CN105175659A - Transparent hydrogenated polystyrene-b-random copolymerized conjugated diene/styrene resin and preparation method therefor - Google Patents
Transparent hydrogenated polystyrene-b-random copolymerized conjugated diene/styrene resin and preparation method therefor Download PDFInfo
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Abstract
The invention discloses transparent hydrogenated polystyrene-b-random copolymerized conjugated diene/styrene resin and a preparation method therefor. The transparent resin is composed of a styrene block and a random copolymerized block of styrene, conjugated diene and divinyl benzene, and the double bond degree of hydrogenation in the conjugated diene unit in the block copolymer reaches over 98%. The preparation method comprises: firstly homopolymerizing a styrene monomer under initiation of lithium alkyl; then carrying out random copolymerization with mixed monomers of styrene, conjugated diene and divinyl benzene; and carrying out hydrogenation reaction on the copolymerized product to obtain the resin. The preparation method is simple, and the prepared hydrogenated polystyrene-b-random copolymerized conjugated diene/styrene resin is high in strength, has the characteristics of being relatively good in processing property and aging resistance, low in turbidity, high in transparency and the like, can be molded by injection and film-drawing, and is wide in application field.
Description
Technical field
The present invention relates to a kind of transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin and preparation method thereof; Belong to modification butadiene styrene resin Material Field.
Background technology
Vinylbenzene and divinyl synthesize random copolymers or segmented copolymer with orientable polymerization under the initiation of lithium alkylide in a solvent, as inlay character S/B=(20-40)/(80-60) in SBS, are generally triblock copolymer; In SBR molecule, S/B=(20-40)/(80-60), is generally random copolymers; SEBS is the hydrogenated products of SBS; SEPS is the hydrogenated products of SIS.These materials are applicable to manufacture resilient material as footwear material, glue paste, handle for tool, tire, medical material etc.Commercially available KR-03, KR-01 is styrene-butadiene transparent resin, wherein S/B=(70-80)/(30-20), molecular structure is the molecular composition of line style and coupling chain, molecular-weight average is Mn=80000-100000, styrene-butadiene transparent resin makes initiator with lithium alkylide in a solvent by vinylbenzene and divinyl, tactic polymerization synthesis has random copolymers and block copolymerization section, finally carry out by epoxidised soybean oil the polymkeric substance that coupling forms side chain, after this polymkeric substance eventually passes dry method desolventizing, form through pelletizing, belong to non-hydrogenated styrene-butadiene polymer, a large amount of unsaturated double-bonds is contained in polyhutadiene section in its molecular structure.Its main characteristic be have high transparent and good shock resistance concurrently, density is little, strong coloring force, processing characteristics excellent, nontoxicity, be widely used in refrigerator manufacture, shoemaking, toy, food product containers, packaging, medicine equipment, daily goods, electrical instrumentation dish and with the field such as other materials (as GPPS, SAN, SMA, PP, HIPS etc.) mixing modification.Compared with other transparent polymer, the feature of K-resin copolymer is that density is low, see more attractive economically, meet the regulation of U.S. food drug control FDA21CFR1771640 clause and European EEC guide 90/128/EEC revised provision, can be used as the packaging of food.Butadiene styrene resin is partially crystalline polymer, good fluidity, the product surface processed is smooth, good luster, transparency are high, traditional processing mode can be adopted to process, although as injected, extruding, the working method such as blown film and curtain coating, hollow blow molding, thermoforming. after styrene-butadiene transparent resin injection molding, mist degree is low, the transparency is high, not ageing-resistant as outdoor use equipment panel and packaging equipment etc., easy yellowing and be full of cracks, the shortcomings such as the life cycle life-span is short.
In existing styrene-butadiene transparent resin technology, to describe with vinylbenzene, divinyl as monomer in (Wang Xingya etc.; the synthesis of transparent butadiene-styrene impact resin and performance [J]; China Synthetic Rubber Industry; 1995) literary composition; s-BuLi is initiator; hexanaphthene is solvent; organoalkoxysilane is coupling agent; by anionic polymerization and coupled reaction; obtained two trade mark transparent butadiene-styrene impact resin with star block structure again through chemical treatment, the experiment investigation impact of polymerization temperature on speed of reaction, the relation of monomer ratio, copolymer structure and resin property.In addition, (QiJun, Studyonstructureandpropertiesofstar-typetransparentimpac tstyrenebutadieneresin [J] .Chinasyntheticresinandplastics, 2011.05.) have studied in a literary composition and make monomer with vinylbenzene and divinyl, initiator is made with n-Butyl Lithium, coupler is made by epoxidised soybean oil, the styrene-butadiene transparent resin synthesized by anionoid polymerization, the molecular mass that have studied polymkeric substance controls and random block control method, examine the relation of shock strength and fluidity of molten and relative molecular mass, and be de-lithium agent with Soda Ash Light 99.2min. or oil-soluble organic acids after polymerization, reach to transparent object to make the resin obtained.
(ZambelliA, Binarycopolymerizationsofstyreneandconjugateddiolefinsin thepresenceofcyclopentadienyltitaniumtrichloride-methyla luminoxane [J], MacromolChemPhys, 1994.) describe in a literary composition conventional styrene-ethylene/butylene-vinylbenzene triblock polymer (SEBS) preparation be in cyclohexane solvent, there is divinyl, vinylbenzene is raw material, metallocene is catalyzer, n-Butyl Lithium is initiator, polar solvent tetrahydrofuran (THF) obtains for control contents of ethylene carries out polymerization.
At present, to cyclopentadienyl titanium dichloride/butyllithium, investigator is that two-pack catalyst system Hydrogenated SBS prepares the research of SEBS more, as USA4501875, USA3595942, CN1166498A etc.
The hydrogenation of block type styrene-conjugated diolefine lithium series of polymer uses luxuriant-titanium system catalysis and nickel system shortening usually, and wherein luxuriant-titanium catalyst system can by the whole hydrogenation of polyhutadiene section in SBS.As Chinese patent ZL97108078.4, US Patent No. P4980421 (1990), European patent EP 0471415 (1991) etc. provide a kind of method for hydrogenation to styrene-butadiene polymer, its degree of hydrogenation reaches 99.5%.US Patent No. P5132372 (1992), US Patent No. P5206307 (1993) etc. provide the method for a kind of nickel system shortening styrene-conjugated diene polymkeric substance, and in polymkeric substance, particularly polyisoprene section can all hydrogenation.Above-mentioned block type polymers embodies the behavior of thermoplastic elastomer.
In addition, SSBR is raw material by divinyl, vinylbenzene, and n-Butyl Lithium is initiator, Lewis base is conditioning agent, contents of ethylene when controlling polymerizing butadiene in polyreaction and obtain random copolymers, does not carry out hydrotreatment, is mainly used as tire in SSBR preparation process.The business-like product of SSBR has Solprene1204, Y-031 and HPR-850 etc.
At present, the polymkeric substance carrying out hydrogenation as the butylbenzene copolymer of high styrenic percentage does not also have reported in literature.
Summary of the invention
Exist not ageing-resistant for after styrene-butadiene transparent resin injection molding in prior art as outdoor use equipment, panel and packaging equipment etc., easy yellowing and be full of cracks, the shortcomings such as the life cycle life-span is short; The object of the invention is to be to provide that a kind of chemical stability is good, ultraviolet light, heat-resisting, weather-proof, resistance to ozone, and there is the transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin of higher elasticity, high-impact, high extension at break, high strength, this resin is applicable to preparation outdoor instrument, wrapping material, sheet material and instrument panel etc., can also in preparing the medical devices such as tubing, infusion bag, needle tubing.
Another object of the present invention be to provide a kind of simple to operate, reaction conditions is gentle, prepares the method for described transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin.
In order to realize technical purpose of the present invention, the invention provides a kind of transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin, this resin is obtained by the segmented copolymer hydrogenation with formula 1 chemical expression:
S
1-B/S/D
Formula 1
Wherein,
S
1for the homopolymerization block that styrene units be made up of of number-average molecular weight in 40000 ~ 45000 scopes;
B/S/D is the random copolymerization block that styrene units, conjugated diene unit and divinylbenzene units be made up of of number-average molecular weight in 50000 ~ 55000 scopes;
Hydrogenation degree >=98% of conjugated diene unit in B/S/D random copolymerization block;
S
1in-B/S/D segmented copolymer, styrene units total mass is 45 ~ 80:55 ~ 20 with the ratio of conjugated diene unit total mass.
In preferred transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin, conjugated diene unit is made up of divinyl and/or isoprene.
More preferably in transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin, the quality of the butadiene unit of 1,2-structure and/or the isoprene unit of 3,4-structure accounts for 50% ~ 68% of conjugated diene unit total mass.
More preferably in transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin, conjugated diene unit is made up of divinyl.The quality of the butadiene unit of 1,2-structure accounts for 50% ~ 68% of conjugated diene unit total mass.
More preferably in transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin, the inlay character S/B of styrene units and conjugated diene unit is 35 ~ 80:65 ~ 20.
In preferred transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin, the quality of divinylbenzene units is S
10.08 ‰ ~ 0.14 ‰ of-B/S/I/D block copolymerization amount.By introducing a small amount of divinylbenzene units by S
1-B/S/D segmented copolymer carries out cladodification.
In preferred transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene copolymer resin, S
1in homopolymerization block, the quality of styrene units is 50 ~ 60% of total styrene units quality; Remaining styrene units is distributed in B/S/D random copolymerization block.Styrene units is at S
1distribution form in-B/S/I/D segmented copolymer, prevents S
1polymer formation crystallization after-B/S/I/D segmented copolymer hydrogenation, increases the transparency and the intensity of polymkeric substance.
Present invention also offers a kind of method preparing transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin, the method first styrene monomer is carried out homopolymerization by anionoid polymerization system, after homopolymerization completes, in anionoid polymerization system, add vinylbenzene, conjugated diolefine and Vinylstyrene mix monomer again carry out random copolymerization, obtain polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer, gained polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer carries out hydrogenation reaction, to obtain final product.
In preferred method, homopolymerization temperature is 50 DEG C ~ 60 DEG C, and the homopolymerization time is 20min ~ 25min.
In preferred method, random copolymerization temperature is 50 DEG C ~ 75 DEG C, and the copolymerization time is 20min ~ 25min.
In preferred method, add Lewis base in random copolymerization process and to regulate in polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer in B/S/D random copolymerization block 1 as structure regulator, the butadiene unit of 2-structure and/or the isoprene unit quality of 3,4-structure account for the ratio 50% ~ 68% of conjugated diene unit total mass.The appropriate butadiene unit of 1,2-structure or the isoprene unit of 3,4-structure can ensure the S that hydrogenation is closed
1-B/S/D segmented copolymer has suitable elasticity and extension at break.
In preferred method, structure regulator is at least one in tetrahydrofurfuryl alcohol ethyl ether, two tetrahydrochysene chaff propane.Preferred structure regulator is more conducive to the fine adjustment ability of 1,2-structure of butadiene unit or 3,4-structural contents of isoprene.
In preferred method, structure regulator consumption is 0.30 ~ 0.40% of total monomer quality.
In preferred method, hydrogenation reaction temperature is 70 DEG C ~ 85 DEG C, and hydrogenation reaction pressure is 1.2MPa ~ 1.5MPa, hydrogenation reaction time 2 h ~ 2.5 hour.
In preferred method, hydrogenation reaction is carried out under dicyclopentadiene titanium dichloride catalytic condition, and the consumption of dicyclopentadiene titanium dichloride is 0.030 ~ 0.035g/100g polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer.
In preferred method, the iodine number < 4.5g iodine/100g hydrogenated copolymer after polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer hydrogenation.
In preferred preparation method, the iodine number < 4.5g iodine after polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer hydrogenation/100g hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer; Hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer hydrogenation degree >=98%.
In preferred preparation method, in the glue of hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer, add that the cyclohexane solution of 4 ~ 5wt% isocaprylic acid and active catalyst carry out stopping, decomposition reaction forms water miscible isocaprylic acid lithium, lithium chloride and water miscible titaniferous compound in being soluble in the aqueous phase.Wherein, isocaprylic acid/butyllithium (molecular ratio)=(1.1 ~ 1.2): 1.
The concrete preparation method of transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin of the present invention is as follows:
1, in polymeric kettle, add cyclohexane and normal hexane mixed solvent, then add structure regulator, after stirring, styrene monomer is joined after stirring further in polymeric kettle, with the reaction of appropriate butyllithium-initiated polymerization, at 50 ~ 60 DEG C, after reaction 20 ~ 25min; Add the mix monomer of vinylbenzene, divinyl and Vinylstyrene again, react 20 ~ 25min at 50 ~ 75 DEG C after, obtain polystyrene-block-random copolymerization conjugated diolefine/styrol copolymer, molecular weight and the contents of ethylene that gpc analysis surveys polymkeric substance is done in sampling.
2, polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer is moved in hydriding reactor, and add hydrogenation catalyst dicyclopentadiene titanium dichloride, the temperature of hydrogenation reaction is 70 ~ 85 DEG C, it is 1.2 ~ 1.5MPa that hydrogen passes into pressure, the hydrogenation time is 2 ~ 2.5 hours, after hydrogenation completes, the cyclohexane solution and the hydrogenation activity catalyzer that add isocaprylic acid stop, decomposition reaction 15min, then add deionized water and carry out washing stirring 10 ~ 15min, after finally separating aqueous phase, add the antioxidant 1076 of total resin demand 0.25wt% again and stir 10 ~ 20min, afterwards by glue discharging, condense glue with ethanol and separate out resin, again resin carried out hot-air dry and obtain, finally survey the iodine number of hydropolymer.
Hinge structure, the invention has the beneficial effects as follows:
The present invention obtains one end first and has styrene block, and the other end has the hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer of side chain distribution or lightly crosslinked S/B/D block of random copolymer; Its special molecular structure imparts the hydrogenated polystyrene-block-random copolymerization conjugated diolefine/styrol copolymer good springiness of the good thermotolerance of block polymer, resistance to deterioration, weather-proof, resistance to ozone, uvioresistant, stretch breaking strength, resistance to impact shock, the transparency, processibility and film-forming properties, particularly high butadienyl content, elongation at break is high; This block polymer can injection molding and two-way stretch film forming, the features such as its product surface is clear, goods turbidity is low.
Transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin prepared by the present invention, during inlay character S/B=(35 ~ 80)/(65 ~ 20) of phenylethylene/butadiene, its elongation rate of tensile failure >=200%, hardness (ShoreD)≤65, then be applicable to transparent film material, as packing film, tubing, infusion bag, electric wire foreskin, handle for tool etc.If S/B=(70-80)/(30-20) elongation rate of tensile failure < 150%, hardness (ShoreD) > 70, then be applicable to plastic material, as clear sheet, instrument panel, packing box etc.
Hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer mature preparation process of the present invention, raw material sources are wide, meet demand of industrial production.
Embodiment
Following examples are intended to be described content of the present invention, and the protection domain of the claims in the present invention is not by the restriction of embodiment.
Measure the number-average molecular weight of polymkeric substance with gel permeation chromatograph (GPC) in the following example.
H-NMR is adopted to compose the microtexture content of quantitative assay polymkeric substance.
INSTRON-5565 electronic tensile machine is adopted to measure the physicals of polymkeric substance.
Embodiment 1
The cyclohexane solution 3500mL that massfraction is the normal hexane of 10% is added in 5 liters of steel steel polymeric kettles under nitrogen protection, then 1.36mL tetrahydrofurfuryl alcohol ethyl ether is added, after being warming up to 50 ~ 60 DEG C with hot water, 80g vinylbenzene to be added in polymeric kettle and to open stirring, then polymeric kettle is entered, after reaction 20 ~ 25min with the n-Butyl Lithium 12mL of syringe injection 0.5mol/L; Add the mix monomer of the divinylbenzene of 292.5g divinyl and 77.5g vinylbenzene and 0.03mL again, react 25min at 50 ~ 75 DEG C after; Record the vinyl mass content 50.6% of butadiene segment in polymkeric substance, polymkeric substance number-average molecular weight Mn=82000.
Then, after polymkeric substance is pressed into hydriding reactor, add the dicyclopentadiene titanium dichloride 0.13g of mass fraction 99%, control hydrogen pressure 1.2MPa, at 70 ~ 85 DEG C, stirring reaction is after 2 hours, hydrogenation glue is moved into and stops still, the cyclohexane solution 25mL and the hydrogenation activity catalyzer that now add 4.2wt% isocaprylic acid stop, decomposition reaction 15min, then add deionized water 300mL to carry out washing and stirring 10-15min, after finally separating aqueous phase, in glue, add antioxidant 1076 1.2g again and stir 15min, afterwards by glue discharging, glue is condensed with ethanol, now resin segregation, again resin carried out 70 DEG C of hot-air dries and obtain, record hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer hydrogenation degree 98.2%, melt flow rate (MFR) (MFR) is 10.43g/10min (testing under conventional criteria condition).
Embodiment 2
The cyclohexane solution 3500mL that massfraction is the normal hexane of 10% is added in 5 liters of steel steel polymeric kettles under nitrogen protection, then 1.54mL tetrahydrofurfuryl alcohol ethyl ether is added, after being warming up to 50 ~ 60 DEG C with hot water, 100g vinylbenzene to be added in polymeric kettle and to open stirring, then polymeric kettle is entered, after reaction 20 ~ 25min with the n-Butyl Lithium 11mL of syringe injection 0.5mol/L; Add the mix monomer of the divinylbenzene of 247.5g divinyl and 102.5g vinylbenzene and 0.04mL again, react 25min at 50 ~ 75 DEG C after; Record the vinyl mass content 57.6% of butadiene segment in polymkeric substance, polymkeric substance number-average molecular weight Mn=96000.
Then, after polymkeric substance is pressed into hydriding reactor, add the dicyclopentadiene titanium dichloride 0.14g of mass fraction 99%, control hydrogen pressure 1.3MPa, at 70 ~ 85 DEG C, stirring reaction is after 2 hours, hydrogenation glue is moved into and stops still, the cyclohexane solution 25mL and the hydrogenation activity catalyzer that now add 4.2wt% isocaprylic acid stop, decomposition reaction 15min, then add deionized water 300mL to carry out washing and stirring 10-15min, after finally separating aqueous phase, in glue, add antioxidant 1076 1.2g again and stir 15min, afterwards by glue discharging, glue is condensed with ethanol, now resin segregation, again resin carried out the hot-air dry at 70 DEG C and obtain, record hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer hydrogenation degree 99.1%, MFR is 9.47g/10min (testing under conventional criteria condition).
Embodiment 3
The cyclohexane solution 3500mL that massfraction is the normal hexane of 10% is added in 5 liters of steel steel polymeric kettles under nitrogen protection, then the two tetrahydrochysene chaff chaff propane of 1.60mL is added, after being warming up to 50 ~ 60 DEG C with hot water, 140g vinylbenzene to be added in polymeric kettle and to open stirring, then polymeric kettle is entered, after reaction 20 ~ 25min with the n-Butyl Lithium 10mL of syringe injection 0.5mol/L; Add the mix monomer of the divinylbenzene of 202.5g divinyl and 107.5g vinylbenzene and 0.06mL again, react 25min at 50 ~ 75 DEG C after; Record the vinyl mass content 62.5% of butadiene segment in polymkeric substance, polymkeric substance number-average molecular weight Mn=104000.
Then, after polymkeric substance is pressed into hydriding reactor, add the dicyclopentadiene titanium dichloride 0.14g of mass fraction 99%, control hydrogen pressure 1.5MPa, at 70 ~ 85 DEG C, stirring reaction is after 2 hours, hydrogenation glue is moved into and stops still, the cyclohexane solution 25mL and the hydrogenation activity catalyzer that now add 4.2wt% isocaprylic acid stop, decomposition reaction 15min, then add deionized water 300mL to carry out washing and stirring 10-15min, after finally separating aqueous phase, in glue, add antioxidant 1076 1.2g again and stir 15min, afterwards by glue discharging, glue is condensed with ethanol, now resin segregation, again resin carried out the hot-air dry at 70 DEG C and obtain, record hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer hydrogenation degree 99.4%, MFR is 8.14g/10min (testing under conventional criteria condition).
Embodiment 4
The cyclohexane solution 3500mL that massfraction is the normal hexane of 10% is added in 5 liters of steel steel polymeric kettles under nitrogen protection, then the two tetrahydrochysene chaff chaff propane of 1.70mL is added, after being warming up to 50 ~ 60 DEG C with hot water, 180g vinylbenzene to be added in polymeric kettle and to open stirring, then polymeric kettle is entered, after reaction 20 ~ 25min with the n-Butyl Lithium 9.5mL of syringe injection 0.5mol/L; Add the mix monomer of the divinylbenzene of 157.5g divinyl and 112.5g vinylbenzene and 0.05mL again, react 25min at 50 ~ 75 DEG C after; Record the vinyl mass content 65.3% of butadiene segment in polymkeric substance, polymkeric substance number-average molecular weight Mn=113000.
Then, after polymkeric substance is pressed into hydriding reactor, add the dicyclopentadiene titanium dichloride 0.13g of mass fraction 99%, control hydrogen pressure 1.5MPa, at 70 ~ 85 DEG C, stirring reaction is after 2 hours, hydrogenation glue is moved into and stops still, the cyclohexane solution 25mL and the hydrogenation activity catalyzer that now add 4.2wt% isocaprylic acid stop, decomposition reaction 15min, then add deionized water 300mL to carry out washing and stirring 10-15min, after finally separating aqueous phase, in glue, add antioxidant 1076 1.2g again and stir 15min, afterwards by glue discharging, glue is condensed with ethanol, now resin segregation, again resin carried out the hot-air dry at 70 DEG C and obtain, record hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer hydrogenation degree 98.6%, MFR is 8.03g/10min (testing under conventional criteria condition).
Embodiment 5
The cyclohexane solution 3500mL that massfraction is the normal hexane of 10% is added in 5 liters of steel steel polymeric kettles under nitrogen protection, then 1.80mL tetrahydrofurfuryl alcohol ethyl ether is added, after being warming up to 50 ~ 60 DEG C with hot water, 150g vinylbenzene to be added in polymeric kettle and to open stirring, then polymeric kettle is entered, after reaction 20 ~ 25min with the n-Butyl Lithium 8.0mL of syringe injection 0.5mol/L; Add the mix monomer of the divinylbenzene of 135g divinyl and 165g vinylbenzene and 0.06mL again, react 25min at 50 ~ 75 DEG C after; Record the vinyl mass content 68.6% of butadiene segment in polymkeric substance, polymkeric substance number-average molecular weight Mn=124000.
Then, after polymkeric substance is pressed into hydriding reactor, add the dicyclopentadiene titanium dichloride 0.15g of mass fraction 99%, control hydrogen pressure 1.5MPa, at 70 ~ 85 DEG C, stirring reaction is after 2 hours, hydrogenation glue is moved into and stops still, the cyclohexane solution 25mL and the hydrogenation activity catalyzer that now add 4.2wt% isocaprylic acid stop, decomposition reaction 15min, then add deionized water 300mL to carry out washing and stirring 10-15min, after finally separating aqueous phase, in glue, add antioxidant 1076 1.2g again and stir 15min, afterwards by glue discharging, glue is condensed with ethanol, now resin segregation, again resin carried out the hot-air dry at 70 DEG C and obtain, record hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer hydrogenation degree 99.4%, MFR is 7.65g/10min (testing under conventional criteria condition).
Embodiment 6
The cyclohexane solution 3500mL that massfraction is the normal hexane of 10% is added in 5 liters of steel steel polymeric kettles under nitrogen protection, then the two tetrahydrochysene chaff chaff propane of 1.80mL is added, after being warming up to 50 ~ 60 DEG C with hot water, 150g vinylbenzene to be added in polymeric kettle and to open stirring, then polymeric kettle is entered, after reaction 20 ~ 25min with the n-Butyl Lithium 8.5mL of syringe injection 0.5mol/L; Add the mix monomer of the divinylbenzene of 112.5g divinyl and 187.5g vinylbenzene and 0.04mL again, react 25min at 50 ~ 75 DEG C after; Record the vinyl mass content 71.3% of butadiene segment in polymkeric substance, polymkeric substance number-average molecular weight Mn=115000.
Then, after polymkeric substance is pressed into hydriding reactor, add the dicyclopentadiene titanium dichloride 0.15g of mass fraction 99%, control hydrogen pressure 1.4MPa, at 70 ~ 85 DEG C, stirring reaction is after 2 hours, hydrogenation glue is moved into and stops still, the cyclohexane solution 25mL and the hydrogenation activity catalyzer that now add 4.2wt% isocaprylic acid stop, decomposition reaction 15min, then add deionized water 300mL to carry out washing and stirring 10-15min, after finally separating aqueous phase, in glue, add antioxidant 1076 1.2g again and stir 15min, afterwards by glue discharging, glue is condensed with ethanol, now resin segregation, again resin carried out the hot-air dry at 70 DEG C and obtain, record hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer hydrogenation degree 99.5%, MFR is 8.32g/10min (testing under conventional criteria condition).
Embodiment 7
The cyclohexane solution 3500mL that massfraction is the normal hexane of 10% is added in 5 liters of steel steel polymeric kettles under nitrogen protection, then the two tetrahydrochysene chaff chaff propane of 1.60mL is added, after being warming up to 50 ~ 60 DEG C with hot water, 180g vinylbenzene to be added in polymeric kettle and to open stirring, then polymeric kettle is entered, after reaction 20 ~ 25min with the n-Butyl Lithium 8.5mL of syringe injection 0.5mol/L; Add the mix monomer of the divinylbenzene of 90g divinyl and 180g vinylbenzene and 0.03mL again, react 25min at 50 ~ 75 DEG C after; Record the vinyl mass content 65.3% of butadiene segment in polymkeric substance, polymkeric substance number-average molecular weight Mn=119000.
Then, after polymkeric substance is pressed into hydriding reactor, add the dicyclopentadiene titanium dichloride 0.13g of mass fraction 99%, control hydrogen pressure 1.4MPa, at 70 ~ 85 DEG C, stirring reaction is after 2 hours, hydrogenation glue is moved into and stops still, the cyclohexane solution 25mL and the hydrogenation activity catalyzer that now add 4.2wt% isocaprylic acid stop, decomposition reaction 15min, then add deionized water 300mL to carry out washing and stirring 10-15min, after finally separating aqueous phase, in glue, add antioxidant 1076 1.2g again and stir 15min, afterwards by glue discharging, glue is condensed with ethanol, now resin segregation, again resin carried out the hot-air dry at 70 DEG C and obtain, record hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer hydrogenation degree 98.4%, MFR is 8.02g/10min (testing under conventional criteria condition).
Embodiment 9
After hydrogenated polystyrene-block-random copolymerization conjugated diolefine/styrene copolymerized transparent resin in embodiment 1 ~ 8 is carried out injection moulding, its physicals is as table 1.
Hydrogenated polystyrene-block-random copolymerization conjugated diolefine in table 1 embodiment 1 ~ 8/styrene copolymerized transparent resin physicals
Claims (12)
1. transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin, its spy is, is obtained by the segmented copolymer hydrogenation with formula 1 chemical expression:
S
1-B/S/D
Formula 1
Wherein,
S
1for the homopolymerization block that styrene units be made up of of number-average molecular weight in 40000 ~ 45000 scopes;
B/S/D is the random copolymerization block that styrene units, conjugated diene unit and divinylbenzene units be made up of of number-average molecular weight in 50000 ~ 55000 scopes;
Hydrogenation degree >=98% of conjugated diene unit in B/S/D random copolymerization block;
S
1in-B/S/D segmented copolymer, styrene units total mass is 45 ~ 80:55 ~ 20 with the ratio of conjugated diene unit total mass.
2. transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin according to claim 1, is characterized in that, S
1in homopolymerization block, the quality of styrene units is 50 ~ 60% of total styrene units quality.
3. transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin according to claim 1, it is characterized in that, described conjugated diene unit is made up of divinyl and/or isoprene.
4. transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin according to claim 3, it is characterized in that, the quality of the butadiene unit of 1,2-structure and/or the isoprene unit of 3,4-structure accounts for 50% ~ 68% of conjugated diene unit total mass.
5. transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin according to claim 3, it is characterized in that, described conjugated diene unit is made up of divinyl.
6. transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin according to claim 1, it is characterized in that, the inlay character S/B of styrene units and conjugated diene unit is 35 ~ 80:65 ~ 20.
7. transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin according to claim 1, it is characterized in that, the quality of divinylbenzene units is S
10.08 ‰ ~ 0.14 ‰ of-B/S/I/D block copolymerization amount.
8. prepare the method for the transparent type hydrogenated polystyrene-b-random copolymerization conjugated diolefine/styrene resin described in any one of claim 1 ~ 7, it is characterized in that, first styrene monomer is carried out homopolymerization by anionoid polymerization system, after homopolymerization completes, in anionoid polymerization system, add vinylbenzene, conjugated diolefine and Vinylstyrene mix monomer again carry out random copolymerization, obtain polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer, gained polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer carries out hydrogenation reaction, to obtain final product.
9. method according to claim 8, is characterized in that, homopolymerization temperature is 50 DEG C ~ 60 DEG C, and the homopolymerization time is 20min ~ 25min; Random copolymerization temperature is 50 DEG C ~ 75 DEG C, and the copolymerization time is 20min ~ 25min.
10. method according to claim 8, it is characterized in that, Lewis base is added as structure regulator in random copolymerization process, to regulate in polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer in B/S/D random copolymerization block 1, the butadiene unit of 2-structure and/or the isoprene unit quality of 3,4-structure account for 50% ~ 68% of conjugated diene unit total mass ratio; Described structure regulator is at least one in tetrahydrofurfuryl alcohol ethyl ether, two tetrahydrochysene chaff propane; Described structure regulator consumption is 0.30 ~ 0.40% of total monomer quality.
11. methods according to claim 8, is characterized in that, hydrogenation reaction temperature is 70 DEG C ~ 85 DEG C, and hydrogenation reaction pressure is 1.2MPa ~ 1.5MPa, hydrogenation reaction time 2 h ~ 2.5 hour; Hydrogenation reaction is carried out under dicyclopentadiene titanium dichloride catalytic condition, and the consumption of dicyclopentadiene titanium dichloride is 0.030 ~ 0.035g/100g polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer.
12. methods according to claim 8, is characterized in that, the iodine number < 4.5g iodine/100g hydrogenated copolymer after polystyrene-b-random copolymerization conjugated diolefine/styrol copolymer hydrogenation.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107236102A (en) * | 2016-03-29 | 2017-10-10 | 中国石油化工股份有限公司 | A kind of powdered polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber and its preparation method and application |
| CN109071741A (en) * | 2016-04-25 | 2018-12-21 | 旭化成株式会社 | Hydrogenated block copolymer, polypropylene resin composite and formed body |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1153183A (en) * | 1996-10-09 | 1997-07-02 | 北京燕山石油化工公司研究院 | Butadiene-isoprene-styrene block copolymer and preparing method thereof |
| CN1269371A (en) * | 2000-04-20 | 2000-10-11 | 江苏圣杰实业有限公司 | Preparation of conjugated diene and/or monovinyl arene polymer |
| CN1640903A (en) * | 2004-01-17 | 2005-07-20 | 中国石化北京燕化石油化工股份有限公司 | Phenylethylene-isoprene/butadiene-phenylethylene ternary block copolymer and its preparation method |
| CN101475674A (en) * | 2009-01-15 | 2009-07-08 | 浙江三博聚合物有限公司 | Preparation of phenylethylene-dialkene special copolymer |
| CN101495527A (en) * | 2006-08-08 | 2009-07-29 | 旭化成化学株式会社 | Hydrogenated block copolymers and crosslinking compositions conatining the same |
-
2015
- 2015-07-23 CN CN201510437128.9A patent/CN105175659B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1153183A (en) * | 1996-10-09 | 1997-07-02 | 北京燕山石油化工公司研究院 | Butadiene-isoprene-styrene block copolymer and preparing method thereof |
| CN1269371A (en) * | 2000-04-20 | 2000-10-11 | 江苏圣杰实业有限公司 | Preparation of conjugated diene and/or monovinyl arene polymer |
| CN1640903A (en) * | 2004-01-17 | 2005-07-20 | 中国石化北京燕化石油化工股份有限公司 | Phenylethylene-isoprene/butadiene-phenylethylene ternary block copolymer and its preparation method |
| CN101495527A (en) * | 2006-08-08 | 2009-07-29 | 旭化成化学株式会社 | Hydrogenated block copolymers and crosslinking compositions conatining the same |
| CN101475674A (en) * | 2009-01-15 | 2009-07-08 | 浙江三博聚合物有限公司 | Preparation of phenylethylene-dialkene special copolymer |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107236102A (en) * | 2016-03-29 | 2017-10-10 | 中国石油化工股份有限公司 | A kind of powdered polystyrene-b- random copolymerizations conjugated diene/divinylbenzene rubber and its preparation method and application |
| CN109071741A (en) * | 2016-04-25 | 2018-12-21 | 旭化成株式会社 | Hydrogenated block copolymer, polypropylene resin composite and formed body |
| CN109071741B (en) * | 2016-04-25 | 2021-03-16 | 旭化成株式会社 | Hydrogenated block copolymer, polypropylene resin composition, and molded article |
| CN113966350A (en) * | 2019-06-25 | 2022-01-21 | 日铁化学材料株式会社 | Modified vinyl aromatic copolymer and method for producing same, modified conjugated diene copolymer obtained therefrom, composition of modified conjugated diene copolymer, crosslinked rubber, and tire member |
| 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 |
| CN112480341A (en) * | 2019-09-12 | 2021-03-12 | 中国石油化工股份有限公司 | Branched polystyrene-b-conjugated diene diblock copolymer and preparation method and application thereof |
| CN112480341B (en) * | 2019-09-12 | 2024-05-03 | 中国石油化工股份有限公司 | Branched polystyrene-b-conjugated diene diblock copolymer, and preparation method and application thereof |
| CN113563548A (en) * | 2020-04-29 | 2021-10-29 | 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 |
| 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 |
| CN113563549A (en) * | 2020-04-29 | 2021-10-29 | 中国石油化工股份有限公司 | Asymmetric branched polystyrene-b-polyethylene-butylene-propylene-isopropylene multi-micro block copolymer and preparation method 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 |
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| CN113563514B (en) * | 2020-04-29 | 2024-06-07 | 中国石油化工股份有限公司 | Hydrogenated polystyrene-conjugated diene random copolymer and preparation method and application thereof |
| CN113278119A (en) * | 2021-07-08 | 2021-08-20 | 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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