CN102453304B - Monovinylarene-conjugated diene block copolymer composition and preparation method and application thereof - Google Patents
Monovinylarene-conjugated diene block copolymer composition and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a linear monovinylarene-conjugated diene block copolymer composition and a preparation method and application thereof. The block copolymer composition comprises a penta-block copolymer with a structural formula being S1-B-C-D-S2 and a tri-block copolymer with a structural formula being C-D-S2, wherein S1 and S2 represent terminal polymer blocks which have the same or different degrees of polymerization and are derived from a monovinylarene monomer; B and C respectively represent two polymer blocks derived from conjugated diene; D represents a random copolymer block derived from monovinylarene and conjugated diene; and based on the weight of the block copolymer composition, the content of the penta-block copolymer is 60-90wt%, and the content of the tri-block copolymer with the structural formula being C-D-S2 is 10-40wt%.
Description
Technical field
The present invention relates to monovinylarene and conjugated diene block copolymer composition, particularly, the copolymer compositions that comprises two kinds of linear monovinylarenes and conjugated diene block that relates to a kind of novel structure, wherein a kind of is that linear monovinylarene and conjugated diene five block polymers are linear monovinylarene and conjugated diene triblock polymer with another kind.The invention still further relates to described monovinylarene and conjugated diene block copolymer preparation of compositions method and application thereof.
Technical background
The composition of linear segmented copolymer, particularly comprise a) triblock copolymer (at least two styrene block with at least one conjugated diene block) and b) composition of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock (have to component a) the similar block type of three block section multipolymers), be applied to adhesives industry.
The preparation of segmented copolymer is well-known.In representative synthetic method, utilize the organic lithium initiator compound to cause a kind of polymerization of monomer, up to ruing out of all monomers, obtain active homopolymer (first polymkeric substance); Add second kind of chemically different with first monomer monomers in this activity first polymkeric substance, the activity end of first polymkeric substance is as the point that continues polymerization, thereby second monomer is attached on the linear polymer with different blocks.The block polymer of growth all was active before end-blocking, end-blocking changes the activity end of segmented copolymer into do not increase material, thereby make polymkeric substance not have reactivity to monomer or coupling agent, the so-called Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of the polymkeric substance of end-blocking like this.If polymkeric substance does not have end-blocking, so reactive block copolymers can with the linear multi-block multipolymer of other monomer reaction formation order, perhaps reactive block copolymers contacts with the multi-functional group reagent of so-called coupling agent, two active chain ends is coupled together to form have the linear three block copolymer that doubles initial active di-block copolymer molecular weight.Connect the star block copolymer structure that plural active Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock obtains having at least three arms.Be US Patent No. 3,149 about one of first patent of the linear ABA segmented copolymer made by vinylbenzene and divinyl, 182.The scientific research personnel of Research Institute of Beijing Yanshan Petrochemical Corp adopts the reinforced polymerization process that distributes, and has synthesized multiple segmented copolymer, as Chinese patent CN1350012A, CN1350013A, CN1350014A, CN1350015A and CN1263117A etc.Chemical general factory synthetic rubber plant, Yueyang patent CN1175595A adopts three step charging technologies and reinforced coupling method prepared styrene isoprene styrene block copolymer (SIS) of two steps.
Disclosed a kind of polymer composition that is applied to peelable hot-fusible pressure-sensitive adhesive as US Patent No. 6025071, it comprises SIS triblock polymer and SI bi-block copolymer, and wherein the content of SI bi-block copolymer is higher than 50% (be benchmark with the SIS triblock polymer).The hot-fusible pressure-sensitive adhesive of using the said composition preparation with under molten state, have excellent tack between the substrates coated, simultaneously, can be easily between the skin-material of applying after the cooling, intactly peel off.
The low melting viscosity hot-fusible pressure-sensitive adhesive composition that US Patent No. 5853874 provides a kind of bond properties to be improved contains the thermoplastic elastomer (S-I) of (a) 100 weight parts
N-1S and (b) the oil tackifying resin of 70-150 weight part, wherein S represents polystyrene block, and I is polyisoprene blocks, and n is the integer of 2-10.The polystyrene weight content is 10-20wt% in the thermoplastic elastomer, and the number-average molecular weight of thermoplastic elastomer is 50000-175000, and in the thermoplastic elastomer weight content of SI diblock thing less than 0.1wt%.On the basis of above-mentioned composition, this patent further provides the composition of the S-I diblock thing of a kind of 0.1-10wt% of containing, and the polystyrene weight content of described diblock thing is 10-30wt%.
The hot-fusible pressure-sensitive adhesive that can be used for disposable product is provided in the US Patent No. 5750623, it comprises the linear A-B-A type segmented copolymer of 5-15wt% and the solid tackifier of 45-85wt%, plasticizing oil or the liquid tackifying resin of 0-35wt%, wherein B is polyisoprene, and A is polystyrene; A ingredients constitute 25-35 weight part in per 100 parts of block copolymer; This A-B-A type segmented copolymer contains and is less than 5% remaining A-B type diblock thing.This A-B-A type segmented copolymer is by the preparation of technology (1) coupling process, and its coupling efficiency is greater than 95%; Or the preparation of technology (2) order charging technology, its A-B type diblock thing content is less than 2%.
Patent EP1229059 provides a kind of segmented copolymer, and it comprises at least two the polymer blocks S and the one or more polymer blocks B that contain or contain simultaneously isoprene unit and 1,3-butadiene unit that contain vinyl aromatic monomer unit; Be benchmark with multipolymer weight, vinyl aromatic monomer unit content is 60-95wt%, and the total content of isoprene monomer unit and 1,3-butadiene monomeric unit is 40-5wt%, isoprene monomer unit/1,3-butadiene monomeric unit weight ratio is 45/55 to 97/3; Wherein based on the gross weight of vinyl aromatic monomer unit in the multipolymer, vinyl aromatic monomer unit partly contains the short chain section of 0-30wt%.Described segmented copolymer has superior stiffness, elongation, shock resistance, properties of transparency and thermal contraction performance, is used for molded article.
GB1387594 provides a kind of segmented copolymer for preparing the terminal nonrubber block of intermediate rubber block, and its preparation technology comprises (a) in inert solvent, uses alkyl lithium initiator to cause at least a monovinylarene and generates the catalytic activity polymer blocks; (b) at least a replacement or unsubstituted conjugated diene are contacted until the monomer completely consumed with the formed catalytic activity polymer blocks of step (a), reaction product is contacted with at least a monomer that is selected from monovinylarene finish polyreaction; Or (c) make the formed catalytic activity polymer blocks of step (a) and contacted with the mixture that at least a mono vinyl arenes monomer is formed by at least a replacement or unsubstituted conjugated diene monomer, finish polyreaction.
Patent WO03082985 provides a kind of bituminous composition, it comprises asphalt component and contains at least two conjugated diene block and the segmented copolymer of at least two monovinylarene blocks (S1-B1-S2-B2), wherein the B1 representative contains the isoprene of at least 50 moles of % and the poly-conjugated-diolefin block that apparent molecular weight is 180000-400000, S1 and S2 represent that molecular-weight average is the poly-monovinylarene block of 12000-40000, and B2 represents to contain the isoprene of at least 50 moles of % and the poly-conjugated-diolefin block that apparent molecular weight is 15000-60000; The weight ratio W of B1 and B2 is 3.0-12.0, and the content of poly-monovinylarene is 10-35wt%.
US Patent No. 5194500 discloses a kind of branching three arm styrene-isoprene block copolymer compositions for the pressure-sensitive adhesive mixture, wherein based on the weight of block copolymer composition, polystyrene content is 17-23wt%, as the S I arm content of load-bearing greater than 85wt%.This patented invention also provides a kind of method for preparing described three arm segmented copolymers, can cause by trifunctional initiator and synthesize, and a step feeds intake or feeds intake synthetic (S-I) step by step
3Segmented copolymer.This patent further provides a kind of coupling process to prepare three arm segmented copolymers (S-I)
3The method of-X, it adopts the polyfunctional group coupling agent with three reflecting points, 65-75 ℃ of linked reaction temperature, coupling efficiency 80-100%, products obtained therefrom contain the SI two block things of 0-20%.
For being applied to adhesive field particularly for the monovinylarene-conjugated diene block copolymer in hot-fusible pressure-sensitive adhesive field, lower melt viscosity means that being beneficial to coating processes, and better tack is beneficial to bonding and suitable stripping strength so that remove.Therefore, undoubted, exploitation is satisfied the novel block copolymer of hot-fusible pressure-sensitive adhesive performance requriements, is further optimized synthesis technique, is the direction of paying close attention in the industry and making great efforts always.
Summary of the invention
Based on above-mentioned prior art situation, the present inventor furthers investigate and explores structure and the performance of monovinylarene and conjugated diene polymer, carries out molecular designing by anionoid polymerization and prepares monovinylarene and the conjugated diene block copolymer composition with the performance that requires.
The object of the invention is to provide a kind of monovinylarene and conjugated diene block copolymer composition, this copolymer compositions comprises the copolymer compositions of two kinds of linear monovinylarenes and conjugated diene block, and wherein a kind of is that linear monovinylarene and conjugated diene five block polymers are linear monovinylarene and conjugated diene triblock polymer with another kind.This block copolymer composition is because the existence of monovinylarene and conjugated diene random copolymerization block and contain essentially identical monovinylarene and the introducing of the triblock polymer of conjugated diene random copolymerization block in five block polymers, can reduce the melt viscosity of monovinylarene and conjugated diene block copolymer, when being applied to the hot melt adhesive preparation process, be beneficial to coating; Have good tack simultaneously, hold viscosity and stripping strength, thereby polymkeric substance is more suitable in the base polymer as the sanitary product pressure sensitive adhesive.
Another object of the present invention is to provide a kind of preparation method of above-mentioned block copolymer composition.
A further object of the present invention is to provide the application of above-mentioned block copolymer composition in hot melt adhesive.
Particularly, one aspect of the present invention provides a kind of novel monovinylarene and conjugated diene block copolymer composition, and this block copolymer composition comprises:
(1) a kind of structural formula is five segmented copolymers of S1-B-C-D-S2, and wherein S1 and S2 represent the end polymer blocks that is derived from mono vinyl arenes monomer that the polymerization degree is identical or different; B and C represent two kinds of polymer blocks that are derived from conjugated diene respectively; D represents to be derived from the block of random copolymer of monovinylarene and conjugated diene; With
(2) a kind of structural formula is the triblock copolymer of C-D-S2 structure, and wherein C represents to be derived from the polymer blocks of conjugated diene; D represents to be derived from the block of random copolymer of monovinylarene and conjugated diene; S2 represents to be derived from the polymer blocks of mono vinyl arenes monomer.
For block copolymer composition of the present invention, based on the weight of block copolymer composition, the content of five segmented copolymer S1-B-C-D-S2 is 60-90 weight %, preferred 70-80 weight %; The content of triblock copolymer C-D-S2 is 10-40 weight %, preferred 20-30 weight %; The content of monovinylarene is 15-40 weight %, preferred 20-30 weight %; The conjugated diolefine hydrocarbon content is 60-85 weight %, preferred 70-80 weight %; Wherein the content of S1 section is 5-20 weight %, preferred 6-15 weight %; The content of B section is 1-60 weight %, preferred 10-30 weight %; The content of C section is 25-84 weight %, preferred 35-60 weight %; The content of D section is 1-25 weight %, preferred 5-15 weight %; The content of S2 section is 4-20 weight %, preferred 8-15 weight %.
For block copolymer composition of the present invention, based on the weight of five segmented copolymer S1-B-C-D-S2, the monovinylarene content in this five segmented copolymer is 15-40 weight %, preferred 20-30 weight %.Based on the weight of triblock copolymer C-D-S2, the monovinylarene content in this triblock copolymer is 10-40 weight %, preferred 15-25 weight %.
In block copolymer composition of the present invention, the number-average molecular weight of five segmented copolymer S1-B-C-D-S2 is generally 100000-160000, preferred 100000-135000; The number-average molecular weight of three block thing C-D-S2 is generally 30000-85000, is preferably 50000-80000; Wherein the number-average molecular weight of S1 section is 8500-24000, is preferably 10000-16000; The number-average molecular weight of B section is 20000-110000, is preferably 20000-50000; The number-average molecular weight of C section is 17000-70000, is preferably 30000-65000; The number-average molecular weight of D section is 500-25000, preferred 1000-15000; The number-average molecular weight of S2 section is 8500-24000, is preferably 10000-16000.
In block copolymer composition of the present invention, B and C represent two kinds of polymer blocks that are derived from conjugated diene respectively, wherein B and C both can be the homopolymer blocks that is derived from single conjugated diene, also can be the block of random copolymer that is derived from two or more conjugated dienes; Preferred B and C are the homopolymer blocks that is derived from single conjugated diene; More preferably B is the homopolymer block that is derived from identical single conjugated diene with C.
In block copolymer composition of the present invention, described conjugated diene refers to have any monomer of conjugated double bond in its molecule, and the example includes but not limited to C
4-C
8Conjugated diene monomer is as divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene and composition thereof.Described conjugated diene is preferably isoprene and/or divinyl.
In block copolymer composition of the present invention, described monovinylarene refers to have at its aromatic ring the aromatic monomer of a vinyl substituted base, the example includes but not limited to the vinylbenzene that vinylbenzene or alkyl replace, as vinylbenzene, Vinyl toluene, alpha-methyl styrene, 4-t-butyl styrene, 4-vinyl toluene, 3,5-diethylbenzene ethene, 3,5-di-n-butyl vinylbenzene, 4-n-propylbenzene ethene, 4-dodecyl vinylbenzene and composition thereof; Optimization styrene, Vinyl toluene, alpha-methyl styrene and composition thereof; Vinylbenzene most preferably.
Therefore, in block copolymer composition of the present invention, preferably use vinylbenzene, isoprene and/or divinyl as comonomer.
In another aspect of this invention, also provide the preparation method of described block copolymer composition, it comprises the step of following order:
(a) under the condition that non-polar hydrocarbon kind solvent Semi-polarity conditioning agent exists, add first part's organic lithium initiator and make mono vinyl arenes monomer be polymerized to conversion substantially fully, obtain active poly-monovinylarene section S1;
(b) add one or more conjugated diene monomers in above-mentioned polymerization system, utilize the poly-monovinylarene section S1 of the activity that obtains in the step (a) to cause conjugated diolefin homopolymerization or copolymerization, polymerization obtains poly-conjugated-diolefin section B up to transforming substantially fully;
(c) add the organic lithium initiator of second section in the polymerization system, add one or more conjugated diene monomers after a while, when monomer conversion reaches design requirements, carry out next step polymerization;
(d) add mono vinyl arenes monomer in polymerization system, monomer polymerization is to transforming substantially fully in polymerization system;
(e) add terminator and stop polyreaction.
This it is pointed out that among the preparation method at block copolymer composition of the present invention all related technical characterictics all have with above about the described identical implication of block copolymer composition of the present invention.
In addition, till the implication of the term when describing the preparation method of block copolymer composition of the present invention " polymerization is up to transforming substantially fully " refers to that monomer that polyreaction proceeds to adding exhausts substantially, that is to say that polymerization will be performed until the monomer conversion of adding greater than 99%.
The preparation method of block copolymer composition of the present invention carries out under inert gas environment protection, and operable rare gas element is the gas used always as nitrogen, argon gas, helium etc.
In the preparation method of block copolymer composition of the present invention, in step (a), used the non-polar hydrocarbon kind solvent.At this, those skilled in the art should be appreciated that obviously this solvent should be in a liquid state under the polymeric reaction condition of step (a), and can not participate in polyreaction, also can not react with the polymkeric substance that reaction obtains, and namely this solvent is inertia.This kind solvent is apparent for the those of ordinary skill in anionoid polymerization field, and can easily select.However, for the purpose of the present invention, this non-polar hydrocarbon kind solvent is preferably benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil or aforementioned solvents in two or more arbitrary combination.For the polymerization of step (a), the consumption of non-polar hydrocarbon kind solvent is conventional, for example can control solvent consumption so that monomer concentration at 5-30wt%, be preferably in the scope of 8-20wt%.
In the preparation method of block copolymer composition of the present invention, can adopt disclosed various organic lithium initiators in the prior art, the preferred alkyl lithium initiator.The limiting examples of alkyl lithium initiator can be lithium methide, lithium ethide, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, hexyllithium, uncle's octyl group lithium, positive decyl lithium etc., and the preferred alkyl lithium initiator that uses comprises n-Butyl Lithium, s-butyl lithium and tert-butyl lithium.In the methods of the invention, also can use two or more alkyl lithium initiator, for example use the arbitrary combination of the cited alkyl lithium catalyst in front.Particularly preferably be, method of the present invention uses n-Butyl Lithium as polymerization starter.
For the preparation method of block copolymer composition of the present invention, the consumption of the first part's organic lithium initiator that adds in the step (a) depends on the molecular weight of the polymer blocks S1 that is derived from mono vinyl arenes monomer that will synthesize and the catalytic activity that depends on initiator itself; The consumption of the second section organic lithium initiator that adds in the step (c) then depends on the molecular weight of the five segmented copolymer S1-B-C-D-S2 that will synthesize, the weight content of triblock copolymer C-D-S2 and the catalytic activity of initiator itself.
For the specific organic lithium initiator of use synthesizes the polymkeric substance with specified molecular weight, those skilled in the art can determine the consumption of this organic lithium initiator according to the disclosure of prior art, and for example " lithium is synthetic rubber and thermoplastic elastomer " Wang Dechong, Liang Aimin, Han Bingyong etc. write: the 19-20 page or leaf; Perhaps " polymer chemistry " Pan Zuren edits the 4th edition: the 162nd page; These documents all are incorporated herein this paper as a reference.In the present invention, the feasible number-average molecular weight that is derived from the polymer blocks S1 of mono vinyl arenes monomer of the consumption of first part's organic lithium initiator is 8500-24000, is preferably 10000-16000; The consumption of second section organic lithium initiator makes that the number-average molecular weight of five segmented copolymer S1-B-C-D-S2 is 100000-160000, preferred 100000-135000; The number-average molecular weight of three block thing C-D-S2 is generally 30000-85000, is preferably 50000-80000; And the consumption of second section organic lithium initiator makes that the content of three block thing C-D-S2 is 10-40 weight % based on the weight of block copolymer composition, preferred 20-30 weight %.
In the preparation method of block copolymer composition of the present invention, step (a) is carried out in the presence of polar modifier.For the present invention, used polar modifier is the conventional reagent in the synthetic field of rubber, comprises containing oxygen, nitrogenous, sulfur-bearing or phosphorous compound or their mixture, and its specific examples includes but not limited to ether, dibutyl ether, tetrahydrofuran (THF), glycol dimethyl ether, diglyme, tetrahydrofurfuryl alcohol ether, dioxane, crown ether, triethylamine, Tetramethyl Ethylene Diamine, HMPA, potassium tert.-butoxide, tertiary amyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate (ABS) potassium, sodium alkyl benzene sulfonate, the perhaps arbitrary combination of two or more in the aforementioned polar modifier.The preferred tetrahydrofuran (THF) that uses is as polar modifier.The mol ratio of polar modifier and initiator can be 0.5-5, preferred 0.8-2.
In the preparation method of block copolymer composition of the present invention, the temperature that step (a) uses organic lithium initiator to cause the monovinylarene polymerization can change in wide region.Usually, this kick off temperature is 20-100 ℃, is preferably 40-80 ℃.
In the preparation method of block copolymer composition of the present invention, after the polyreaction of step (a) causes, subsequent step (b), (c) and temperature (d) there is not special requirement, as long as can keep the carrying out of polyreaction.As the alternative technology scheme, in the step (b), when adding conjugated diene monomer, the Controllable Temperature of polymerization reaction mixture is built in 50-90 ℃, in preferred 60-80 ℃ the scope; In the step (c), when adding conjugated diene monomer, the Controllable Temperature of polymerization reaction mixture is built in 50-100 ℃, in preferred 60-90 ℃ the scope; In the step (d), when adding mono vinyl arenes monomer, the Controllable Temperature of polymerization reaction mixture is built in 50-100 ℃, in preferred 60-90 ℃ the scope.
In block copolymer composition preparation method's of the present invention step (c), whether the polymerization of one or more conjugated diene monomers of adding reaches the design transformation efficiency, can measure by gas chromatography.
After the polyreaction of block copolymer composition preparation method's of the present invention step (d) is finished, in step (e), can use terminator to stop polyreaction.The terminator that is used for this step is conventional to those skilled in the art.Common operable terminator comprises deionized water, alcohol, acid etc.At this, preferably water and contain 4-12 carbon atom higher fatty acid reactive polymer solution is stopped, this is useful to the color and luster that improves polymkeric substance.
Randomly, can further handle block copolymer composition of the present invention, for example before drying treatment, anti-aging agent be joined in the reaction mixture (that is polymkeric substance glue).After stopping, can also in reaction mixture (that is polymkeric substance glue), add anti-aging agent.For the present invention, conventional anti-aging agent can use.Preferably, operable anti-aging agent comprises according to the present invention: 2,6-ditertbutylparacresol (264), Irganox 1520 (Switzerland vapour Bagong department), four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (namely 1010)/tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) compound anti-aging agent (wherein 168 content is not higher than 50 weight %) ester (namely 168)), and β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester (namely 1076)/compound anti-aging agent of three (nonyl is for phenyl) phosphorous acid ester (being TNPP) (wherein 1076 content is not higher than 50 weight %).According to the present invention, the consumption of anti-aging agent is 0.05-2 weight % based on dried glue weight (being polymer weight).At last, the polymkeric substance glue can precipitate from solvent by similar fashion such as alcoholization precipitation, centrifugation, filtration, decant, hot water cohesions separates out, and also can adopt the stripping mode that the volatile organic solvent in the multipolymer is separated.
In one side more of the present invention, above-mentioned monovinylarene and the application of conjugated diene block copolymer composition in hot melt adhesive are also provided.
As mentioned above, in preparation method of the present invention, adopt to add organic lithium initiator and reinforced method of four steps of polymerization single polymerization monomer for twice, obtained the block copolymer composition of novel structure.Simple, the control easily of preparation method's technology of the present invention, can control five segmented copolymers and the weight ratio of triblock copolymer and the molecular weight of two kinds of multipolymers in the block copolymer composition efficiently and accurately simultaneously, obtain having the tailor-made polymer compositions of wishing performance.And because the existence of monovinylarene and conjugated diene random copolymerization block and contain essentially identical monovinylarene and the introducing of the triblock polymer of conjugated diene random copolymerization block in five block polymers, can reduce the melt viscosity of monovinylarene and conjugated diene block copolymer composition, when being applied to the hot melt adhesive preparation process, be beneficial to coating; Have good tack simultaneously, hold viscosity and stripping strength, thereby polymkeric substance is more suitable in the base polymer as the sanitary product pressure sensitive adhesive.
Embodiment
Enumerate some embodiments of the present invention below, so as to further specifying characteristics of the present invention, but do not limit the scope of the invention with this.
Testing method:
1, the content of molecular weight and each block adopts the U.S. 150C of WATERS company type gel permeation chromatograph (GPC) to measure, and THF is moving phase, and narrow distribution polystyrene is standard specimen, and temperature is 25 ℃.
2, the testing method of the physicals of product is as shown in table 2.
3, each of product section content obtains according to each step monomer add-on and nuclear magnetic resonance spectroscopy in the polymerization process, wherein nucleus magnetic resonance adopts the AV400 type nuclear magnetic resonance spectrometer mensuration that Switzerland Bruker company produces, method is proton nmr spectra, and solvent is deuterochloroform.
Embodiment 1
Under nitrogen atmosphere, in 5 liters of stainless steel stirring tanks, add tetrahydrofuran (THF) and the 50g vinylbenzene of 2457g hexanaphthene, 0.5g and under 55 ℃, add the 3.06mmol n-butyl lithium initiator, reacted 15 minutes.Add the 60g isoprene, reacted 25 minutes.Add the 2.0mmol n-Butyl Lithium, after 1 minute, add the 240g isoprene, transformation efficiency reaches at 90% o'clock, adds 50g vinylbenzene, reacts the deionized water that adds 0.6g after 15 minutes and reacts 10 minutes.The glue that obtains adds anti-aging agent, anti-aging agent be 1076 and TNPP composite, 1076 content is 33.3 weight % in this anti-aging agent, the content of TNPP is 66.7 weight %, and add-on is 0.9% of dried glue weight, mixes after 10 minutes, get polymers soln and condense with hot water, the hot-rolling drying treatment.Sample is carried out the physicals test, and the result is as shown in table 1 below.
Embodiment 2
Under nitrogen atmosphere, in 5 liters of stainless steel stirring tanks, add tetrahydrofuran (THF) and the 40g vinylbenzene of 2457g hexanaphthene, 0.6g and under 55 ℃, add the 3.8mmol n-butyl lithium initiator, reacted 15 minutes.Add the 67g isoprene, reacted 25 minutes.Add the 1.7mmol n-Butyl Lithium, after 1 minute, add the 232g isoprene, reaction conversion ratio reaches at 90% o'clock, adds 60g vinylbenzene, reacts the deionized water that adds 0.6g after 15 minutes and reacts 10 minutes.The glue that obtains adds anti-aging agent, anti-aging agent be 1076 and TNPP composite, 1076 content is 33.3 weight % in this anti-aging agent, the content of TNPP is 66.7 weight %, and add-on is 0.9% of dried glue weight, mixes after 10 minutes, get polymers soln and condense with hot water, the hot-rolling drying treatment.Sample is carried out the physicals test, and the result is as shown in table 1 below.
Embodiment 3
Under nitrogen atmosphere, in 5 liters of stainless steel stirring tanks, add tetrahydrofuran (THF) and the 49g vinylbenzene of 2457g hexanaphthene, 0.35g and under 55 ℃, add the 3.83mmol n-butyl lithium initiator, reacted 15 minutes.Add the 60g isoprene, reacted 25 minutes.Add the 1.71mmol n-Butyl Lithium, after 1 minute, add the 220g isoprene, transformation efficiency reaches at 85% o'clock, adds 71g vinylbenzene, reacts the deionized water that adds 0.6g after 15 minutes and reacts 10 minutes.The glue that obtains adds anti-aging agent, anti-aging agent be 1076 and TNPP composite, 1076 content is 33.3 weight % in this anti-aging agent, the content of TNPP is 66.7 weight %, and add-on is 0.9% of dried glue weight, mixes after 10 minutes, get polymers soln and condense with hot water, the hot-rolling drying treatment.Sample is carried out the physicals test, and the result is as shown in table 1 below.
Embodiment 4
Under nitrogen atmosphere, in 5 liters of stainless steel stirring tanks, add tetrahydrofuran (THF) and the 50g vinylbenzene of 2457g hexanaphthene, 0.3g and under 55 ℃, add the 3.06mmol n-butyl lithium initiator, reacted 15 minutes.Add the 60g isoprene, reacted 25 minutes.Add the 2.04mmol n-Butyl Lithium, after 1 minute, add the 240g isoprene, transformation efficiency reaches at 75% o'clock, adds 50g vinylbenzene, reacts the deionized water that adds 0.6g after 15 minutes and reacts 10 minutes.The glue that obtains adds anti-aging agent, anti-aging agent be 1076 and TNPP composite, 1076 content is 33.3 weight % in this anti-aging agent, the content of TNPP is 66.7 weight %, and add-on is 0.9% of dried glue weight, mixes after 10 minutes, get polymers soln and condense with hot water, the hot-rolling drying treatment.Sample is carried out the physicals test, and the result is as shown in table 1 below.
Embodiment 5
Under nitrogen atmosphere, in 5 liters of stainless steel stirring tanks, add tetrahydrofuran (THF) and the 37g vinylbenzene of 2457g hexanaphthene, 0.24g and under 55 ℃, add the 3.8mmol n-butyl lithium initiator, reacted 15 minutes.Add the mixture of 42.8g isoprene and 26.8g divinyl, reacted 25 minutes.Add the 1.5mmol n-Butyl Lithium, after 1 minute, the mixture that adds 149g isoprene and 93g divinyl reacts, and transformation efficiency reaches at 90% o'clock, adds 51g vinylbenzene, reacts the deionized water that adds 0.6g after 15 minutes and reacts 10 minutes.The glue that obtains adds anti-aging agent, anti-aging agent be 1076 and TNPP composite, 1076 content is 33.3 weight % in this anti-aging agent, the content of TNPP is 66.7 weight %, and add-on is 0.9% of dried glue weight, mixes after 10 minutes, get polymers soln and condense with hot water, the hot-rolling drying treatment.Sample is carried out the physicals test, and the result is as shown in table 1 below.
Embodiment 6
Under nitrogen atmosphere, in 5 liters of stainless steel stirring tanks, add tetrahydrofuran (THF) and the 30g vinylbenzene of 2457g hexanaphthene, 0.24g and under 55 ℃, add the 2.8mmol n-butyl lithium initiator, reacted 15 minutes.Add the mixture of 46g isoprene and 29g divinyl, reacted 25 minutes.Add the 2.5mmol n-Butyl Lithium, after 1 minute, the mixture that adds 146g isoprene and 91g divinyl reacts, and transformation efficiency reaches at 85% o'clock, adds 58g vinylbenzene, reacts the deionized water that adds 0.6g after 15 minutes and reacts 10 minutes.The glue that obtains adds anti-aging agent, anti-aging agent be 1076 and TNPP composite, 1076 content is 33.3 weight % in this anti-aging agent, the content of TNPP is 66.7 weight %, and add-on is 0.9% of dried glue weight, mixes after 10 minutes, get polymers soln and condense with hot water, the hot-rolling drying treatment.Sample is carried out the physicals test, and the result is as shown in table 1 below.
Embodiment 7
In nitrogen atmosphere, in 5 liters of stainless steel stirring tanks, add tetrahydrofuran (THF) and the 27g vinylbenzene of 2457g hexanaphthene, 0.3g and under 55 ℃, add the 3.4mmol n-butyl lithium initiator, reacted 15 minutes.Add the mixture of 40g isoprene and 40g divinyl, reacted 25 minutes.Add the 2.1mmol n-Butyl Lithium, after 1 minute, the mixture that adds 120g isoprene and 120g divinyl reacts, and transformation efficiency reaches at 90% o'clock, adds 53g vinylbenzene, reacts the deionized water that adds 0.6g after 15 minutes and reacts 10 minutes.The glue that obtains adds anti-aging agent, anti-aging agent be 1076 and TNPP composite, 1076 content is 33.3 weight % in this anti-aging agent, the content of TNPP is 66.7 weight %, and add-on is 0.9% of dried glue weight, mixes after 10 minutes, get polymers soln and condense with hot water, the hot-rolling drying treatment.Sample is carried out the physicals test, and the result is as shown in table 1 below.
Embodiment 8
In nitrogen atmosphere, in 5 liters of stainless steel stirring tanks, add tetrahydrofuran (THF) and the 56g vinylbenzene of 2457g hexanaphthene, 0.30g and under 55 ℃, add the 4.1mmol n-butyl lithium initiator, reacted 15 minutes.Add the 107g divinyl, reacted 25 minutes.Add the 1.0mmol n-Butyl Lithium, after 1 minute, add the 173g divinyl and react, transformation efficiency reaches at 85% o'clock, adds 64g vinylbenzene, reacts the deionized water that adds 0.6g after 15 minutes and reacts 10 minutes.The glue that obtains adds anti-aging agent, anti-aging agent be 1076 and TNPP composite, 1076 content is 33.3 weight % in this anti-aging agent, the content of TNPP is 66.7 weight %, and add-on is 0.9% of dried glue weight, mixes after 10 minutes, get polymers soln and condense with hot water, the hot-rolling drying treatment.Sample is carried out the physicals test, and the result is as shown in table 1 below.
Embodiment 9
In nitrogen atmosphere, in 5 liters of stainless steel stirring tanks, add tetrahydrofuran (THF) and the 53g vinylbenzene of 2457g hexanaphthene, 0.36g and under 55 ℃, add the 3.6mmol n-butyl lithium initiator, reacted 15 minutes.Add the 108g divinyl, reacted 25 minutes.Add the 1.5mmol n-Butyl Lithium, after 1 minute, add the 176g divinyl and react, transformation efficiency reaches at 80% o'clock, adds 63g vinylbenzene, reacts the deionized water that adds 0.6g after 15 minutes and reacts 10 minutes.The glue that obtains adds anti-aging agent, anti-aging agent be 1076 and TNPP composite, 1076 content is 33.3 weight % in this anti-aging agent, the content of TNPP is 66.7 weight %, and add-on is 0.9% of dried glue weight, mixes after 10 minutes, get polymers soln and condense with hot water, the hot-rolling drying treatment.Sample is carried out the physicals test, and the result is as shown in table 1 below.
Claims (35)
1. a linear monovinylarene and conjugated diene block copolymer composition, described block copolymer composition comprises:
(1) a kind of structural formula is five segmented copolymers of S1-B-C-D-S2, and wherein S1 and S2 represent the end polymer blocks that is derived from mono vinyl arenes monomer that the polymerization degree is identical or different; B and C represent two kinds of polymer blocks that are derived from conjugated diene respectively; D represents to be derived from the block of random copolymer of monovinylarene and conjugated diene; With
(2) a kind of structural formula is the triblock copolymer of C-D-S2 structure, and wherein C represents to be derived from the polymer blocks of conjugated diene; D represents to be derived from the block of random copolymer of monovinylarene and conjugated diene; S2 represents to be derived from the polymer blocks of mono vinyl arenes monomer;
Wherein based on the weight of block copolymer composition, the content of five segmented copolymer S1-B-C-D-S2 is 60-90 weight %; The content of triblock copolymer C-D-S2 is 10-40 weight %.
2. according to the block copolymer composition of claim 1, wherein based on the weight of block copolymer composition, the content of five segmented copolymer S1-B-C-D-S2 is 70-80 weight %; The content of triblock copolymer C-D-S2 is 20-30 weight %.
3. according to the block copolymer composition of claim 1, wherein based on the weight of block copolymer composition, the content of monovinylarene is 15-40 weight %; The conjugated diolefine hydrocarbon content is 60-85 weight %.
4. according to the block copolymer composition of claim 3, wherein based on the weight of block copolymer composition, the content of monovinylarene is 20-30 weight %; The conjugated diolefine hydrocarbon content is 70-80 weight %.
5. according to each block copolymer composition among the claim 1-4, wherein based on the weight of block copolymer composition, wherein the content of S1 section is 5-20 weight %; The content of B section is 1-60 weight %; The content of C section is 25-84 weight %; The content of D section is 1-25 weight %; The content of S2 section is 4-20 weight %.
6. according to the block copolymer composition of claim 5, wherein based on the weight of block copolymer composition, wherein the content of S1 section is 6-15 weight %; The content of B section is 10-30 weight %; The content of C section is 35-60 weight %; The content of D section is 5-15 weight %; The content of S2 section is 8-15 weight %.
7. according to each block copolymer composition among the claim 1-4, wherein based on the weight of five segmented copolymer S1-B-C-D-S2, the monovinylarene content in this five segmented copolymer is 15-40 weight %; Based on the weight of triblock copolymer C-D-S2, the monovinylarene content in this triblock copolymer is 10-40 weight %.
8. according to the block copolymer composition of claim 7, wherein based on the weight of five segmented copolymer S1-B-C-D-S2, the monovinylarene content in this five segmented copolymer is 20-30 weight %; Based on the weight of triblock copolymer C-D-S2, the monovinylarene content in this triblock copolymer is 15-25 weight %.
9. according to each block copolymer composition among the claim 1-4, the number-average molecular weight of wherein said five segmented copolymer S1-B-C-D-S2 is 100000-160000; The number-average molecular weight of triblock copolymer C-D-S2 is 30000-85000.
10. according to the block copolymer composition of claim 9, the number-average molecular weight of wherein said five segmented copolymer S1-B-C-D-S2 is 100000-135000; The number-average molecular weight of triblock copolymer C-D-S2 is 50000-80000.
11. according to each block copolymer composition among the claim 1-4, the number-average molecular weight of wherein said S1 section is 8500-24000; The number-average molecular weight of B section is 20000-110000; The number-average molecular weight of C section is 17000-70000; The number-average molecular weight of D section is 500-25000; The number-average molecular weight of S2 section is 8500-24000.
12. according to the block copolymer composition of claim 9, the number-average molecular weight of wherein said S1 section is 8500-24000; The number-average molecular weight of B section is 20000-110000; The number-average molecular weight of C section is 17000-70000; The number-average molecular weight of D section is 500-25000; The number-average molecular weight of S2 section is 8500-24000.
13. according to the block copolymer composition of claim 11, the number-average molecular weight of wherein said S1 section is 10000-16000; The number-average molecular weight of B section is 20000-50000; The number-average molecular weight of C section is 30000-65000; The number-average molecular weight of D section is 1000-15000; The number-average molecular weight of S2 section is 10000-16000.
14. according to the block copolymer composition of claim 12, the number-average molecular weight of wherein said S1 section is 10000-16000; The number-average molecular weight of B section is 20000-50000; The number-average molecular weight of C section is 30000-65000; The number-average molecular weight of D section is 1000-15000; The number-average molecular weight of S2 section is 10000-16000.
15. according to each block copolymer composition among the claim 1-4, wherein B and C are the homopolymer blocks that is derived from single conjugated diene, perhaps are derived from the block of random copolymer of two or more conjugated dienes.
16. according to the block copolymer composition of claim 15, wherein B and C are the homopolymer blocks that is derived from single conjugated diene.
17. according to the block copolymer composition of claim 16, wherein B is the homopolymer block that is derived from identical single conjugated diene with C.
18. according to each block copolymer composition among the claim 1-4, wherein said monovinylarene is selected from vinylbenzene, Vinyl toluene, alpha-methyl styrene, 4-t-butyl styrene, 4-vinyl toluene, 3,5-diethylbenzene ethene, 3,5-di-n-butyl vinylbenzene, 4-n-propylbenzene ethene, 4-dodecyl vinylbenzene and composition thereof.
19. according to the block copolymer composition of claim 18, wherein said monovinylarene is vinylbenzene.
20. according to each block copolymer composition among the claim 1-4, wherein said conjugated diene is selected from divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene and composition thereof.
21. according to the block copolymer composition of claim 20, wherein said conjugated diene is isoprene and/or divinyl.
22. according to the preparation method of each block copolymer composition among the claim 1-21, it comprises the step of following order:
(a) under the condition that non-polar hydrocarbon kind solvent Semi-polarity conditioning agent exists, add first part's organic lithium initiator and make mono vinyl arenes monomer be polymerized to conversion substantially fully, obtain active poly-monovinylarene section S1;
(b) add one or more conjugated diene monomers in above-mentioned polymerization system, utilize the poly-monovinylarene section S1 of the activity that obtains in the step (a) to cause conjugated diolefin homopolymerization or copolymerization, polymerization obtains poly-conjugated-diolefin section B up to transforming substantially fully;
(c) add the organic lithium initiator of second section in the polymerization system, add one or more conjugated diene monomers after a while, when monomer conversion reaches design requirements, carry out next step polymerization;
(d) add mono vinyl arenes monomer in polymerization system, monomer polymerization is to transforming substantially fully in polymerization system;
(e) add terminator and stop polyreaction.
23. according to the method for claim 22, wherein said non-polar hydrocarbon kind solvent is benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, raffinate oil or aforementioned solvents in two or more arbitrary combination.
24. according to the method for claim 22, wherein said organic lithium initiator is selected from lithium methide, lithium ethide, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, hexyllithium, uncle's octyl group lithium or their arbitrary combination.
25. according to the method for claim 24, wherein said organic lithium initiator is selected from n-Butyl Lithium, s-butyl lithium, tert-butyl lithium or their arbitrary combination.
26. according to the method for claim 25, wherein said organic lithium initiator is n-Butyl Lithium.
27. according to each method among the claim 22-26, wherein said polar modifier is ether, dibutyl ether, tetrahydrofuran (THF), glycol dimethyl ether, diglyme, tetrahydrofurfuryl alcohol ether, dioxane, crown ether, triethylamine, Tetramethyl Ethylene Diamine, HMPA, potassium tert.-butoxide, tertiary amyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate (ABS) potassium, sodium alkyl benzene sulfonate, the perhaps arbitrary combination of two or more in the aforementioned polar modifier.
28. according to the method for claim 27, wherein said polar modifier is tetrahydrofuran (THF).
29. according to the method for claim 27, the mol ratio of wherein said polar modifier add-on and organic lithium initiator is 0.5-5.
30. according to the method for claim 29, the mol ratio of wherein said polar modifier add-on and organic lithium initiator is 0.8-2.
31. according to the method for claim 28, the mol ratio of wherein said polar modifier add-on and organic lithium initiator is 0.5-5.
32. according to the method for claim 31, the mol ratio of wherein said polar modifier add-on and organic lithium initiator is 0.8-2.
33. according to each method among the claim 22-26, wherein said terminator is selected from water, carbonic acid gas or contains the higher fatty acid of 4-12 carbon atom.
34. according to each method among the claim 22-26, further be included in after polyreaction stops, in polymerization reaction mixture, add anti-aging agent.
35. according to each the application of block copolymer composition in hot melt adhesive among the claim 1-21.
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| CN1120342A (en) * | 1993-03-30 | 1996-04-10 | 国际壳牌研究有限公司 | Process for the preparation of a block copolymer composition and block copolymer composition |
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