wt% isooctyl acids is terminated with hydrogenation activity catalyst, decomposition reaction 15min, is then added
Deionized water 300mL is washed and is stirred 10-15min, is finally separated after aqueous phase, then adds in glue antioxidant
10761.2g simultaneously stirs 15min, and glue discharges afterwards, and glue is condensed with ethanol, and now resin is isolated, then resin is carried out
70 DEG C of hot-air is dried and obtained, and measures hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer hydrogenation degree
99.4%, MFR are 8.14g/10min (being tested under the conditions of conventional criteria).
Embodiment 4
Cyclohexane solution of the mass fraction for 10% normal hexane is added in 5 liters of steel steel polymeric kettles under nitrogen protection
3500mL, then adds the double tetrahydrochysene chaff chaff propane of 1.70mL, is warming up to hot water after 50~60 DEG C, 180g styrene is added poly-
Close in kettle and open stirring, the n-BuLi 9.5mL for then injecting 0.5mol/L with syringe enters in polymeric kettle, reaction 20~
After 25min；The mix monomer of 157.5g butadiene and 112.5g styrene and 0.05mL divinylbenzene is added, 50~75
Reacted at DEG C after 25min；Measure the vinyl mass content 65.3% of butadiene segment in polymer, polymer number-average molecular weight
Mn=113000.
Then, pump the polymer into after hydriding reactor, add the dicyclopentadiene titanium chloride 0.13g of mass fraction 99%,
Hydrogen Vapor Pressure 1.5MPa is controlled, hydrogenation glue is moved into after 2 hours and terminate kettle, now added by stirring reaction at 70~85 DEG C
The cyclohexane solution 25mL of 4.2wt% isooctyl acids is terminated with hydrogenation activity catalyst, decomposition reaction 15min, is then added
Deionized water 300mL is washed and is stirred 10-15min, is finally separated after aqueous phase, then adds in glue antioxidant
10761.2g simultaneously stirs 15min, and glue discharges afterwards, and glue is condensed with ethanol, and now resin is isolated, then resin is carried out
70 DEG C of hot-air is dried and obtained, and measures hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer hydrogenation degree
98.6%, MFR are 8.03g/10min (being tested under the conditions of conventional criteria).
Embodiment 5
Cyclohexane solution of the mass fraction for 10% normal hexane is added in 5 liters of steel steel polymeric kettles under nitrogen protection
3500mL, then adds 1.80mL tetrahydrofurfuryl alcohol ethylethers, is warming up to hot water after 50~60 DEG C, 150g styrene is added poly-
Close in kettle and open stirring, the n-BuLi 8.0mL for then injecting 0.5mol/L with syringe enters in polymeric kettle, reaction 20~
After 25min；The mix monomer of 135g butadiene and 165g styrene and 0.06mL divinylbenzene is added, at 50~75 DEG C
React after 25min；Measure the vinyl mass content 68.6% of butadiene segment in polymer, polymer number-average molecular weight Mn=
124000.
Then, pump the polymer into after hydriding reactor, add the dicyclopentadiene titanium chloride 0.15g of mass fraction 99%,
Hydrogen Vapor Pressure 1.5MPa is controlled, hydrogenation glue is moved into after 2 hours and terminate kettle, now added by stirring reaction at 70~85 DEG C
The cyclohexane solution 25mL of 4.2wt% isooctyl acids is terminated with hydrogenation activity catalyst, decomposition reaction 15min, is then added
Deionized water 300mL is washed and is stirred 10-15min, is finally separated after aqueous phase, then adds in glue antioxidant
10761.2g simultaneously stirs 15min, and glue discharges afterwards, and glue is condensed with ethanol, and now resin is isolated, then resin is carried out
70 DEG C of hot-air is dried and obtained, and measures hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer hydrogenation degree
99.4%, MFR are 7.65g/10min (being tested under the conditions of conventional criteria).
Embodiment 6
Cyclohexane solution of the mass fraction for 10% normal hexane is added in 5 liters of steel steel polymeric kettles under nitrogen protection
3500mL, then adds the double tetrahydrochysene chaff chaff propane of 1.80mL, is warming up to hot water after 50~60 DEG C, 150g styrene is added poly-
Close in kettle and open stirring, the n-BuLi 8.5mL for then injecting 0.5mol/L with syringe enters in polymeric kettle, reaction 20~
After 25min；The mix monomer of 112.5g butadiene and 187.5g styrene and 0.04mL divinylbenzene is added, 50~75
Reacted at DEG C after 25min；Measure the vinyl mass content 71.3% of butadiene segment in polymer, polymer number-average molecular weight
Mn=115000.
Then, pump the polymer into after hydriding reactor, add the dicyclopentadiene titanium chloride 0.15g of mass fraction 99%,
Hydrogen Vapor Pressure 1.4MPa is controlled, hydrogenation glue is moved into after 2 hours and terminate kettle, now added by stirring reaction at 70~85 DEG C
The cyclohexane solution 25mL of 4.2wt% isooctyl acids is terminated with hydrogenation activity catalyst, decomposition reaction 15min, is then added
Deionized water 300mL is washed and is stirred 10-15min, is finally separated after aqueous phase, then adds in glue antioxidant
10761.2g simultaneously stirs 15min, and glue discharges afterwards, and glue is condensed with ethanol, and now resin is isolated, then resin is carried out
70 DEG C of hot-air is dried and obtained, and measures hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer hydrogenation degree
99.5%, MFR are 8.32g/10min (being tested under the conditions of conventional criteria).
Embodiment 7
Cyclohexane solution of the mass fraction for 10% normal hexane is added in 5 liters of steel steel polymeric kettles under nitrogen protection
3500mL, then adds the double tetrahydrochysene chaff chaff propane of 1.60mL, is warming up to hot water after 50~60 DEG C, 180g styrene is added poly-
Close in kettle and open stirring, the n-BuLi 8.5mL for then injecting 0.5mol/L with syringe enters in polymeric kettle, reaction 20~
After 25min；The mix monomer of 90g butadiene and 180g styrene and 0.03mL divinylbenzene is added, at 50~75 DEG C
React after 25min；Measure the vinyl mass content 65.3% of butadiene segment in polymer, polymer number-average molecular weight Mn=
119000.
Then, pump the polymer into after hydriding reactor, add the dicyclopentadiene titanium chloride 0.13g of mass fraction 99%,
Hydrogen Vapor Pressure 1.4MPa is controlled, hydrogenation glue is moved into after 2 hours and terminate kettle, now added by stirring reaction at 70~85 DEG C
The cyclohexane solution 25mL of 4.2wt% isooctyl acids is terminated with hydrogenation activity catalyst, decomposition reaction 15min, is then added
Deionized water 300mL is washed and is stirred 10-15min, is finally separated after aqueous phase, then adds in glue antioxidant
10761.2g simultaneously stirs 15min, and glue discharges afterwards, and glue is condensed with ethanol, and now resin is isolated, then resin is carried out
70 DEG C of hot-air is dried and obtained, and measures hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrol copolymer hydrogenation degree
98.4%, MFR are 8.02g/10min (being tested under the conditions of conventional criteria).
Embodiment 9
By hydrogenated polystyrene-block-random copolymerization conjugated diene/styrene copolymerized transparent resin in embodiment 1~8
Carry out after injection molding, its physical property such as table 1.
Hydrogenated polystyrene-block-random copolymerization conjugated diene/styrene copolymerized transparent tree in the embodiment 1~8 of table 1
Fat physical property
Claims (10)
1. a kind of transparent type hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene resin, its spy is, by with formula 1
The block copolymer hydrogenation of chemical expression is obtained：
S1-B/S/D
Formula 1
Wherein,
S1The equal poly block being made up of styrene units for being number-average molecular weight in the range of 40000~45000；
B/S/D be number-average molecular weight in the range of 50000~55000 by styrene units, conjugated diene unit and divinyl
The random copolymerization block that base benzene unit is constituted；
Hydrogenation degree >=98% of conjugated diene unit in B/S/D random copolymerization blocks；
S1The ratio between styrene units gross mass and conjugated diene unit gross mass are 45~80 in-B/S/D block copolymers:55~
20；
The quality of divinylbenzene units is S10.08 ‰~the 0.14 ‰ of-B/S/D block copolymerization amount of substance.
2. transparent type hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene resin according to claim 1, its
It is characterised by, S1The quality of styrene units is the 50~60% of total styrene units quality in equal poly block.
3. transparent type hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene resin according to claim 1, its
It is characterised by, described conjugated diene unit is made up of butadiene and/or isoprene.
4. transparent type hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene resin according to claim 3, its
It is characterised by, the quality of the butadiene unit of 1,2- structure and/or the isoprene unit of 3,4- structure accounts for conjugated diene unit
The 50%~68% of gross mass.
5. transparent type hydrogenated polystyrene-b- random copolymerizations conjugated diene/styrene resin according to claim 3, its
It is characterised by, described conjugated diene unit is made up of butadiene.
6. prepare transparent type hydrogenated polystyrene-b- random copolymerizations conjugated diene/benzene second described in any one of Claims 1 to 5
The method of olefine resin, it is characterised in that styrene monomer is first subjected to homopolymerization by anionic polymerisation system, after the completion of homopolymerization,
Styrene, conjugated diene and divinylbenzene mix monomer are added in anionic polymerisation system again and carries out random copolymerization, is obtained
Polystyrene-b- random copolymerizations conjugated diene/styrol copolymer, gained polystyrene-b- random copolymerizations conjugated diene/benzene second
Alkene copolymer carries out hydrogenation reaction, produces.
7. method according to claim 6, it is characterised in that homopolymerization temperature is 50 DEG C~60 DEG C, the homopolymerization time is 20min
~25min；Random copolymerization temperature is 50 DEG C~75 DEG C, and the copolymerization time is 20min~25min.
8. method according to claim 6, it is characterised in that lewis base is added during random copolymerization and is adjusted as structure
1,2- is tied in B/S/D random copolymerization blocks in section agent, regulation polystyrene-b- random copolymerizations conjugated diene/styrol copolymer
The butadiene unit of structure and/or the isoprene unit quality of 3,4- structures account for conjugated diene unit gross mass ratio 50%~
68%；Described structure regulator is at least one of tetrahydrofurfuryl alcohol ethylether, double tetrahydrochysene chaff propane；Described structure regulation
Agent consumption is the 0.30~0.40% of total monomer quality.
9. method according to claim 6, it is characterised in that hydrogenation reaction temperature is 70 DEG C~85 DEG C, hydrogenation reaction pressure
Power is 1.2MPa~1.5MPa, hydrogenation reaction time 2 h~2.5 hour；Hydrogenation reaction is in dicyclopentadiene titanium chloride
Carried out under catalytic condition, the consumption of dicyclopentadiene titanium chloride is randomly common for 0.030~0.035g/100g polystyrene-b-
Polymerized conjugated diene/styrol copolymer.
10. method according to claim 6, it is characterised in that polystyrene-b- random copolymerizations conjugated diene/styrene
Iodine number ＜ 4.5g iodine/100g hydrogenated copolymers after copolymer hydrogenation.
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| CN107236102B (en) * | 2016-03-29 | 2020-08-07 | 中国石油化工股份有限公司 | Powdery polystyrene-b-random copolymerization conjugated diene/divinylbenzene rubber and preparation method and application thereof |
| EP3572444B1 (en) * | 2016-04-25 | 2023-06-14 | Asahi Kasei Kabushiki Kaisha | Hydrogenated block copolymer, polypropylene resin composition, and molded body |
| EP4005819A4 (en) * | 2019-06-25 | 2023-09-27 | Nippon Steel Chemical & Material Co., Ltd. | Modified vinylaromatic copolymer, production method therefor, modified conjugated-diene copolymer obtained therefrom and composition thereof, crosslinked rubber object, and tire member |
| CN113563514A (en) * | 2020-04-29 | 2021-10-29 | 中国石油化工股份有限公司 | Hydrogenated polystyrene-conjugated diene random copolymer and preparation method and application thereof |
| CN113563548B (en) * | 2020-04-29 | 2024-01-30 | 中国石油化工股份有限公司 | Hydrogenated bi-component polystyrene-b-conjugated diene copolymer, and preparation method and application thereof |
| CN113278119B (en) * | 2021-07-08 | 2022-09-30 | 广东众和高新科技有限公司 | Hydrogenated styrene-butadiene block copolymer and preparation method and application thereof |
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