CN103030756B - Styrene-butadiene copolymer as well as preparation and applications thereof - Google Patents
Styrene-butadiene copolymer as well as preparation and applications thereof Download PDFInfo
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Abstract
The invention relates to a styrene-butadiene copolymer as well as a preparation method and applications thereof. The styrene-butadiene copolymer is obtained by regulating an arrangement mode of a polystyrene chain segment and a polybutadiene chain segment, wherein the polybutadiene chain segment can freely move. The copolymer is mainly used for preparing high-gloss and high-impact-resistance polystyrene. According to the styrene-butadiene copolymer provided by the invention, the viscosity of 5 % styrene solution of the styrene-butadiene copolymer is low, the styrene-butadiene copolymer exists in a polystyrene polymer molecular chain mainly in a block mode when being added into the polystyrene, can also freely flow in the polystyrene, can be used for improving the physical and mechanical properties of the polystyrene and is particularly used for keeping high gloss of the polystyrene when the properties are impacted.
Description
Technical field
The present invention relates to a kind of styrene-butadiene copolymer and its preparation method and application.In particular, the present invention is by the adjustment of the arrangement mode of p-poly-phenyl ethene segment, polybutadiene segments, obtain the polymerization process of the freely movable styrene-butadiene copolymer of polybutadiene segments energy and this multipolymer, and the application of this multipolymer, hit polystyrene for the preparation of high-gloss high-impact.
Background technology
High-impact polystyrene, for add synthetic rubber in styrene monomer, carries out radical polymerization, obtained chemical graft type high-impact polystyrene.Wherein used synthetic rubber is mainly polybutadiene rubber, is divided into low cis polybutadiene rubber and cis-rich polybutadiene rubber.Adopt the shock strength of the polystyrene of polybutadiene rubber modification greatly to increase, but while polystyrene shock strength improves, the gloss of product decline greatly.In order to both improve the shock strength of polystyrene, can retain again the high gloss of polystyrene, people have done a lot of research.
Beijing swallowization CN 1031406 discloses and is a kind ofly applicable to high-cis 1，4-polybutadiene preparing high impact resistance polystyrene and preparation method thereof.Adopt nickel-aluminium-B catalyst system, product polyhutadiene cis-Isosorbide-5-Nitrae structural content >=93% of this invention preparation, 25 DEG C of 5% vinylbenzene viscosity is 50-139mpa.s, and vinylbenzene insolubles content is less than 0.03%.The high-cis 1，4-polybutadiene of this invention is for the preparation of high-impact polystyrene, and obtained high-impact polystyrene shock strength is high, slightly improves the glossiness of goods.
Beijing swallowization CN 1289551C discloses a kind of 1, the polymerization process of 3 divinyl, under it is included in batchwise polymerization system, lithium alkylide is adopted to make initiator, containing in the saturated hydrocarbon solvent of polar modifier, caused the homopolymer generating different molecular weight and distribution by two steps, then with four-functional group Lewis acid for coupling agent, the low-cis-polybutadiene of wide molecular weight distribution is prepared in coupling.Its distinguishing feature is to broaden molecular weight distribution, improves the colourity of rubber 5% vinylbenzene glue, for polystyrene resin modification, obviously improves the glossiness of high-impact polystyrene.The polybutadiene rubber of this invention is used for modified polystyrene, and glossiness increases, but glossiness is no more than 50.
Styrene-butadiene block copolymer, due to containing polystyrene block, very high with the phase solubility of polystyrene energy, the product that particle diameter is less than 1 μm can be produced like this, make modified polystyrene have high gloss and high impact resistance.
Tradition block SBS molecular composition by polystyrene segment (S)-polybutadiene segments (B)-polystyrene segment (S) this three pitch chains section is mutually embedding forms, PS segment is as physical crosslinking point, limit the ability to act of SBS, make to be easy to form cross-linked polymer in toughness reinforcing HIPS process, form supramolecular.
Summary of the invention
An object of the present invention is to provide a kind of styrene-butadiene copolymer, 5% styrene solution viscosity of this multipolymer is low, when hitting polystyrene for the preparation of high-gloss high-impact, can improve glossiness and the impact property of polystyrene.
Another object of the present invention is to provide the preparation method of the styrene-butadiene copolymer of linear structure of the present invention, reduces by 5% styrene solution viscosity of multipolymer.
Another object of the present invention is to provide the preparation method of the styrene-butadiene copolymer of star structure of the present invention, reduces by 5% styrene solution viscosity of multipolymer, and improves coupling degree and the coupling efficiency of multipolymer.
Last object of the present invention is to provide the application of styrene-butadiene copolymer of the present invention, for the preparation of hitting property of high-gloss high-impact polystyrene HIPS.
Technical scheme design of the present invention is as follows:
Traditional polystyrene segment (S)-polybutadiene segments (B)-polystyrene segment (S) SBS molecule is because PS segment is as physical crosslinking point, limit the ability to act of SBS, therefore original SBS product due to 5% styrene solution viscosity high, easily be cross-linked when preparing high impact polystyrene, during toughening rubber as polystyrene, shock strength increases, but glossiness is no more than 50.In order to reduce by 5% styrene solution viscosity of styrene-butadiene copolymer, some adjustment must be done to the structure of styrene-butadiene copolymer, removing the physical crosslinking of PS segment, make polybutadiene segments energy freely movable.And this multipolymer is adapted at original SBS device is produced.The different structure of what the present inventor was extensive and deep have studied styrene-butadiene block copolymer, develop a kind of styrene-butadiene copolymer, by the design to this styrene-butadiene copolymer structure, enable to hit polystyrene for making high-gloss high-impact, 5% styrene solution viscosity of the styrene-butadiene block copolymer of this structure is low, be conducive to the polymerization process that high-gloss high-impact hits polystyrene, be free state preparing when high-gloss high-impact hits polystyrene, can unrestricted flow in polystyrene, be conducive to the glossiness keeping polystyrene, and greatly can improve the physical and mechanical property of polystyrene, especially impact property.
In the present invention, the standard of " high impact-resistant " is: the shock strength of ISO 180 setup test polystyrene batten reaches 9-15kJ/m
2.After described " high impact-resistant " refers in polystyrene and add 2-15% massfraction styrene-butadiene copolymer of the present invention, shock strength not only meets the standard of " high impact-resistant ", and is greatly enhanced.
In the present invention, described " high gloss " refers to that the HIPS particle size that styrene-butadiene copolymer of the present invention obtains is little, has good glossiness.Concrete, the standard of " high gloss " is: ASTM D2457 tests polystyrene batten glossiness and reaches more than 50.
Kinetic viscosity when term " 5% vinylbenzene viscosity " refers to that 5% (wt) of the present invention styrene-butadiene copolymer is dissolved in liquid styrene 25 DEG C in the present invention.
A kind of styrene-butadiene block copolymer of the present invention, has the linear structure of general formula I, or has the star structure of general formula I I, or have the combination of the linear structure of general formula I and the star structure of general formula I I; The number-average molecular weight of described styrene-butadiene block copolymer is 150,000-60 ten thousand, molecular weight distribution is 1.01-1.2, styrene units accounts for the 10-60% of copolymer quality, butadiene unit accounts for the 40-90% of copolymer quality, the butadiene unit of 1,2-structure accounts for the 10-45% of butadiene unit total mass;
The general formula I of described linear structure is: (PS
a-PB
b),
The general formula I I of described star structure is: (PB
n-PS
m-PB
k)
zr,
PS represents the polymer segment derived from styrene monomer,
PB represents the polymer segment of derived from butadiene monomer,
A, b, m, n and k represent the polymerization degree of respective polymer segment,
A or m is independently selected within the scope of 100-2000 separately, preferably within the scope of 150-1800, more preferably within the scope of 200-1500;
B or n is independently selected within the scope of 1000-8000 separately, preferably within the scope of 1500-7000, more preferably within the scope of 2000-6500;
K is 1-100, is preferably 1-80, is more preferably 1-50;
Z represents the arm number of star structure, and z is the integer of 2-8;
R represents the coupling centers " core " of star structure, and the alkyl that R is Si, Sn, total C number is 4-18 or total C number are the aromatic base etc. of 8-22.
In styrene-butadiene copolymer of the present invention, styrene units accounts for the 10-60% of copolymer quality, is preferably 20-60%, is more preferably 25-55%.Styrene units accounts for the content of copolymer quality lower than 10%, and obtained HIPS glossiness is lower, and content is higher than 60%, and the shock resistance of obtained HIPS reduces.
In styrene-butadiene copolymer of the present invention, butadiene unit accounts for the 40-90% of copolymer quality, is preferably 40-80%, be more preferably 45-75%, wherein, 1, the butadiene hydrocarbon unit of 2-structure accounts for 10 ~ 45% of butadiene hydrocarbon unit total mass, is preferably 10-35%.The content that the butadiene hydrocarbon unit of 1,2-structure accounts for butadiene hydrocarbon unit total mass lower than 10% time, enough cross-linking set can not be provided when preparing HIPS, shock resistance reduces, content, higher than 45%, easily forms cross-linked macromolecular when preparing HIPS, and glossiness declines.
Styrene-butadiene copolymer of the present invention, its number-average molecular weight (M
n) be 150000-600000, be preferably 150000-500000.The molecular weight distribution mw/mn of styrene-butadiene copolymer of the present invention can be 1.01-1.2, preferred 1.01-1.1.The number-average molecular weight of styrene-butadiene copolymer is lower than 150,000, and multipolymer has cold flow, is not suitable for SBS aftertreatment and produces, and higher than 600,000, is also not suitable for SBS aftertreatment and produces.
The invention provides the method preparing styrene-butadiene block copolymer, comprise the preparation method of the styrene-butadiene copolymer of linear structure and the styrene-butadiene copolymer of star structure.
The styrene-butadiene copolymer of linear structure of the present invention, its preparation method is as follows:
(1), after adding solvent and activator in reactor, 50-100 DEG C is warmed up to;
(2) after adding styrene monomer, initiator initiation reaction is added, reaction 20-60 minute;
(3) add divinylic monomer, reaction 20-60 minute, controls temperature of reaction 40-115 DEG C, obtains the styrene-butadiene block copolymer of linear structure;
In described preparation method, the quality proportioning of vinylbenzene total amount and divinyl total amount is 10 ~ 60: 90 ~ 40; The add-on of solvent is 5 ~ 30% to be as the criterion to make vinylbenzene and the total mass concentration of divinylic monomer; The quality proportioning of activator and solvent is: 0 ~ 1: 1000; The add-on of initiator is the 1-5% of the total quality of vinylbenzene and divinyl.
After polymerization terminates, add terminator and carry out termination reaction.Terminator used in the present invention can be any terminator that this area adopts usually, such as water, alcohol and other compound containing proton hydrogen.
Finally, the styrene-butadiene copolymer of the linear structure produced is reclaimed by ordinary method.
The styrene-butadiene copolymer of star structure of the present invention, its preparation method is as follows:
(1), after adding solvent and activator in reactor, 50-100 DEG C is warmed up to;
(2) after adding initiator, then add divinylic monomer in reactor, reaction 20-60 minute, controls temperature of reaction 40-115 DEG C;
(3) add styrene monomer, react after 20-60 minute, then add divinylic monomer, reaction 5-30 minute;
(4) add coupler, reaction 10-40 minute, obtains the styrene-butadiene block copolymer of star structure;
In described preparation method, the quality proportioning of vinylbenzene total amount and divinyl total amount is 10 ~ 60: 90 ~ 40,2) add-on of divinyl accounts for the 80-99% of divinyl total mass in step; The add-on of solvent is 5 ~ 30% to be as the criterion to make vinylbenzene and the total mass concentration of divinylic monomer; The quality proportioning of activator and solvent is: 0 ~ 1: 1000; The add-on of initiator is the 1-5% of the total quality of vinylbenzene and divinyl, and the add-on of coupler is the 0.2-3% of the total quality of vinylbenzene and divinyl.
Finally, the styrene-butadiene copolymer of the star structure produced is reclaimed by ordinary method.
The styrene-butadiene copolymer of the star structure of the present invention's synthesis, has the technical difficulty in synthesis relative to the styrene-butadiene copolymer of general star structure.Styrene-butadiene copolymer active chain end before coupling of general star structure is polystyrene section, then due to larger sterically hindered, coupling degree and coupling efficiency are reduced, and the present invention is by accessing a small amount of butadiene segment at the active polystyrene end of the chain before coupling, increase kindliness, to improve coupling degree and coupling efficiency.
According to styrene-butadiene copolymer prepared by the inventive method, molecular weight can control, and 5% styrene solution viscosity is low, and vinylbenzene insolubles content is very low, and salient features is in table 1.
The salient features of table 1 styrene-butadiene block copolymer of the present invention
The preparation method of the styrene-butadiene block copolymer of the linear or star structure of the present invention, solvent can be generally used for solution polymerized butadiene styrene rubber produce in any solvent.The example includes but not limited to hexanaphthene, normal hexane, benzene, toluene and dimethylbenzene and they one or more.In the methods of the invention, the consumption of solvent can make the concentration of monomer be 5 ~ 30% (quality), based on the total mass meter of reaction mixture.
The styrene-butadiene block copolymer preparation method of the linear or star structure of the present invention, initiator comprises the various lithium alkylides being generally used for anionoid polymerization, such as n-Butyl Lithium and s-butyl lithium.The consumption of described initiator can be selected by molecular weight of product as required, the molecular weight of product needed is high, and the consumption of initiator reduces a little, and the molecular weight of product of needs is low, then the consumption of initiator is added a little, and this in the knowledge of those skilled in the range.
The styrene-butadiene block copolymer preparation method of the linear or star structure of the present invention, the example of activator is tetrahydrofuran (THF), and its amount that can be 0 ~ 1000mg/kg with the content in polymer solvent uses.
The styrene-butadiene block copolymer preparation method of star structure of the present invention, coupler comprises common chlorinated silane, such as dichlorodimethylsilane, three chlorodimethylsilane, silicon tetrachloride; Chlorination stannane, such as tin tetrachloride; Vinylstyrene etc.The consumption of described coupler can regulate according to the consumption of initiator activity lithium, and this in the knowledge of those skilled in the range.
Finally, the styrene-butadiene block copolymer of the linear or star structure of producing can be reclaimed by technology well known to those skilled in the art.Such as, the oxidation inhibitor (phenols or thioether class primary antioxidant, phosphorous acid lipid auxiliary antioxidant) of a certain amount of routine can be added in reaction mixture, then product be condensed and drying, to obtain finished product multipolymer.
The application of a kind of styrene-butadiene copolymer of the present invention, hits polystyrene for the preparation of high-gloss high-impact.
Adopt general technology mechanical blending method or the bulk graft polymerization of high impact polystyrene, make high-gloss high-impact and hit polystyrene HIPS product.
Described mechanical blending method adopts the polystyrene of styrene-butadiene copolymer of the present invention and general purpose grade, makes high impact polystyrene HIPS pellet, blending temperature 130-150 DEG C by twin screw extruder is blended; The consumption of styrene-butadiene copolymer is the 2-15% of polystyrene quality.
In described bulk graft polymerization, styrene-butadiene copolymer of the present invention is dissolved in styrene monomer, add a certain amount of ethylbenzene and 1,1-cyclohexane di-tert-butyl peroxide, reaction 3.5-4.5 hour is carried out at 155-175 DEG C of temperature, then remove fugitive constituent, cooling, obtains high impact polystyrene HIPS product; The consumption of styrene-butadiene copolymer is the 2-15% of styrene monomer quality, and ethylbenzene and 1,1-cyclohexane di-tert-butyl peroxide consumption are respectively 10-25% and 0.02-0.1% of styrene monomer quality.
Styrene-butadiene copolymer of the present invention joins in polystyrene, mainly be present in poly styrene polymer molecular chain with the form of block, and can unrestricted flow in polystyrene, vinylbenzene PS phase in styrene-butadiene copolymer is well separated with can reach between divinyl PB phase, and vinylbenzene PS phase in styrene-butadiene copolymer and can better be compatible between polystyrene, can at the physical and mechanical property improving polystyrene, especially, during impact property, the high glossiness of polystyrene is kept.
Accompanying drawing explanation
Fig. 1 is the styrene-butadiene copolymer of the linear structure of embodiment 1
1h NMR spectrogram.
Fig. 2 is the GPC spectrogram of the styrene-butadiene copolymer of the linear structure of embodiment 1.
Fig. 3 is the styrene-butadiene copolymer of the star structure of embodiment 2
1h NMR spectrogram.
Fig. 4 is the GPC spectrogram of the styrene-butadiene copolymer of the star structure of embodiment 2.
Embodiment
Herein, molecular weight and molecular weight distribution adopt Japanese Shimadzu LC-10AT series gel permeation chromatograph GPC to test; Gel content (Gel%) is employing 300 order stainless (steel) wire, and vinylbenzene is solvent, is filtered 5% styrene solution of rubber, with the vinylbenzene insolubles in weighting method testing rubber by ejector pump.Colourity is measured by the universal method-APHP method of chemical reagent determination of colority, with platinum-cobalt reference liquid for reference colour, measures the colourity of 5% styrene solution of rubber by visual colorimetry.Microtexture detects and adopts NMR (Nuclear Magnetic Resonance) spectrum (HNMR): Bruker AVANCE-400 type nuclear magnetic resonance spectrometer, CDCl
3make solvent.5% styrene solution viscosity is after rubber is made into 5% styrene solution, adopts Cannon-Fenske type viscosity apparatus to test under 25 ± 1 DEG C of conditions.The shock strength of HIPS, flexural strength and modulus in flexure, breaking tenacity and elongation adopt ASTM-D256, ASTM-D747 and ASTM-D638 method to carry out analytical test respectively.Surface gloss (45 °) adopts Switzerland ZLR1050 vancometer, ASTMD1003 standard testing.
Provide following examples to further illustrate the present invention, instead of limit the scope of the invention.
Embodiment 1
In 5 liters of polymeric kettles through nitrogen purge, add 2.5 liters of hexanaphthenes and mixture of raffinating oil (hexanaphthene and the ratio of mixture of raffinating oil are 9: 1), the amount being wherein 300mg/kg with the content in polymer solvent adds tetrahydrofuran (THF).This mixture is warming up to 50 DEG C, first adds 100g vinylbenzene, then add the initiation reaction of 1.0mmol n-Butyl Lithium.After stirring reaction 20-60 minute, 150g divinyl is joined in reactive polymer, control temperature of reaction 40 ~ 115 DEG C therebetween, stirring reaction 20-60min, then add 5ml water with termination reaction.Add the oxidation inhibitor of the quality 0.2-0.6% based on polymkeric substance in the reactive mixture, stir 5 minutes.Finally joined by product in the mixture of water vapor and water, solvent is evaporated, and polymkeric substance is then emanated out with the state of solid and is suspended in water.Solid is separated, with extruding-desiccation machine water squeezing, loft drier devolatilization, obtains the styrene-butadiene copolymer of linear structure.The molecular weight of this multipolymer is 290000 (Mn).In this polymkeric substance, vinylbenzene is polymerized in the mode of block with divinyl, and nuclear magnetic spectrogram and GPC spectrogram are shown in Fig. 1, Fig. 2 respectively.
Comparative example 1
In 5 liters of polymeric kettles through nitrogen purge, add 2.5 liters of hexanaphthenes and mixture of raffinating oil (hexanaphthene and the ratio of mixture of raffinating oil are 9: 1), the amount being wherein 300mg/kg with the content in polymer solvent adds tetrahydrofuran (THF).This mixture is warming up to 50 DEG C, first adds 50g vinylbenzene, then add the initiation reaction of 1.0mmol n-Butyl Lithium.After stirring reaction 20-60 minute, 150g divinyl is joined in reactive polymer, control maximum temperature therebetween and be less than 105 DEG C, stirring reaction 20-60 minute, at interpolation 50g vinylbenzene, stirring reaction 20-60 minute, then adds 5ml water with termination reaction.Add the oxidation inhibitor of the quality 0.2-0.6% based on polymkeric substance in the reactive mixture, stir 5 minutes.Finally joined by product in the mixture of water vapor and water, solvent is evaporated, and polymkeric substance is then emanated out with the state of solid and is suspended in water.Solid is separated, with extruding-desiccation machine water squeezing, loft drier devolatilization, obtains the styrene-butadiene copolymer of linear structure.The molecular weight of this multipolymer is 290000 (Mn).
Vinylbenzene, the divinyl consumption of embodiment 1 and comparative example 1 are identical, and molecular weight is also close, and same polymeric kettle synthesizes, and difference is that the structure of embodiment 1 makes polybutadiene segments be placed in outer end.Table 2 is the contrast of embodiment 1 and comparative example 1 5% styrene solution viscosity 25 DEG C time.
The contrast of table 2 embodiment 1 and comparative example 1
| Index name | Embodiment 1 | Comparative example 1 |
| 5% styrene solution viscosity, mpa.s | 45 | 380 |
Embodiment 2
In 5 liters of polymeric kettles through nitrogen purge, add 2.5 liters of hexanaphthenes and mixture of raffinating oil (hexanaphthene and the ratio of mixture of raffinating oil are 9: 1), the amount being wherein 300mg/kg with the content in polymer solvent adds tetrahydrofuran (THF).This mixture is warming up to 50 DEG C, and adds 2.15mmol n-Butyl Lithium.After stirring for 5 min, join in polymeric kettle by 162.6g divinylic monomer, control temperature of reaction 40 ~ 110 DEG C therebetween, 20-60 minute is carried out in reaction.Then in reactor, add 75g vinylbenzene, 20-60 minute is carried out in reaction.In reactor, add the divinyl of 12.4g again, reaction 5-30 minute, finally adds coupler silicon tetrachloride 5ml, and reaction 10-40 minute, adds the oxidation inhibitor of the quality meter 0.2-0.6% based on polymkeric substance, stir 5 minutes in mixture.Finally joined by product in the mixture of water vapor and water, solvent is evaporated, and polymkeric substance is then emanated out with the state of solid and is suspended in water.Solid is separated, with extruding-desiccation machine water squeezing, loft drier devolatilization, obtains the styrene-butadiene copolymer of star structure.The molecular weight of this multipolymer is 400000 (Mn), and nuclear magnetic spectrogram and GPC spectrogram are shown in Fig. 3, Fig. 4 respectively.
Comparative example 2
In 5 liters of polymeric kettles through nitrogen purge, add 2.5 liters of hexanaphthenes and mixture of raffinating oil (hexanaphthene and the ratio of mixture of raffinating oil are 9: 1), the amount being wherein 300mg/kg with the content in polymer solvent adds tetrahydrofuran (THF).This mixture is warming up to 50 DEG C, then in reactor, adds 75g vinylbenzene, and add 2.15mmol n-Butyl Lithium, 20-60 minute is carried out in reaction.Then join in polymeric kettle by 175g divinylic monomer, control maximum temperature therebetween and be less than 110 DEG C, 20-60 minute is carried out in reaction.In reactor, add coupler silicon tetrachloride 5ml, reaction 10-40 minute, adds the oxidation inhibitor of the quality meter 0.2-0.6% based on polymkeric substance, stirs 5 minutes in mixture.Finally joined by product in the mixture of water vapor and water, solvent is evaporated, and polymkeric substance is then emanated out with the state of solid and is suspended in water.Solid is separated, with extruding-desiccation machine water squeezing, loft drier devolatilization, obtains the styrene-butadiene copolymer of star structure.The molecular weight of this multipolymer is 400000 (Mn).
Vinylbenzene, the divinyl consumption of embodiment 2 and comparative example 2 are identical, and molecular weight is also close, and same polymeric kettle synthesizes, and difference is that the structure of embodiment 2 makes polybutadiene segments be placed in outer end.
Comparative example 3
Comparative example 3, compared with embodiment 2, just lacks the step adding 12.4g divinylic monomer in reactor, does not use a small amount of divinyl end-blocking, and make the direct coupling of active vinylbenzene segment, other steps follow same embodiment 2 completely.The coupling efficiency of comparative example 3 can only reach 50%.
Table 3 is embodiment 2 and the contrast of the coupling efficiency of comparative example 2,3 and the contrast of 5% styrene solution viscosity 25 DEG C time.
The contrast of table 3 embodiment 2 and comparative example 2,3
| Index name | Embodiment 2 | Comparative example 2 | Comparative example 3 |
| Coupling efficiency, % | 95 | 95 | 50 |
| 5% styrene solution viscosity, mpa.s | 78 | 265 | 59 |
Embodiment 3
By the styrene-butadiene copolymer of the linear structure of 0.48 kilogram of embodiments of the invention 1, mix, join in twin screw extruder and cause HIPS particle with 6 kilograms of general purpose polystyrenes, the temperature of dual-screw-stem machine is 140 DEG C.
Embodiment 4
By the styrene-butadiene copolymer of the star structure of 0.48 kilogram of embodiments of the invention 2, mix, join in twin screw extruder and cause HIPS particle with 6 kilograms of general purpose polystyrenes, the temperature of dual-screw-stem machine is 140 DEG C.
Embodiment 5
By the styrene-butadiene copolymer of the linear structure of 0.48 kilogram of embodiments of the invention 1, after dissolving with 6 kilograms of vinylbenzene, join in 10 liters of polymeric kettles, adding 0.96 kilogram of ethylbenzene and 0.003 kilogram 1,1-cyclohexane di-tert-butyl peroxide, under agitation react 4 hours, polymerization temperature 160 DEG C, obtains high-viscosity polymer.
High-viscosity polymer is heated to 245 DEG C, removes fugitive constituent, cooling, obtains HIPS product.
Embodiment 6
By the styrene-butadiene copolymer of the star structure of 0.48 kilogram of embodiments of the invention 2, after dissolving with 6 kilograms of vinylbenzene, join in 10 liters of polymeric kettles, adding 0.96 kilogram of ethylbenzene and 0.003 kilogram 1,1-cyclohexane di-tert-butyl peroxide, under agitation react 4 hours, polymerization temperature 160 DEG C, obtains high-viscosity polymer.High-viscosity polymer is heated to 245 DEG C, removes fugitive constituent, cooling, obtains HIPS product.
The performance of table 4 high-gloss high-impact polystyrene
| Index name | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Fracture tensile strength, MPa | 20.7 | 21.4 | 24.0 | 25.8 |
| Elongation, % | 4 | 4 | 2 | 2 |
| Flexural strength, MPa | 36.7 | 37.3 | 43.8 | 44.5 |
| Modulus in flexure, GPa | 2.05 | 2.06 | 2.20 | 2.21 |
| Shock strength, KJ/m 2 | 12.8 | 12.9 | 16.0 | 16.6 |
| Surface gloss (45 °) | 70 | 70 | 88 | 85 |
Can learn from table 4, styrene-butadiene block copolymer of the present invention can prepare hitting property of the high-gloss high-impact polystyrene of high-quality.
Claims (2)
1. a styrene-butadiene block copolymer, is characterized in that, has the star structure of general formula II, or has the combination of the linear structure of formula I and the star structure of general formula II; The number-average molecular weight of described styrene-butadiene block copolymer is 150,000-60 ten thousand, molecular weight distribution is 1.01-1.2, styrene units accounts for the 10-60% of copolymer quality, butadiene unit accounts for the 40-90% of copolymer quality, the butadiene unit of 1,2-structure accounts for the 10-45% of butadiene unit total mass;
Described formula I is: (PS
a-PB
b),
Described general formula II is: (PB
n-PS
m-PB
k)
zr,
PS represents the polymer segment derived from styrene monomer,
PB represents the polymer segment of derived from butadiene monomer,
A, b, m, n and k represent the polymerization degree of respective polymer segment,
A or m is independently selected within the scope of 100-2000 separately, b or n is independently selected within the scope of 1000-8000 separately, and k is 1-100,
Z represents the arm number of star structure, and z is the integer of 2-8,
R represents the coupling centers of star structure, and the alkyl that R is Si, Sn, total C number is 4-18 or total C number are the aromatic base of 8-22.
2. multipolymer as claimed in claim 1, it is characterized in that, a or m is independently selected within the scope of 150-1800 separately, b or n is independently selected within the scope of 1500-7000 separately, and k is 1-80.
3. multipolymer as claimed in claim 2, it is characterized in that, a or m is independently selected within the scope of 200-1500 separately, b or n is independently selected within the scope of 2000-6500 separately, and k is 1-50.
4. multipolymer as described in any one of claim 1-3, it is characterized in that, described number-average molecular weight is 15-50 ten thousand, molecular weight distribution is 1.01-1.1, styrene units accounts for the 20-60% of copolymer quality, butadiene unit accounts for the 40-80% of copolymer quality, and the butadiene unit of 1,2-structure accounts for the 10-35% of butadiene unit total mass.
5. multipolymer as claimed in claim 4, it is characterized in that, styrene units accounts for the 25-55% of copolymer quality, and butadiene unit accounts for the 45-75% of copolymer quality.
6. a preparation method for the styrene-butadiene block copolymer of star structure described in claim 1, is characterized in that, comprises the steps:
(1), after adding solvent and activator in reactor, 50-100 DEG C is warmed up to;
(2) after adding initiator, then add divinylic monomer in reactor, reaction 20-60 minute, controls temperature of reaction 40-115 DEG C;
(3) add styrene monomer, react after 20-60 minute, then add divinylic monomer, reaction 5-30 minute;
(4) add coupler, reaction 10-40 minute, obtains the styrene-butadiene block copolymer of star structure;
The quality proportioning of vinylbenzene total amount and divinyl total amount is 10 ~ 60:90 ~ 40,2) in step, the add-on of divinyl accounts for the 80-99% of divinyl total mass; The add-on of solvent is 5 ~ 30% to be as the criterion to make vinylbenzene and the total mass concentration of divinylic monomer; The quality proportioning of activator and solvent is: 0 ~ 1:1000; The add-on of initiator is the 1-5% of the total quality of vinylbenzene and divinyl, and the add-on of coupler is the 0.2-3% of the total quality of vinylbenzene and divinyl.
7. preparation method as claimed in claim 6, it is characterized in that, described solvent is one or more in hexanaphthene, normal hexane, benzene,toluene,xylene, hexane; Described activator is tetrahydrofuran (THF); Described initiator is n-Butyl Lithium or s-butyl lithium; Described coupler is chlorinated silane, chlorination stannane or Vinylstyrene.
8. preparation method as claimed in claim 7, it is characterized in that, described chlorinated silane is dichlorodimethylsilane, three chlorodimethylsilane or silicon tetrachloride; Described chlorination stannane is tin tetrachloride.
9. the application of styrene-butadiene block copolymer described in claim 1, hits polystyrene for the preparation of high-gloss high-impact.
10. apply as claimed in claim 9, it is characterized in that, styrene-butadiene copolymer and polystyrene are joined in twin screw extruder blended, blending temperature 130-150 DEG C; The consumption of styrene-butadiene copolymer is the 2-15% of polystyrene quality.
11. apply as claimed in claim 9, it is characterized in that, styrene-butadiene copolymer is dissolved in styrene monomer, then after adding ethylbenzene and 1,1-cyclohexane di-tert-butyl peroxide, at 155-175 DEG C of temperature, react 3.5-4.5 hour; The consumption of styrene-butadiene copolymer is the 2-15% of styrene monomer quality, and ethylbenzene and 1,1-cyclohexane di-tert-butyl peroxide consumption are respectively 10-25% and 0.02-0.10% of styrene monomer quality.
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| CN104558454B (en) * | 2013-10-17 | 2017-06-06 | 中国石油化工股份有限公司 | A kind of butylbenzene copolymer mixture and preparation method thereof |
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| CN105860406B (en) * | 2015-01-20 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of olefin polymer and its preparation method and application |
| CN105985488B (en) * | 2015-02-03 | 2018-08-17 | 中国石油化工股份有限公司 | Butylbenzene copolymer and preparation method thereof and rubber composition and vulcanized rubber |
| TWI630231B (en) * | 2017-07-27 | 2018-07-21 | 遠東新世紀股份有限公司 | Transparent impact resistant polyester composition |
| CN111978495A (en) * | 2019-05-24 | 2020-11-24 | 中国石油化工股份有限公司 | Asymmetric star-shaped hydrogenated block copolymer and preparation method and application thereof |
| CN114478956B (en) * | 2020-11-12 | 2023-11-28 | 中国石油天然气股份有限公司 | Preparation method of high-width-distribution three-hetero-arm comb-shaped star-shaped branched butyl rubber |
| CN114478955B (en) * | 2020-11-12 | 2023-11-28 | 中国石油天然气股份有限公司 | Preparation method of wide-distribution four-arm comb-shaped star-branched butyl rubber |
| CN114478953B (en) * | 2020-11-12 | 2023-11-28 | 中国石油天然气股份有限公司 | Preparation method of three-arm comb-shaped star-branched butyl rubber |
| CN114478954B (en) * | 2020-11-12 | 2023-11-28 | 中国石油天然气股份有限公司 | Preparation method of wide-distribution four-arm comb-shaped star-branched butyl rubber |
| CN114478949B (en) * | 2020-11-12 | 2023-11-28 | 中国石油天然气股份有限公司 | Preparation method of wide-distribution three-arm comb-shaped star-branched butyl rubber |
| CN114478951B (en) * | 2020-11-12 | 2023-11-28 | 中国石油天然气股份有限公司 | Preparation method of wide-distribution three-arm comb-shaped star-branched butyl rubber |
| CN114478950B (en) * | 2020-11-12 | 2023-11-28 | 中国石油天然气股份有限公司 | Three-arm comb-shaped star-shaped branched butyl rubber and preparation method thereof, and preparation method of three-arm star-shaped nucleating agent |
| CN114478957B (en) * | 2020-11-12 | 2023-11-28 | 中国石油天然气股份有限公司 | Preparation method of four-arm comb-shaped star-branched butyl rubber |
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