CN102952363B - A kind of wide distribution block copolymer mixture and preparation method thereof - Google Patents
A kind of wide distribution block copolymer mixture and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of wide distribution copolymer mixture formed by monovinylarene and conjugated diene and preparation method thereof, product shows high working property energy, high transparent and high impact properties in the course of processing, and it is modified to can be used for high-grade resin.Being polymerized by double stills, material is blended the method synthesis simultaneously carried out with polyreaction and obtains simultaneously.Described copolymer mixture comprises the monovinylarene star block copolymer of 5%～10%, and its structural formula is: X [B2‑S2/B1‑S1]n, the single vinyl polymer S of 1%～5%3, the X [B of 2%～5%2‑S3‑S2/B1‑S1]nWith X [B2‑S3‑(S2→B1)S2/S1‑B1]n, the conjugated diene containing random graded chain segment of 84%～90% and monovinylarene star block copolymer X [B2‑(S2→B1)S2/S1‑B1]n。
Description
Technical field
The present invention relates to a kind of wide distribution block copolymer mixture and preparation method thereof, particularly a kind of high transparent, height are anti-
Impact and there is excellent machinability, may be used for resin modified, conjugated diene and monovinylarene prepare
Wide distribution block copolymer mixture and preparation method thereof.
Background technology
In the prior art, the method using block copolymer prepared by butadiene and styrene is more, as EP0492490,
US4925899, US5130377, CN85100418 etc..The wherein butadiene of US4925899, US5130377 report
Being polymorphic with styrene block copolymer, initiator adds at twice, and monomer divides 4～9 additions, and preparation technology is multiple
Miscellaneous, and repeatedly addition monomer and initiator may bring impurity into system, affect polymer performance.
Patent CN1628150A reports a kind of containing styrene block copolymer, can improve mechanical performance and processing
The block copolymer composition of performance.Employing lithium alkylide is initiator, employing stannum coupling agent, polystyrene-poly (ethylene-
Butylene)-polystyrene elastomer block copolymer is compounded with other material such as polyolefin and tackifying resin, thus formation can
The elastic composition of extrusion, they are more easy to the polymer being extruded as having processing characteristics and adhesive property.But this block
Copolymer compositions uses Mechanical Method to be blended, and homogenization degree is the highest, can affect the serviceability of product.
Patent CN88106184.0 reports a kind of rubber-modified styrene copolymer, wherein contains and changes as impact strength
The rubber polymer of property agent.Use anionic polymerisation process, use styrene-butadiene block copolymer to gather as rubber
Compound is dispersed in the continuous phase that SAN is constituted.Although this resin modified copolymer has preferably
Mobility, but complicated process of preparation, after modified styrol copolymer needs with one or more resin alloys again
Mold.
Patent CN85100418 reports a kind of craze-resistant transparent resinous copolymers, uses butadiene and styrene altogether
Poly-block copolymer.But the copolymer of this preparation method is the pattern of employing order charging copolyreaction to be prepared, three kinds
The charging number of times of component is 8～9 times.
Patent CN91111388.6 reports a kind of styrene-butadiene block copolymer and preparation method thereof, uses six steps
Method synthesizing styrene-butadiene block copolymer, and impact strength and other physicochemical property of the block copolymer prepared
Can not get both.
Patent EP0492490 reports the block copolymer of a kind of Butadiene/Styrene, a kind of initiator of employing and two kinds
Monomer simultaneous reactions, the most again with one or more monomer reactions, then reacts with two kinds of monomer mixtures, then with
One or more monomer reaction generates block copolymer.The method charging times is many, and preparation method is complicated.
Patent US4925899 reports a kind of bimodal star block copolymer, and wherein 60～90% is vinyl,
10～40% is conjugated diene.The method initiator adds the most several times with monomer, and the change of polymerization temperature condition is frequent,
And need add filling oil and meet stabilizer, complex process.
Patent US5130377 reports a kind of Butadiene/Styrene block copolymer, this copolymer be by divinylic monomer,
Styrene monomer and butadiene-styrene polymer, copolymerization forms.Reactions steps is carried out in six steps, reaction controlling condition
Complexity, reacts poor controllability.
Monovinylarene and the molecular weight of conjugated diene polymer and distribution thereof are to affect the physics of polymer, mechanicalness
Can be with the two of processed and applied characteristic key factor.Distribution of polymer width is conducive to post-treatment, and polymer molecular weight is less,
Gelatin viscosity is little, beneficially resin modified.
From the point of view of existing synthetic technology, use block copolymer synthesis prepared by conjugated diene and monovinylarene at present
Complex process, though having preferable optical property and impact property, but the processing characteristics of product is poor, thus limits material
The range of application of material.
Summary of the invention
It is an object of the invention to provide a kind of wide distribution block copolymerization formed by monovinylarene and conjugated diene
Mixture and preparation method thereof, synthesis technique of the present invention is simple, and on the premise of ensureing optics, mechanical performance, enters one
Step improves processing characteristics, the processing characteristics that especially resin is good and high transparent, the combination of high impact property, and can use
In other resin modified.
A kind of wide distributing transparent block copolymerization mixture, comprises the monovinylarene star block copolymer of 5%～10%,
Its structural formula is: X-[B2-S2/B1-S1]n, the single vinyl polymer S of 1%～5%3, 2%～5%
X-[B2-S3-S2/B1-S1]nWith X-[B2-S3-(S2→B1)S2/S1-B1]n, the conjugation containing random graded chain segment of 84%～90%
Alkadienes and monovinylarene star block copolymer, its structural formula is: X-[B2-(S2→B1)S2/S1-B1]n；
Wherein, X is Si, Sn；S1, S2Represent mono vinyl arenes monomer；B1For conjugated diene monomer；B2For
End-blocking conjugated diene monomer, accounts for B2-S2The 3%～5% of amount of monomer；Described B1-S1Number-average molecular weight be 30000～
50000；The span 2 ＜ n ＜ 4 of n.
S2/B1Represent conjugated diene and the random section of monovinylarene；(S2→B1) represent conjugated diene and mono-vinyl
Aromatic hydrocarbons transition；B2-(S2→B1)S2/S1-B1Number-average molecular weight be 30000～50000.
Copolymer mixture of the present invention can obtain in the following way:
I walks: in polymeric kettle 1, in the presence of the activator accounting for total monomer weight 0.01%～0.3%, adds single second
Alkenyl arene S and initiator I, monovinylarene accounts for the 40%～80% of total monomer weight, forms S1-Me, wherein
Me is the metal ion of initiator, and the addition of initiator I is that initiator always adds the 1/15～1/5 of weight, reaction temperature
Degree is 50～80 DEG C, and reaction pressure is 0.08～0.20MPa, and the response time is 30～60min, now mono-vinyl virtue
Hydrocarbon monomer conversion ratio reaches 100%.
Ii walks: add mono vinyl arenes monomer S and the mixture of conjugated diene monomer B in polymeric kettle 1, mixed
Compound accounts for the 10%～50% of total monomer weight, and in mixture, monovinylarene accounts for the 5%～23% of total monomer weight,
Conjugated diene accounts for the 7%～29% of total monomer weight, and reaction temperature is 50 DEG C～80 DEG C, reaction pressure be 0.08～
0.20MPa, the response time is 50～120min, and monovinylarene and conjugated diene hydrocarbon mixture are continuously added to, charging
Speed is in terms of the percentage by weight of mixture, and for per minute 1.6%～5.0%, the charging rate at mixture initial stage is less than anti-
Answer speed, form random section S1-B1/S2-Me, the charging rate in mixture later stage is higher than reaction rate, forms transition
S1-B1/S2(B1→S2)-Me；
Meanwhile, in polymeric kettle 2, add the mono vinyl arenes monomer S accounting for monomer mass 3%～10%, add and cause
Agent I, the initiator I of addition account for initiator and always add the 1/10～1/20 of weight, are polymerized 5～10min, and polymerization temperature is
50～80 DEG C, now mono vinyl arenes monomer conversion ratio is 40%～50%, forms the poly-of mono vinyl arenes monomer S
Compound S3；
Ii I walks: the material in polymeric kettle 2 is added in polymeric kettle 1, and reaction is performed until substantially free of free monomer
Till in the presence of；
Iv walks: in polymeric kettle 1, adds the conjugated diene monomer B accounting for monomer total amount 3%～10%2End-blocking, body
Containing S in system3, and form four kinds of living chain P:S1-B1/S2(B1→S2)-B2-Me、S1-B1/S2-B2-Me、
S1-B1/S2(B1→S2)-S3-B2-Me、S1-B1/S2-S3-B2-Me；
V walks: in polymeric kettle 1, adds coupling agent, and coupling temperature is 50～80 DEG C, and Coupling time is 30～60min,
Coupling terminates, and adds water and antioxidant in a polymer solution, and stirs, and the consumption of water is initiator amount
100～300 times, then, use steam stripping coacervation method or use devolatilization type screw extruder, polymer is divided from solution
Separate out, thus form mixture: X-[B2-S2/B1-S1]n、X-[B2-(S2→B1)S2/S1-B1]n、X-[B2-S3-S2/B1-S1]n、
X-[B2-S3-(S2→B1)S2/S1-B1]n、S3, wherein, X is Sn or Si, and the span of n is 2 ＜ n ＜ 4.
It is an object of the invention to prepare processing characteristics and resin modified transparent block copolymer of good performance mixture.The present invention
In X-[B2-(S2→B1)S2/S1-B1]nDue to containing random transition so that product has preferable light transmission and excellence
Mechanical property.X-[B2-S2/B1-S1]nMolecular weight, viscosity is relatively low, both can suitably widen this copolymer mixture
It is good that molecular weight distribution obtains preferable post-treatment performance, can ensure this copolymer mixture by regulating its content again
Good mechanical performance.S in the present invention3Minimum in this copolymer mixture middle-molecular-weihydroxyethyl, it plays lubrication in the course of processing
The effect of agent, makes the molecular weight distribution of this copolymer mixture widen, have good post-treatment performance, high impact property,
High transparency performance.This copolymer mixture, owing to having the features such as molecular weight is little, viscosity is little, high glaze, can change as resin
Property glue.This polymer has the highest light transmittance and excellent impact strength, has the most elastic and goods under room temperature
ESCR, shaping can be plastified under high temperature, the fields such as packaging for foodstuff, medical apparatus and instruments, toy for children can be used for.
The mode being formed by continuous feed of the random graded chain segment of the present invention, monovinylarene and conjugated diene are mixed
The charging rate initial stage of compound is less than reaction rate, forms random section, and later stage charging rate is higher than reaction rate, thus obtains
To the random graded chain segment with certain length.The random graded chain segment using this technique to prepare adequately achieves from fourth two
Alkene, to cinnamic gradual transition, efficiently avoid and forms gel or the generation of other side reaction under pyroreaction, it is ensured that
Polymer has good light transmission and excellent mechanics mechanical performance.The present invention uses polymeric kettle 1 and polymeric kettle 2
Being polymerized, when the conversion ratio of monovinylarene reaches 40%～50%, double still material mixing, now material is altogether simultaneously
Mixed carry out with polyreaction simultaneously, make the molecular weight distribution of this copolymer mixture widen, viscosity diminishes, have good after
Processing characteristics.
In order to make copolymer mixture have the performance of excellence, the invention provides its optimal preparation method, preparation process describes
As follows:
I walks: in polymeric kettle 1, in the presence of the activator accounting for monomer total amount 0.01%～0.3%, adds single ethylene
Base aromatic hydrocarbons S and initiator I, monovinylarene accounts for the 50%～70% of total monomer weight, forms S1-Me, wherein Me
For the metal ion of initiator, the addition of initiator I is (1/10)～(1/8) of the total addition of initiator, reaction
Temperature is 60～75 DEG C, and reaction pressure is 0.10～0.18MPa, and the response time is 35～50min, now mono-vinyl
Aromatic monomer conversion ratio reaches 100%.
Ii walks: add mono vinyl arenes monomer S and the mixture of conjugated diene monomer B in polymeric kettle 1, mixed
Compound accounts for the 20%～40% of total monomer weight, and in mixture, monovinylarene accounts for the 10%～20% of total monomer weight
(wt), conjugated diene accounts for 10%～20% (wt) of total monomer weight, and reaction temperature is 55 DEG C～75 DEG C, reaction
Pressure is 0.10～0.18MPa, and the response time is 60～100min, and monovinylarene and conjugated diene hydrocarbon mixture are even
Continuous addition, charging rate is in terms of the percentage by weight of mixture, for per minute 2.0%～4.5%, adding of mixture initial stage
Material speed, less than reaction rate, forms random section S1-B1/S2-Me, the charging rate in mixture later stage is higher than reaction rate,
Form transition S1-B1/S2(B1→S2)-Me；
Meanwhile, in polymeric kettle 2, add the mono vinyl arenes monomer S accounting for monomer mass 3%～5%, add and cause
Agent I, the initiator I of addition account for initiator and always add the 1/10～1/20 of weight, and polymerization time is 5～10min, polymerization
Temperature is 55～80 DEG C, and now mono vinyl arenes monomer conversion ratio is 40%～50%, forms mono vinyl arenes monomer
The polymer S of S3。
Ii I walks: the material in polymeric kettle 2 is added in polymeric kettle 1, and reaction is performed until substantially free of free monomer
Till in the presence of；
Iv walks: in polymeric kettle 1, adds the conjugated diene monomer B accounting for monomer total amount 3%～8%2End-blocking, body
Containing S in system3, and form four kinds of living chain P:S1-B1/S2(B1→S2)-B2-Me、S1-B1/S2-B2-Me、
S1-B1/S2(B1→S2)-S3-B2-Me、S1-B1/S2-S3-B2-Me。
V walks: in polymeric kettle 1, adds coupling agent, and coupling temperature is 55～75 DEG C, and Coupling time is 40～55min,
After coupling terminates, adding water and antioxidant in a polymer solution, and stir, the consumption of water is initiator amount
150～250 times, then, use steam stripping coacervation method or use devolatilization type screw extruder, polymer is divided from solution
Separate out, thus form mixture: X-[B2-S2/B1-S1]n、X-[B2-(S2→B1)S2/S1-B1]n、X-[B2-S3-S2/B1-S1]n、
X-[B2-S3-(S2→B1)S2/S1-B1]n、S3, wherein, X is Sn or Si, and the span of n is 2 ＜ n ＜ 4.
In order to improve the transparency of this copolymer mixture, the polymer solution reacted adds water.The consumption one of water
As be 100～300 times of initiator amount, preferably 150～250 times, use CO simultaneously2Regulation polymer solution
PH value is to 7.0 scholars 0.5.
Antioxidant can with hydrocarbon for bisphenols (such as 1010), thiobis phenols, Diamines, phosphoric acid ester (such as TNP),
Sulfolipins etc., above-mentioned substance can be used alone, it is also possible to two kinds of compound uses, addition be total monomer weight 0.5%～
5%, preferably 0.5%～2%.The polymer so obtained has good transparency.
The mono vinyl arenes monomer of the present invention refers generally to containing 8～18 carbon atoms, and substituent group can be alkyl, cycloalkanes
Base, aromatic substituent and the material of their complex substituents, wherein the total number of carbon atoms of substituent group is usually no more than 12
Individual.Mainly include styrene, a-methyl styrene, 4-n-propylbenzene ethylene, 4-cyclohexylstyrenes, 4-detergent alkylate
Ethylene, 1-vinyl naphthalene, 2,4-DMS etc., or their mixture.It is most commonly used that styrene, this
It is to be determined by its practical value industrially.
The conjugated diene of the present invention typically contains 4～12 carbon atoms, and preferably 4～8 carbon atoms, including 1,3-
Butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-butadiene etc.,
Or their mixture.Have industrial value is 1,3-butadiene, and isoprene is most commonly used that 1,3-butadiene.
Initiator of the present invention is preferably organo monolithium compounds, and conventional is alkyl list lithium compound, i.e. RLi,
Wherein R is the representative examples of saturated aliphatic alkyl containing 1～20 carbon atom, alicyclic alkyl, aryl or above-mentioned group
Composite base.This organo-lithium compound include n-BuLi, s-butyl lithium, methyl butyl lithium, phenyl butyl lithium, naphthalene lithium,
Cyclohexyl lithium, dodecyl lithium etc..It is most commonly used that n-BuLi and s-butyl lithium.The addition of organolithium is by designing
The molecular weight of polymer determines.
Polyreaction of the present invention, in substantially anaerobic, anhydrous, is preferably carried out in inert gas argon compression ring border.Polymerization
Process completes in varsol, and preferable varsol includes linear paraffin and cycloalkane, such as pentane, and hexane, octane,
Heptane, hexamethylene and their mixture, preferably hexamethylene.
Paradigmatic system of the present invention needs add a small amount of polar organic compound and improves alkyl as activator, one side
The reactivity of lithium initiator such as n-BuLi, on the other hand the randomization degree of the random transition of scalable and gradual change journey
Degree.This kind of polar organic compound include oxolane (THF), ether, ethyl methyl ether, methyl phenyl ethers anisole, diphenyl ether,
Glycol dimethyl ether (DME), diethylene glycol dimethyl ether (2G), triethylamine, 6-methyl phosphonic triamide etc..Wherein four
The using effect of hydrogen furan is best, and its consumption is the 0.01%～0.3% of total monomer weight, preferably 0.02%～0.2%.
Coupling agent used by the present invention is the coupling agent such as butter of tin, Silicon chloride., uses the coupling agent of dynamics model.
The consumption of coupling agent is depending on the amount of initiator, and general coupling agent consumption is 0.1～3.0 with the mol ratio of organolithium.
Monovinylarene and the molecular weight of conjugated diene polymer and distribution thereof are to affect the physics of polymer, mechanicalness
Can be with the two of processed and applied characteristic key factor.The present invention uses two polymeric kettles to be polymerized simultaneously, and material is blended and is polymerized
The method that reaction is carried out simultaneously synthesizes the copolymer mixture obtained, and adds monovinylarene S reaction in polymeric kettle 2,
When in polymeric kettle 2, conversion ratio is 40%～50%, and the total material of polymeric kettle 1 is blended so that polymer molecular weight divides
Cloth is wider, and molecular weight is relatively small.Distribution of polymer width is conducive to post-treatment, and polymer molecular weight is less, gelatin viscosity
Little, beneficially resin modified.
The copolymer mixture of the various structures contained by the present invention can reach high working property and can (can represent with eddy flow, its value
The highest, processability is the best) with good transparency (can represent with light transmittance, its value is the highest, and the transparency is the best), high
Effective combination of impact property (can represent by impact strength, its value is the highest, shows that impact property is the best), has width
The features such as distribution, viscosity is little, can be as resin modified glue (carrying out SBS modification experiment, respond well).It is suitable for
The application in the fields such as packaging, medical apparatus and instruments and toy for children.It is simple that preparation method provided by the present invention has technique, produces
The feature of product stable performance.
Detailed description of the invention
In order to further illustrate the details of the present invention, name some embodiments, but should not be limited thereto.Embodiment
The copolymerization of the wide distribution that the 1～6 preparation method synthesis of conjugate alkadienes-monovinylarenes describing the application present invention are formed
Mixture, embodiment 7 describes the copolymer mixture modified SBS using the distribution of this width.
Embodiment 1～6
In the 10L stainless steel cauldron with chuck, in varsol, under the protection of argon, carry out polyreaction.Poly-
Close and coupling process needs to be stirred continuously reactant mixture.Addition step is as follows:
I walks: in polymeric kettle 1, in the presence of the activator accounting for monomer total amount 0.01%～0.3%, adds single ethylene
Base aromatic hydrocarbons S and initiator I, monovinylarene accounts for the 40%～80% of total monomer weight, and the addition of initiator I is
The 1/15～1/5 of the total addition of initiator, reaction temperature is 50～80 DEG C, and reaction pressure is 0.08～0.20MPa, instead
It is 30～60min between Ying Shi；
Ii walks: add mono vinyl arenes monomer S and the mixture of conjugated diene monomer B in polymeric kettle 1, mixed
Compound accounts for the 10%～50% of total monomer weight, and in mixture, monovinylarene accounts for the 5%～23% of total monomer weight,
Conjugated diene accounts for the 7%～29% of total monomer weight, and reaction temperature is 50～80 DEG C, and reaction pressure is 0.08～0.20
MPa, the response time is 50～120min；
Meanwhile, in polymeric kettle 2, add and account for the mono vinyl arenes monomer S of monomer mass 3%～10%, polymerization 5～
10min；
Ii I walks: the material in polymeric kettle 2 is added in polymeric kettle 1, and reaction is performed until substantially free of free monomer
Till in the presence of；
Iv walks: in polymeric kettle 1, adds the conjugated diene monomer B accounting for monomer total amount 3%～10%2End-blocking；
V walks: in polymeric kettle 1, adds coupling agent, and coupling temperature is 50～80 DEG C, and Coupling time is 30～60min,
Thus form mixture: X-[B2-S2/B1-S1]n、X-[B2-(S2→B1)S2/S1-B1]n、X-[B2-S3-S2/B1-S1]n、
X-[B2-S3-(S2→B1)S2/S1-B1]n、S3, wherein, X is Sn or Si, and the span of n is 2 ＜ n ＜ 4.
After having reacted, add water and the antioxidant of metering in a polymer solution, and stir.Then, vapour is used
Carry condensing method or use devolatilization type screw extruder, polymer is separated from solution.
Table 1 is embodiment polyreaction raw material, the kind of auxiliary agent；Table 2 lists Example formulations and process conditions.
Comparative example 1:
Other process conditions and raw material addition are same as in Example 1, and difference is: in ii walks, in polymerization
In still 2, it is added without monovinylarene S, forms X-[B2-S2/B1-S1]nWith X-[B2-(S2→B1)S2/S1-B1]nMixed
Compound.
Comparative example 2:
Other process conditions and raw material addition are same as in Example 2, and difference is: in ii walks, in polymerization
In still 2, it is added without monovinylarene S, forms X-[B2-S2/B1-S1]nWith X-[B2-(S2→B1)S2/S1-B1]nMixed
Compound.
Comparative example 3:
Other process conditions and raw material addition are same as in Example 3, and difference is: in ii walks, in polymerization
In still 2, it is added without monovinylarene S, forms X-[B2-S2/B1-S1]nWith X-[B2-(S2→B1)S2/S1-B1]nMixed
Compound.
Comparative example 4:
Other process conditions and raw material addition are the same as in Example 4, and difference is: in ii walks, in polymerization
In still 2, it is added without monovinylarene S, forms X-[B2-S2/B1-S1]nWith X-[B2-(S2→B1)S2/S1-B1]nMixed
Compound.
Comparative example 5:
Other process conditions and raw material addition are same as in Example 5, and difference is: in ii walks, in polymerization
In still 2, it is added without monovinylarene S, forms X-[B2-S2/B1-S1]nWith X-[B2-(S2→B1)S2/S1-B1]nMixed
Compound.
Comparative example 6:
Other process conditions and raw material addition are same as in Example 6, and difference is: in ii walks, in polymerization
In still 2, it is added without monovinylarene S, forms X-[B2-S2/B1-S1]nWith X-[B2-(S2→B1)S2/S1-B1]nMixed
Compound.
Comparative example 7:
Other process conditions and raw material addition are same as in Example 1, and difference is: in ii walks, in polymerization
The monovinylarene S added in still 2, polymerization time is 40min, after i.e. conversion ratio reaches 100%, adds polymerization
In still 1, other step is identical with embodiment 1, forms X-[B2-S2/B1-S1]n、X-[B2-(S2→B1)S2/S1-B1]n、
X-[B2-S3-S2/B1-S1]n、X-[B2-S3-(S2→B1)S2/S1-B1]n、S3。
Comparative example 8:
Other process conditions and raw material addition are same as in Example 2, and difference is: in ii walks, in polymerization
The monovinylarene S added in still 2, polymerization time is 40min, after i.e. conversion ratio reaches 100%, adds polymerization
In still 1, other step is identical with embodiment 1, forms X-[B2-S2/B1-S1]n、X-[B2-(S2→B1)S2/S1-B1]n、
X-[B2-S3-S2/B1-S1]n、X-[B2-S3-(S2→B1)S2/S1-B1]n、S3。
Comparative example 9:
Other process conditions and raw material addition are same as in Example 3, and difference is: in ii walks, in polymerization
The monovinylarene S added in still 2, polymerization time is 40min, after i.e. conversion ratio reaches 100%, adds polymerization
In still 1, other step is identical with embodiment 1, forms X-[B2-S2/B1-S1]n、X-[B2-(S2→B1)S2/S1-B1]n、
X-[B2-S3-S2/B1-S1]n、X-[B2-S3-(S2→B1)S2/S1-B1]n、S3。
Comparative example 10:
Other process conditions and raw material addition are the same as in Example 4, and difference is: in ii walks, in polymerization
The monovinylarene S added in still 2, polymerization time is 40min, after i.e. conversion ratio reaches 100%, adds polymerization
In still 1, other step is identical with embodiment 1, forms X-[B2-S2/B1-S1]n、X-[B2-(S2→B1)S2/S1-B1]n、
X-[B2-S3-S2/B1-S1]n、X-[B2-S3-(S2→B1)S2/S1x-B1]n、S3。
Comparative example 11:
Other process conditions and raw material addition are same as in Example 5, and difference is: in ii walks, in polymerization
The monovinylarene S added in still 2, polymerization time is 40min, after i.e. conversion ratio reaches 100%, adds polymerization
In still 1, other step is identical with embodiment 1, forms X-[B2-S2/B1-S1]n、X-[B2-(S2→B1)S2/S1-B1]n、
X-[B2-S3-S2/B1-S1]n、X-[B2-S3-(S2→B1)S2/S1-B1]n、S3。
Comparative example 12:
Other process conditions and raw material addition are same as in Example 6, and difference is: in ii walks, in polymerization
The monovinylarene S added in still 2, polymerization time is 40min, after i.e. conversion ratio reaches 100%, adds polymerization
In still 1, other step is identical with embodiment 1, forms X-[B2-S2/B1-S1]n、X-[B2-(S2→B1)S2/S1-B1]n、
X-[B2-S3-S2/B1-S1]n、X-[B2-S3-(S2→B1)S2/S1-B1]n、S3。
The physical and mechanical properties test result of the mixture of embodiment and comparative example is shown in Table 3.The survey of notch impact strength
Examination is carried out according to GB/T 1043-93；Light transmittance, mist degree are tested according to GB/T 3410-80；Molecular weight and distribution thereof are adopted
Measure by gel permeation chromatography (GPC) method；5% styrene solution viscosity uses determination of ubbelohde viscometer.
Table 1 embodiment experimental raw and auxiliary agent kind
Table 2 Example formulations and process conditions
Table 3 embodiment, comparative example copolymer mixture performance
Note: eddy flow represents the shot capacity of resin, its value the biggest expression processing characteristics is the best.
It can be seen that be added without conjugated diene (comparative example in step II from table 1, table 2 and table 3
1～6) and only carry out comparing of physical blending (comparative example 7～12), be polymerized by double stills, material simultaneously
The method that with polyreaction simultaneously carry out is blended and synthesizes the copolymer mixture obtained, there is good processability and (divide
Son amount distribution is wide, eddy flow value is big), good shock resistance, 5% styrene gelatin viscosity is little, optical
The performances such as energy good (light transmittance is big, mist degree is little).High working property energy that product shows in the course of processing,
High transparent and high impact properties, the wide distribution copolymer mixture therefore using present invention synthesis can be by extensively
To be applied to high-grade resin modified.
Claims (1)
1. a preparation method for copolymer mixture, it comprises the following steps: at the 10L stainless steel reaction with chuck
In still, in varsol, under the protection of argon, carry out polyreaction；Polymerization and coupling process are stirred continuously reaction mixing
Thing；And feed according to following steps:
Ith step: in polymeric kettle 1, in 4650g cyclohexane solvent, and in the presence of 4.8g activator THF,
Add mono vinyl arenes monomer styrene 1200g and initiator n-BuLi 32mmol, form S1-Me, wherein S1For
Mono vinyl arenes monomer, Me is the metal ion of initiator, and reaction temperature is 50 DEG C, reaction pressure be 0.08～
0.20MPa, the response time is 30min, and now mono vinyl arenes monomer conversion ratio reaches 100%；
IIth step: in polymeric kettle 1, adds mono vinyl arenes monomer styrene 350g in 2820g cyclohexane solvent
With conjugated diene monomer butadiene 330g, reaction temperature is 70 DEG C, and reaction pressure is 0.08～0.20MPa, during reaction
Between be 50min, monovinylarene and conjugated diene hydrocarbon mixture are continuously added to, and charging rate is with the weight hundred of mixture
Proportion by subtraction meter, for per minute 1.6%～5.0%, the charging rate at mixture initial stage is less than reaction rate, forms random section
S1-B1/S2-Me, the charging rate in mixture later stage is higher than reaction rate, forms transition S1-B1/S2(B1→S2)-Me,
Wherein S1、S2For mono vinyl arenes monomer, B1For conjugated diene monomer；
Meanwhile, in polymeric kettle 2, in 1080g cyclohexane solvent, and in the presence of 0.5g activator THF,
Adding mono vinyl arenes monomer styrene 120g and initiator n-BuLi 3.3mmol, be polymerized 5min, polymerization temperature is
50 DEG C, now mono vinyl arenes monomer conversion ratio is 40%～50%, forms the polymer S of mono vinyl arenes monomer3；
IIIth step: the material in polymeric kettle 2 is added in polymeric kettle 1, and reaction is performed until substantially free of free monomer
Till in the presence of；
IVth step: in polymeric kettle 1, in 278g cyclohexane solvent, adds butadiene 120g end-blocking, reaction temperature
Being 70 DEG C, the response time is 20min, containing S in system3, and form four kinds of living chain P:
S1-B1/S2(B1→S2)-B2-Me、S1-B1/S2-B2-Me、S1-B1/S2(B1→S2)-S3-B2-Me、S1-B1/S2-S3-B2-Me；
Vth step: in polymeric kettle 1, adds coupling agent SnCl49.1mmol, coupling temperature is 55 DEG C, Coupling time
For 40min, coupling terminates, and adds water and antioxidant 1010 in a polymer solution, and stirs, and the consumption of water is
100～300 times of initiator amount, the consumption of antioxidant 1010 is 20g, then, uses steam stripping coacervation method or makes
With devolatilization type screw extruder, polymer is separated from solution, thus form mixture: X-[B2-S2/B1-S1]n、
X-[B2-(B1→S2)S2/B1-S1]n、X-[B2-S3-S2/B1-S1]n、X-[B2-S3-(B1→S2)S2/B1-S1]n、S3, wherein,
X be the span of Sn, n be 2 n 4；
Or feed according to following steps:
Ith step: in polymeric kettle 1, in 6200g cyclohexane solvent, and in the presence of 5.6g activator DME,
Add mono vinyl arenes monomer styrene 1600g and initiator n-BuLi 39mmol, form S1-Me, wherein S1For
Mono vinyl arenes monomer, Me is the metal ion of initiator, and reaction temperature is 65 DEG C, reaction pressure be 0.08～
0.20MPa, the response time is 45min, and now mono vinyl arenes monomer conversion ratio reaches 100%；
IIth step: in polymeric kettle 1, adds mono vinyl arenes monomer styrene 170g in 1400g cyclohexane solvent
With conjugated diene monomer butadiene 170g, reaction temperature is 60 DEG C, and reaction pressure is 0.08～0.20MPa, during reaction
Between be 120min, monovinylarene and conjugated diene hydrocarbon mixture are continuously added to, and charging rate is with the weight of mixture
Percentages, for per minute 1.6%～5.0%, the charging rate at mixture initial stage is less than reaction rate, forms random section
S1-B1/S2-Me, the charging rate in mixture later stage is higher than reaction rate, forms transition S1-B1/S2(B1→S2)-Me,
Wherein S1、S2For mono vinyl arenes monomer, B1For conjugated diene monomer；
Meanwhile, in polymeric kettle 2, in 1100g cyclohexane solvent, and in the presence of 0.6g activator DME,
Adding mono vinyl arenes monomer styrene 120g and initiator n-BuLi 3.0mmol, be polymerized 5min, polymerization temperature is
55 DEG C, now mono vinyl arenes monomer conversion ratio is 40%～50%, forms the polymer S of mono vinyl arenes monomer3；
IIIth step: the material in polymeric kettle 2 is added in polymeric kettle 1, and reaction is performed until substantially free of free monomer
Till in the presence of；
IVth step: in polymeric kettle 1, in 139g cyclohexane solvent, adds butadiene 60g end-blocking, reaction temperature
Being 55 DEG C, the response time is 30min, containing S in system3, and form four kinds of living chain P:
S1-B1/S2(B1→S2)-B2-Me、S1-B1/S2-B2-Me、S1-B1/S2(B1→S2)-S3-B2-Me、S1-B1/S2-S3-B2-Me；
Vth step: in polymeric kettle 1, adds coupling agent vinyltrimethoxy silane 11mmol, and coupling temperature is 70 DEG C,
Coupling time is 60min, and coupling terminates, and adds water and antioxidant 1010 in a polymer solution, and stirs, water
Consumption is initiator amount 100～300 times, the consumption of antioxidant 1010 is 20g, then, use steam stripping coacervation
Method or use devolatilization type screw extruder, separate polymer from solution, thus form mixture:
X-[B2-S2/B1-S1]n、X-[B2-(B1→S2)S2/B1-S1]n、X-[B2-S3-S2/B1-S1]n、
X-[B2-S3-(B1→S2)S2/B1-S1]n、S3, wherein, X be the span of Si, n be 2 n 4；
Or feed according to following steps:
Ith step: in polymeric kettle 1, in 3620g cyclohexane solvent, and in the presence of 3.5g activator THF,
Add mono vinyl arenes monomer styrene 800g and initiator s-BuLi 25mmol, form S1-Me, wherein S1For list
Vinyl aromatic monomer, Me is the metal ion of initiator, and reaction temperature is 80 DEG C, reaction pressure be 0.08～
0.20MPa, the response time is 50min, and now mono vinyl arenes monomer conversion ratio reaches 100%；
IIth step: in polymeric kettle 1, adds mono vinyl arenes monomer styrene 424g in 3820g cyclohexane solvent
With conjugated diene monomer isoprene 616g, reaction temperature is 80 DEG C, and reaction pressure is 0.08～0.20MPa, reaction
Time is 80min, and monovinylarene and conjugated diene hydrocarbon mixture are continuously added to, and charging rate is with the weight of mixture
Percentages, for per minute 1.6%～5.0%, the charging rate at mixture initial stage is less than reaction rate, forms random section
S1-B1/S2-Me, the charging rate in mixture later stage is higher than reaction rate, forms transition S1-B1/S2(B1→S2)-Me,
Wherein S1、S2For mono vinyl arenes monomer, B1For conjugated diene monomer；
Meanwhile, in polymeric kettle 2, in 1920g cyclohexane solvent, and in the presence of 0.75g activator THF,
Adding mono vinyl arenes monomer styrene 240g and initiator s-BuLi 5.8mmol, polymerase 17 min, polymerization temperature is
70 DEG C, now mono vinyl arenes monomer conversion ratio is 40%～50%, forms the polymer S of mono vinyl arenes monomer3；
IIIth step: the material in polymeric kettle 2 is added in polymeric kettle 1, and reaction is performed until substantially free of free monomer
Till in the presence of；
IVth step: in polymeric kettle 1, in 315g cyclohexane solvent, adds isoprene 160g end-blocking, reaction temperature
Degree is 80 DEG C, and the response time is 15min, containing S in system3, and form four kinds of living chain P:
S1-B1/S2(B1→S2)-B2-Me、S1-B1/S2-B2-Me、S1-B1/S2(B1→S2)-S3-B2-Me、S1-B1/S2-S3-B2-Me；
Vth step: in polymeric kettle 1, adds coupling agent MTES 6.8mmol, and coupling temperature is 50 DEG C,
Coupling time is 30min, and coupling terminates, and adds water and antioxidant 1010 in a polymer solution, and stirs, water
Consumption is initiator amount 100～300 times, the consumption of antioxidant 1010 is 20g, then, use steam stripping coacervation
Method or use devolatilization type screw extruder, separate polymer from solution, thus form mixture:
X-[B2-S2/B1-S1]n、X-[B2-(B1→S2)S2/B1-S1]n、X-[B2-S3-S2/B1-S1]n、
X-[B2-S3-(B1→S2)S2/B1-S1]n、S3, wherein, X be the span of Si, n be 2 n 4；
Or feed according to following steps:
Ith step: in polymeric kettle 1, in the 5398g 85wt% hexamethylene mixed solvent with 15wt% hexane, and
In the presence of 2.6g activator THF, add mono vinyl arenes monomer styrene 1500g and initiator s-BuLi
22mmol, forms S1-Me, wherein S1For mono vinyl arenes monomer, Me is the metal ion of initiator, reaction temperature
Degree is 70 DEG C, and reaction pressure is 0.08～0.20MPa, and the response time is 50min, and now mono vinyl arenes monomer turns
Rate reaches 100%；
IIth step: in polymeric kettle 1, adds single in the 2012g 85wt% hexamethylene mixed solvent with 15wt% hexane
Vinyl aromatic monomer styrene 220g and conjugated diene monomer butadiene 250g, reaction temperature is 65 DEG C, reaction pressure
Power is 0.08～0.20MPa, and the response time is 70min, and monovinylarene and conjugated diene hydrocarbon mixture are continuously added to,
Charging rate is in terms of the percentage by weight of mixture, and for per minute 1.6%～5.0%, the charging rate at mixture initial stage is low
In reaction rate, form random section S1-B1/S2-Me, the charging rate in mixture later stage is higher than reaction rate, is formed gradually
Become section S1-B1/S2(B1→S2)-Me, wherein S1、S2For mono vinyl arenes monomer, B1For conjugated diene monomer；
Meanwhile, in polymeric kettle 2, in the 2250g 85wt% hexamethylene mixed solvent with 15wt% hexane, and
In the presence of 0.80g activator THF, add mono vinyl arenes monomer styrene 300g and initiator s-BuLi 7.0mmol,
Polymerization 10min, polymerization temperature is 80 DEG C, and now mono vinyl arenes monomer conversion ratio is 40%～50%, forms single second
The polymer S of alkenyl arene monomer3；
IIIth step: the material in polymeric kettle 2 is added in polymeric kettle 1, and reaction is performed until substantially free of free monomer
Till in the presence of；
IVth step: in polymeric kettle 1, in the 315g 85wt% hexamethylene mixed solvent with 15wt% hexane, adds
Butadiene 130g blocks, and reaction temperature is 65 DEG C, and the response time is 25min, containing S in system3, and form four kinds
Living chain P:S1-B1/S2(B1→S2)-B2-Me、S1-B1/S2-B2-Me、S1-B1/S2(B1→S2)-S3-B2-Me、
S1-B1/S2-S3-B2-Me；
Vth step: in polymeric kettle 1, adds coupling agent MTES 5.5mmol, and coupling temperature is 60 DEG C,
Coupling time is 40min, and coupling terminates, and adds water and antioxidant TNP in a polymer solution, and stirs, water
Consumption is initiator amount 100～300 times, the consumption of antioxidant TNP is 20g, then, use steam stripping coacervation
Method or use devolatilization type screw extruder, separate polymer from solution, thus form mixture:
X-[B2-S2/B1-S1]n、X-[B2-(B1→S2)S2/B1-S1]n、X-[B2-S3-S2/B1-S1]n、
X-[B2-S3-(B1→S2)S2/B1-S1]n、S3, wherein, X be the span of Si, n be 2 n 4；
Or feed according to following steps:
Ith step: in polymeric kettle 1, in 4620g cyclohexane solvent, and in the presence of 2.1g activator THF,
Add mono vinyl arenes monomer styrene 1200g and initiator n-BuLi 28mmol, form S1-Me, wherein S1For
Mono vinyl arenes monomer, Me is the metal ion of initiator, and reaction temperature is 70 DEG C, reaction pressure be 0.08～
0.20MPa, the response time is 35min, and now mono vinyl arenes monomer conversion ratio reaches 100%；
IIth step: in polymeric kettle 1, adds mono vinyl arenes monomer styrene 370g in 2910g cyclohexane solvent
With conjugated diene monomer isoprene 310g, reaction temperature is 80 DEG C, and reaction pressure is 0.08～0.20MPa, reaction
Time is 80min, and monovinylarene and conjugated diene hydrocarbon mixture are continuously added to, and charging rate is with the weight of mixture
Percentages, for per minute 1.6%～5.0%, the charging rate at mixture initial stage is less than reaction rate, forms random section
S1-B1/S2-Me, the charging rate in mixture later stage is higher than reaction rate, forms transition S1-B1/S2(B1→S2)-Me,
Wherein S1、S2For mono vinyl arenes monomer, B1For conjugated diene monomer；
Meanwhile, in polymeric kettle 2, in 1688g cyclohexane solvent, and in the presence of 0.71g activator THF,
Adding mono vinyl arenes monomer styrene 200g and initiator n-BuLi 4.5mmol, be polymerized 10min, polymerization temperature is
65 DEG C, now mono vinyl arenes monomer conversion ratio is 40%～50%, forms the polymer S of mono vinyl arenes monomer3；
IIIth step: the material in polymeric kettle 2 is added in polymeric kettle 1, and reaction is performed until substantially free of free monomer
Till in the presence of；
IVth step: in polymeric kettle 1, in 278g cyclohexane solvent, adds isoprene 120g end-blocking, reaction temperature
Degree is 65 DEG C, and the response time is 25min, containing S in system3, and form four kinds of living chain P:
S1-B1/S2(B1→S2)-B2-Me、S1-B1/S2-B2-Me、S1-B1/S2(B1→S2)-S3-B2-Me、S1-B1/S2-S3-B2-Me；
Vth step: in polymeric kettle 1, adds coupling agent SnCl47.7mmol, coupling temperature is 75 DEG C, Coupling time
For 50min, coupling terminates, and adds water in a polymer solution, mass ratio is antioxidant 1010 and the antioxidant of 1:3
TNP, and stir, the consumption of water is 100～300 times of initiator amount, and total consumption of antioxidant is 20g, so
After, use steam stripping coacervation method or use devolatilization type screw extruder, polymer is separated from solution, thus shape
Resulting mixture: X-[B2-S2/B1-S1]n、X-[B2-(B1→S2)S2/B1-S1]n、X-[B2-S3-S2/B1-S1]n、
X-[B2-S3-(B1→S2)S2/B1-S1]n、S3, wherein, X be the span of Sn, n be 2 n 4；
Or feed according to following steps:
Ith step: in polymeric kettle 1, in 5067g hexane solvent, and in the presence of 1.0g activator THF,
Add mono vinyl arenes monomer styrene 1300g and initiator n-BuLi 34mmol, form S1-Me, wherein S1For
Mono vinyl arenes monomer, Me is the metal ion of initiator, and reaction temperature is 60 DEG C, reaction pressure be 0.08～
0.20MPa, the response time is 60min, and now mono vinyl arenes monomer conversion ratio reaches 100%；
IIth step: in polymeric kettle 1, adds mono vinyl arenes monomer styrene 340g in 2523g hexane solvent
With conjugated diene monomer butadiene 235g, reaction temperature is 50 DEG C, and reaction pressure is 0.08～0.20MPa, during reaction
Between be 120min, monovinylarene and conjugated diene hydrocarbon mixture are continuously added to, and charging rate is with the weight of mixture
Percentages, for per minute 1.6%～5.0%, the charging rate at mixture initial stage is less than reaction rate, forms random section
S1-B1/S2-Me, the charging rate in mixture later stage is higher than reaction rate, forms transition S1-B1/S2(B1→S2)-Me,
Wherein S1、S2For mono vinyl arenes monomer, B1For conjugated diene monomer；
Meanwhile, in polymeric kettle 2, in 3100g hexane solvent, and in the presence of 0.89g activator THF, add
Entering mono vinyl arenes monomer styrene 285g and initiator n-BuLi 8.0mmol, be polymerized 8min, polymerization temperature is
65 DEG C, now mono vinyl arenes monomer conversion ratio is 40%～50%, forms the polymer S of mono vinyl arenes monomer3；
IIIth step: the material in polymeric kettle 2 is added in polymeric kettle 1, and reaction is performed until substantially free of free monomer
Till in the presence of；
IVth step: in polymeric kettle 1, in 298g hexane solvent, adds butadiene 125g end-blocking, and reaction temperature is
60 DEG C, the response time is 30min, containing S in system3, and form four kinds of living chain P:S1-B1/S2(B1→S2)-B2-Me、
S1-B1/S2-B2-Me、S1-B1/S2(B1→S2)-S3-B2-Me、S1-B1/S2-S3-B2-Me；
Vth step: in polymeric kettle 1, adds coupling agent SiCl410.5mmol, coupling temperature is 80 DEG C, Coupling time
For 40min, coupling terminates, and adds water and antioxidant TNP in a polymer solution, and stirs, and the consumption of water is
100～300 times of initiator amount, the consumption of antioxidant TNP is 20g, then, uses steam stripping coacervation method or makes
With devolatilization type screw extruder, polymer is separated from solution, thus form mixture: X-[B2-S2/B1-S1]n、
X-[B2-(B1→S2)S2/B1-S1]n、X-[B2-S3-S2/B1-S1]n、X-[B2-S3-(B1→S2)S2/B1-S1]n、S3, wherein,
X be the span of Si, n be 2 n 4.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2004007581A1 (en) * | 2002-07-11 | 2004-01-22 | Kraton Polymers Research B.V. | Coupled styrenic block copolymers and process for preparing same |
| CN101831133A (en) * | 2009-03-13 | 2010-09-15 | 中国石油天然气股份有限公司 | Transparent block copolymer composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2004007581A1 (en) * | 2002-07-11 | 2004-01-22 | Kraton Polymers Research B.V. | Coupled styrenic block copolymers and process for preparing same |
| CN101831133A (en) * | 2009-03-13 | 2010-09-15 | 中国石油天然气股份有限公司 | Transparent block copolymer composition and preparation method thereof |
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