CN1257080A - Coupling type polymer and preparation process thereof - Google Patents
Coupling type polymer and preparation process thereof Download PDFInfo
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Abstract
The present invention provides a coupled type polymer and its preparation method. Said coupled type polymer is made up by using a polymer whose active terminal group is alkali metal and a coupling agent through a certain reaction process. Said invention also provides the chemical formula of said coupling agent, and said coupling agent not only possesses high coupling effect, but also does not produce hazardous material to corrode pipeline, and the coupling constant of the obtained coupled polymer is less than 3, so that it not only possesses excellent mechanical properties of rubber, but also possesses high transparency and good abrasion resistance.
Description
The present invention relates to a kind of coupling type polymer and preparation method thereof, be specially the reactive terminal base and be alkali-metal polymkeric substance and get with novel coupler coupling.
Industrially often make initiator with organic alkali metal compound, polymerized conjugated diene or conjugated diolefine and monovinyl aromatic hydrocarbon monomer contain the carbonyl ion of active anion and the alkalimetal ion of cation to form the polymer ends base.And then utilize this base polymer of coupler coupling to form the multipolymer of linearity or hub-and-spoke configuration.The coupling center of coupler just becomes the core (nucleus) of this base polymer.This type of polymerization has more efficient more than the similar and different monomer polymerization method of contiguous segmentation (promptly not adopting coupling manner), operate more stable, thereby be used in the styrene butadiene rubbers of polybutadiene rubber, solution polymerization process and thermoplastic elastomer (as styrene-butadiene-styrene SBS by industry member widely, and styrene-isoprene-phenylethene SIS, styrene-ethylene/butylene-styrene SEBS, styrene-ethylene/propylene-styrene SEPS) manufacturing of product such as.
All there is following shortcoming in employed in the past coupler: English Patent shows for No. 1014999 with two halogenated hydrocarbons and prepares ABCBA coupling segmented copolymer as coupler, is with coupler and multipolymer negatively charged ion AB
-Reaction and form.There is following problem in this type of coupler: has the by product alkali metal halide after the coupling and produces, and corroded pipeline and residue in the rubber easily with the antiaging agent reaction and make it produce the flavescence phenomenon not only, while synthetic polymkeric substance is also opaque.Adding this type of coupler is listed in poisonous chemical substance and must not use by multinational.
Carbonic acid gas, dithiocarbonic anhydride are used in English Patent 1103939 inventions, and the sulphur carbonoxide is made ABCBA coupling segmented copolymer.The coupling efficiency of this type of coupler is low; Carbonic acid gas is a gas, the concentration of ordinary dissolution in the wayward solution.And dithiocarbonic anhydride has sulfide side products and takes place after the coupling of sulphur carbonoxide.Not only can cause wastewater problem simultaneously by contaminated polymers.
United States Patent (USP) 3668279 inventions use maleic anhydride (maleic anhydride) or dimethyl terephthalic acid ester to make coupler.This compounds coupling rate is low, and coupling post polymerization solution is yellow, and can form by-product alcohols and be present in and reclaim in the solvent and poison the organic alkali metal initiator.
United States Patent (USP) 3244664,3692874,3880954, compounds such as 3725369 invention use silicon halogenide and silica, silicon nitrogen, silicon sulphur are made coupler, this type of coupler multiform becomes star-type polymer, coupling rate height, but can form by products such as alcohols, organic amine and thio-alcohol, they do not exist only in reclaims in the solvent and poisons the organic alkali metal initiator, can make polymkeric substance produce the stench of amine or thio-alcohol simultaneously.
United States Patent (USP) 4039633 inventions use 1,3,5-tricarboxylic acid three benzene halides are made coupler, the result can form a large amount of not coupling polymkeric substance and the indefinite coupling polymkeric substance of coupling number, coupling post polymerization thing is because of containing the easily flavescence of carboxylic-acid functional base, and contain a large amount of alkali halide metallic compounds, also perishable pipeline causes the product transparency not good.
Poly epoxy resin is used in United States Patent (USP) 3468972 inventions, polyisocyanate, and poly-imines, polyacetals, polyketone, poly-acid anhydrides, polyester, poly-halogenide is made coupler.The coupling number of this type of coupler is difficult to control, and its coupling number is the hub-and-spoke configuration more than 3, forms the mixture of the coupling post polymerization thing of different coupling numbers easily.And because of coupler molecular weight height, be difficult for the hydrocarbon cosolvent dissolving, the terminal group of coupling simultaneously easily causes the easy variable color of product if having these functional groups.And its coupling efficiency is usually less than 60%, and strong peculiar smell is easily arranged, and perhaps has byproducts such as alcohols, halogenide.
United States Patent (USP) 3281383 inventions use polymkeric substance such as styrene-acid anhydride copolymer, epoxidation liquid polybutadiene, polyisocyanate benzene to make coupler.The shortcoming of its generation is identical with the situation of United States Patent (USP) 3468972.
United States Patent (USP) 4107236 invention uses diester classes, silicon halide compound to make coupler, can produce alcohols and alkali halide metallic compound after the coupling, and the shortcoming of generation is identical with 3244664 and 3668279 situation.
Between United States Patent (USP) 3985830 invention is used-divinylbenzene makes coupler, coupler efficient is not high, and the range of a chain arm number is too big (by 2 chain arm numbers of linearity, can be changed to 12 starlike chain arm numbers, the same just like brass speculum, placed in the sun to generate enough heat to ignite dry gass foot animal), processing procedure control is difficult for, and the industrial divinylbenzene that gets roughly is all contraposition, ortho position, a position three's mixture, thereby feasibility is not high.
United States Patent (USP) 4049753 inventions use the acid anhydrides of monocarboxylic acid to make coupler has ether or alcohol radical functional group with synthetic coupling center compound.The coupling efficiency of this type of coupler is not high and easily make glue and sizing material flavescence because of the existence of acid anhydrides or carboxylic acid.The transparency of sizing material is not high yet simultaneously.
Purpose of the present invention is for providing the coupling type polymer (polymkeric substance after the coupling of the special coupler preparation of a kind of usefulness; Coupled polymer), not only do not have harmful side product and produce, and the coupling rate is reached more than 70%.
Another object of the present invention provides a coupling type polymer, and its coupling number (arm number) is at most 3.
Another object of the present invention provides a coupling type polymer, and its transparency is higher more than present star-shape polymer.
Another object of the present invention provides a coupling type polymer, and its wear resistant is better more than present star-shape polymer, can be well suited in sole.
A further object of the present invention provides a coupling type polymer, has the existence of tolerating diblock copolymer and the effect of significantly not destroying its mechanical characteristics.
Further purpose of the present invention provides a kind of preparation method of easy enforcement, be that alkali-metal polymkeric substance carries out coupling as coupler and reactive terminal base promptly with aliphatics, aromatic hydrocarbon or its ethers of bis-epoxy base, the compound of ketone, this method does not only have harmful side product and produces, and can make coupling efficiency up to more than 70%.
For realizing the object of the invention, coupling type polymer of the present invention is that alkali-metal polymkeric substance and coupler reaction get by a reactive terminal base; The method that the present invention prepares coupling type polymer comprises that with a reactive terminal base be alkali-metal polymkeric substance and coupler reaction, wherein this reactive terminal base is the chemical formula that alkali-metal polymkeric substance has P-M, wherein M is an alkali metal, P represents polymer molecular chain, be that one or more carbon numbers are the formed polymkeric substance carbonyl of the conjugated diolefine negatively charged ion of 4-12, perhaps one or more carbon numbers are the conjugated diolefine of 4-12 and the formed polymkeric substance carbonyl of the monovinyl aromatic hydrocarbon copolymerization negatively charged ion of one or more 8-18 carbon atoms;
Wherein this coupler class has following chemical formula:
R wherein
1, R
3Be aliphatic alkyl, thiazolinyl or hydrogen atom independently, R
2For alkylidene group (alkylene), alkenylene (alkenylene), divalent cycloalkyl, divalence aryl radical or have the ether of 1 or 1 above Sauerstoffatom or the C of ketone group
1-17Divalent radical.
Can polymerization roughly be selected from 1,3-butadiene with the conjugate diene monomer that enters polymer molecular chain P, 2,3-dimethyl-1,3-butadiene, 3-butyl-1, the 3-octadiene, isoprene, piperylene, 2-phenyl-1,3-butadiene, and composition thereof.
Can polymerization roughly be selected from vinylbenzene with the monovinyl aromatic hydrocarbon that enters polymer molecular chain P, vinyl toluene (3-vinyl toluene especially, alpha-methyl styrene), propylstyrene (especially 4-propylstyrene), phenylcyclohexane ethene (especially 4-phenylcyclohexane ethene), contraposition tolyl vinylbenzene, 1-vinyl-5-hexyl naphthalene, vinylnaphthalene (especially 1-vinylnaphthalene), and composition thereof.
Polymer molecular chain P can be the formed carbonyl negatively charged ion of single polymers of conjugate diene monomer, also can be the formed carbonyl negatively charged ion of multipolymer of conjugate diene monomer and monovinyl aromatic hydrocarbon monomer.This analog copolymer can be the random at random row of all kinds of different monomers, cumulative piecemeal block or block kenel.For example P can be the segmented copolymer of vinylbenzene and divinyl, perhaps the segmented copolymer of vinylbenzene and isoprene.And in this segmented copolymer, divinyl or isoprene or vinylbenzene all can with the alkalimetal ion bond.
Polymer molecular chain P can have the structure of A-B, and wherein A represents single ethene aromatic hydrocarbon block copolymer segments, and the B representative has the polymer molecule segment of rubber property.This B segment can be conjugated diene block, also can be the multipolymer of conjugated diolefine and monovinyl aromatic hydrocarbon, perhaps is other known polymer molecule segments with rubber property.So polymer molecular chain P can have the characteristic of elastomerics and thermoplastically polymkeric substance.Therefore, coupling type polymer of the present invention can be with the standard operating procedure production of the plastic polymkeric substance of known heat, and final product or article can have elastomeric characteristic.
According to the present invention, the reactive terminal base is alkali-metal polymer P-M, and wherein basic metal M is selected from lithium, sodium, potassium, rubidium, caesium.The preferably is a lithium.
Coupling post polymerization thing (coupling type polymer of the present invention; Coupled polymer) molecular weight can change in the larger context.In the scope of using usually, its molecular-weight average can fall into 1000 to 2000000 scope.
According to the present invention, suitable coupler has following chemical formula:
R wherein
1, R
3Be aliphatic alkyl, thiazolinyl or hydrogen atom independently, R
2For alkylidene group (alkylene), alkenylene (alkenylene), divalent cycloalkyl, divalence aryl radical or have the ether of 1 or 1 above Sauerstoffatom or the C1 of ketone group
-17Divalent radical.Work as R
2Be the ether with 1 or 1 above Sauerstoffatom or the C of ketone group
1-17During divalent radical, R for example
2Can be-R
4-O-R
5-or
R wherein
4, R
5Be C independently
0-17Alkylidene group or inferior aryl radical, preferably C
0-10Alkylidene group or inferior aryl radical.
As mentioned above, the used coupler of the present invention is the bis-epoxy based compound, can use commercial known following several methods to prepare voluntarily.On the general industry mode of synthetic bis-epoxy based compound can be divided into following several:
(1) diolefin of synthetic is directly with catalyst and oxygen reaction and form.
(2) diolefin of natural or synthetic and peroxy acid or hydrogen peroxide reaction and forming, because this compounds meeting residual acid or water, its content is reduced to below the 0.1wt%, otherwise easily make the polymkeric substance inactivation of active alkali metal terminating end, make the coupling rate descend, product is easy to change and cause the transparency to descend simultaneously.
(3) be that the epoxy compounds of alcohols and halogenation terminal group removes hydrochloric acid again via the effect of alkaline catalyst (routine NaOH) and gets by bisphenol compound or difunctionality base, its ratio must be controlled well, otherwise easily containing alcohol-based, perhaps halogen in the diepoxides.The reaction raw materials of the epoxy compounds of the terminal group of halogenation simultaneously and two alcohol functional group or bisphenol compound must well remove, its content is reached below the 0.1wt%, otherwise these impurity easily make the polymkeric substance inactivation of active alkali metallic terminations machine, make the coupling rate descend, the transparency is not good, and easily makes the product variable color.
No matter with stating which kind of preparation method, it conforms with epoxy compounds of the present invention must be the no any alcohol radical of molecule itself, ester group, and halogen, functional groups such as carboxylic acid group exist, and related impurities amount (routine H
2O, peroxy acid, carboxylic acid, hydrogen halide, alkali halide metal, salt, the epoxy compounds of halogenation terminal group, two alcohol or bisphenol compound etc.) must be lower than 0.1 weight percent %, be more preferably and be lower than 0.01 weight percent %.
Being applicable to that concrete coupler example of the present invention can be contains alkyls, as the methylpentane dioxide, and the divinyl dioxide, the dimethylpentane dioxide, pentane dioxide, hexane dioxide, the heptane dioxide, octane dioxide, decane dioxide etc.; Can be and contain the cycloalkanes base class, as the vinyl cyclohexane dioxide, dioxygen kautschin (limonene dioxide), hexanaphthene dioxide, cyclooctane dioxide, Dicyclopentadiene (DCPD) dioxide; Can be and contain the aromatic hydrocarbon base class, as divinylbenzene dioxide; Can be and contain the ether class, as diglycidylether, butanediol diglycidyl ether, ethylene glycol diglycidylether, hexanediol diglycidyl ether, Diethylene Glycol diglycidylether, two (2,3-oxirane ring amyl group) ether, the dihydroxy-benzene diglycidylether, 2-Racemic glycidol phenyl glycidyl ether, diepoxy saligenol (epoxidized saligenin), 3-(3,4-epoxy hexane)-8,9-epoxy-2,4-dioxy spiral shell-5,5-hendecene [3-(3,4-epoxy hexane)-8,9-epoxy-2,4-dioxaspiro-5,5-undecane), 4,4 '-isopropylidene diphenol (4,4 '-isopropylidenediphenol) etc.
The usage quantity of coupler, relevant with the coupling rate, and also relevant with the characteristic of the coupling type polymer of coupling gained.Suitable coupler consumption is, this coupler and reactive terminal base are that the mol ratio of the consumption of alkali-metal polymkeric substance is 0.05～3.5, and the preferably is 0.2～2.5.
The temperature of coupled reaction can change in the scope widely, and is for convenience's sake, roughly identical with polymeric reaction temperature.Though temperature can be changed to 200 ℃ from 0 ℃; Preferable scope then drops in 50 ℃～120 ℃ the scope.
Coupled reaction is implemented to get final product in the mode of simple pure coupler or its solution and reactive polymer solution stirring usually.The reaction time of must is quite short.During the normal coupled reaction roughly at 1 minute to 1 hour.But during the long coupled reaction of the next need of lower temperature.
After coupled reaction, the polymers soln of coupling can with the terminator mixing aftertreatment that contains active hydrogen (for example alcohol or water, or the mixture of acidic aqueous solution or these kinds).When before isolating polymer, be better than most and add antioxidant in the reacted polymeric solution earlier.
The treatment process of available standards is separated polymkeric substance from reacted polymers soln, for example steam stripped or condensed with suitable non-solvent (as alcohols).Polymkeric substance behind cohesion or the stripping removes wherein part medium with centrifugal or extrusion mode again.The mode of the then available heating of residual solvent and other volatile matters (can select decompression or under mandatory air draught) is separated with polymkeric substance.
Mixing with addition of man-hour, can add as weighting agent, dyestuff, colorant, tenderizer, treated oil, strengthening agent etc. and mix composition with addition of the worker.
Flesh and blood of the present invention is for providing the method for producing above-mentioned definition polymkeric substance and the polymkeric substance after the coupling thereof.This preparation method is made of two steps.First step is the reactive polymer that forms chemical formula P-M; Second step is the coupler coupling of reactive polymer and the above-mentioned definition of the present invention.
First step of present method is the basic metal initiator with monofunctional, reacts with relevant monomer or monomers to form bioactive molecule chain P-M and implement.This polymerization procedure can be one step and also can be different step and connect continuously.Polymer molecular chain is single polymers or two kinds even two or more monomer disorderly row, the multipolymer of cumulative block piecemeal at random, and these monomers inject simultaneously and all are with basic metal initiator polymeric.Yet when polymer molecular chain P was made up of two or more individuals or copolymer block, these independent separately blocks can be with reinforced monomer of segmentation or cumulative continuously reinforced monomer methods produce piecemeal.
The used basic metal initiator of first step of the defined coupling post polymerization of preparation the present invention object space method all has following general formula R basically
1-M, M is an alkali metal, as lithium, sodium, potassium, rubidium, caesiums etc. are wherein preferably selected elemental lithium for use.And R1 is generally the hydrocarbon polymer carbonyl negatively charged ion of 1 to 20 carbon atom.The initiator that so contains elemental lithium can be lithium methide, sec.-propyl lithium, n-Butyl Lithium, tert-butyl lithium, isobutyl-lithium, the tertiary butyl lithium, Te Xinji lithium, hexyl lithium, n-undecane lithium, phenyl lithium, the naphthyl lithium, contraposition-methylbenzene lithium, 4-phenyl butyl lithium, cyclohexyl lithium, 4-cyclohexyl butyllithium etc.The consumption of employed organic alkali metal initiator is according to the required character of polymkeric substance and molecular weight and determine especially required molecular weight.Normal organic alkali metal initiator consumption is to use in (0.1～100) * 10
-3Whole monomers of mole/double centner.
Polyreaction is carried out in hydrocarbon solvent.Comprising paraffinic solvent, as pentane, hexane, heptane, octane, decane, pure isooctane etc.Also comprise cycloparaffin series's solvent, pentamethylene for example, hexanaphthene, methylcyclohexane, ethylcyclohexane, 1,4-dimethyl cyclohexane etc.Also comprise aromatic hydrocarbon solvent, for example benzene, toluene, ethylbenzene, dimethylbenzene, diethylbenzene and propyl benzene.These solvents can use separately also can mix use, wherein preferably uses hexanaphthene and normal hexane.
Generally speaking, if when being polymerisation medium with pure hydrocarbon cosolvent, because of the rate of polymerization of monovinyl aromatic hydrocarbon or conjugated diolefine slow, and both polymerisation reactivity difference is too big, the adding of available polar solvent reduces reactive difference and promotes rate of polymerization, but when adding when too many, then the arrangement of monovinyl aromatic hydrocarbon and conjugated diolefine is become the molecular structure of random sequence by cumulative block piecemeal.Therefore the usage quantity of polar solvent has certain scope.The polar solvent that the present invention also can add can be ethers, tertiary amine etc.Ethers comprises tetrahydrofuran (THF), diethyl ether, ring amyl ether, dipropyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, glycol ether, dme etc.Wherein best is tetrahydrofuran (THF) and diethyl ether etc.Ternary amine comprises Trimethylamine, triethylamine, and tripropylamine etc., wherein best is triethylamine.
Reaction is normally carried out under solvent and monomer weight ratio exceed 1 situation.More suitable ratio is whole monomer gross weights of solvent 200 to 1200 weight parts/per 100 weight parts.
Step 1 polyreaction usually occur in several minutes to 8 hours during in.More suitable polyreaction is carried out in during 30min to 4 hour.As for polymerization temperature, in 0 ℃～200 ℃ scope, more suitable scope is 40 ℃～130 ℃ usually.
Polyreaction ends, and will implement second step, i.e. coupled reaction.The polymeric reactive polymer is mixed with coupler.This step must add any material to stop polyreaction or just to implement before polymer molecular chain is removed alkali metal atom, therefore, the living polymerization mixture must be at water with mixing of coupler, acid, and this type of thing such as alcohols adds just to carry out before the reactive polymer that deactivates.
In polymerization process, paradigmatic system must keep the inclusion-free state, and impurity comprises water, oxygen, carbonic acid gas, acetylene compound, halogen compounds, alcohol, organic acid and mineral acid.And monovinyl aromatic hydrocarbon and conjugated diolefine also must be through purification process before entering reactive system.Whole purge process must be at nitrogen, and argon gas carries out under the situation that the helium sealing gland exists.
Method of the present invention, be with have coupler that good coupling renders a service come with the reactive terminal base be that alkali-metal polymkeric substance carries out coupled reaction.This coupler not only can not produce the chloride corrosion pipeline in coupling efficiency height and the coupling process, can not produce alcohols, acids yet and forms the poisonous substance of active anionic polymerization.The coupling number of coupling post polymerization thing is lower than 3, is higher than 3 obviously differently with the coupling number of general starlike coupler, not only has good rubber manufacturing machinery characteristic, the heigh clarity that also has known coupling type polymer and lacked.It is well a lot of that the wear resistant that simultaneously polymkeric substance of the present invention presented also is the polymkeric substance of hub-and-spoke configuration than tradition.
Below for several embodiment so that method of the present invention, feature and advantage to be described, but be not that scope of the present invention should be as the criterion with claims in order to restriction the present invention.
In containing the autoclave pressure of agitator, under the nitrogen sealing gland, do the polymkeric substance of terminal group and the reaction of various coupler with 6 kinds with lithium, with the preparation coupling type polymer.
Embodiment 1-3 and comparative example 1-4
95 kilograms of vinylbenzene is dissolved in 1860 kilograms the hexanaphthene, adds the 5wt% n-butyllithium solution that adds 9.3 kilograms behind the tetrahydrofuran (THF) of 0.3cc, formal starting polymerization reaction, and reaction continues 30 minutes, and temperature is by 40 ℃ to 55 ℃.After whole styrene monomers almost reacts completely, the butadiene solution that adds 210 kilograms is in polymeric blends, reaction continues to continue 90 minutes again, temperature approximately is warming up to 80～90 ℃ by 55 ℃, after whole divinylic monomers almost reacts completely, just form the active styrene-butadiene block copolymer of first step.
This active block thing reacts with all kinds of different couplers, continues to continue 30 minutes between 70～85 ℃ again.Polymers soln after this coupling adds the obstruction type phenol antioxidant of 0.2phr, then with steam mode stripping.The molecular weight of the dry post polymerization thing of universe this moment is promptly known, and the coupling of the polymkeric substance ratio of counting is calculated and then can be learnt by the analysis of GPC.All kinds of different coupler experimental results are as shown in table 1.Table 1: the coupling result and the effect of different couplers
Table 1: continuous
Transmitance with the test piece of UV irradiation 2mm thickness.
*The high more table yellow of yellow number of degrees value is dark more
| Embodiment | ?1 | ??2 | ??3 |
| Coupler | 1,2,7,8 diepoxy octanes | 1, the 4-butanediol diglycidyl ether | The divinyl dioxide |
| N-Butyl Lithium/coupler mol ratio | ?2.2 | ??2.0 | ??1.9 |
| Coupling rate (%) | ?93 | ??90 | ??85 |
| The coupling number | ?1.90 | ??1.85 | ??1.91 |
| Weight average molecular weight (* 10 after the coupling -4) | ?13.8 | ??13.7 | ??14.7 |
| The polymers soln color | Transparent watery | Transparent watery | Transparent watery |
| Tensile strength (kg/cm 2) | ?251 | ??283 | ??220 |
| Elongation | ?788 | ??830 | ??873 |
| 300% modulus (kg/cm 2) | ?28.5 | ??23.5 | ??28.9 |
| Hardness (shore A) | ?78 | ??79 | ??68 |
| Micelle color (yellow degree) ** | ?8 | ??7.1 | ??6.5 |
| The coupled reaction by product | Do not have | Do not have | Do not have |
| Comparative example | ??1 | ??2 | ??3 | ?4 |
| Coupler | To xylylene dichlorides | Glycol dibromide | The methylbenzene acid esters | Right-Benzoquinone |
| N-Butyl Lithium/coupler mol ratio | ??2.0 | ??1.8 | ??2.2 | ?2.2 |
| Coupling rate (%) | ??70.4 | ??75.5 | ??74.9 | ?34.8 |
| Molecular-weight average (* 10 after the coupling -4) | ??14.75 | ??14.36 | ??11.7 | ?17.7 |
| The polymers soln color | Translucent vaporific solution | Translucent vaporific solution | Clear, colorless | Green solution |
| Tensile strength (kg/cm 2) | ??267 | ??273 | ??257 | ?200 |
| Elongation | ??920 | ??830 | ??920 | ?＞1200 |
| 300% modulus (kg/cm 2) | ??23 | ??27.5 | ??22.7 | ?14.6 |
| Hardness (Shore A) | ??75 | ??77 | ??77 | ?72 |
| The micelle color ** | ??26.7 | ??7.1 | ??21.3 | ?132.3 |
| The transparency | ??39.2 | ??41.3 | ??21.3 | ?26.6 |
| The coupled reaction by product | Lithium chloride | Lithiumbromide | Methyl alcohol | Do not have |
Comparative example 5-7
41 kilograms vinylbenzene is dissolved in 1100 kilograms the hexanaphthene, adds the formal starting polymerization reaction of 15% n-butyllithium solution that adds 1.2 kilograms behind the tetrahydrofuran (THF) of 0.3cc, and reaction continues 30 minutes, and temperature is by 40 ℃ to 50 ℃.Whole styrene monomers almost total overall reaction fully after, the isoprene solution that adds 123 kilograms is in polymeric blends, reaction continued lasting 90 minutes again, temperature approximately is warming up to 80～90 ℃ by 55 ℃.After whole isoprene monomers almost reacts completely, just form the active styrene-isoprene block copolymer of first step.
This active block thing reacts with all kinds of different couplers, continues to continue 30 minutes in 70～85 ℃ again.Remaining step adds antioxidant, stripping, drying and other steps according to the mode of embodiment 1-3.All kinds of different coupler experimental results are as shown in table 2.
Table 2: the coupling result and the effect of different couplers
| Comparative example | ??5 | ??6 | ??7 |
| Coupler | Acetic anhydride | The butylacetic acid ester | Glycol dibromide |
| N-Butyl Lithium/coupler mol ratio | ??2/3 | ??2/1 | ??2/1 |
| Molecular weight before the coupling | ??8.8 | ??8.1 | ??9.1 |
| Molecular weight after the coupling | ??16.6 | ??14.7 | ??17.5 |
| The coupling number | ??1.89 | ??1.81 | ??1.92 |
| Coupling rate (%) | ??65 | ??77 | ??72 |
| Tensile strength (kg/cm 2) | ??- | ??133 | ??155 |
| Elongation (%) | ??- | ??1160 | ??＞1200 |
| 300% modulus (kg/cm 2) | ??- | ??14 | ??14 |
| The transparency | ??25 | ??60 | ??32 |
| The polymers soln color | Faint yellow vaporific | Transparent watery | Translucent vaporific |
| The coupled reaction by product | Do not have | Ethanol | Lithiumbromide |
Comparative example 8,9
95 kilograms vinylbenzene is dissolved in 1860 kilograms the hexanaphthene, adds 15% n-butyllithium solution that adds 2.94 kilograms behind the tetrahydrofuran (THF) of 0.3 ≈, formal starting polymerization reaction, and reaction continues 30 minutes, and temperature is by 40 ℃ to 50 ℃.Whole styrene monomers almost total overall reaction fully after, the butadiene solution that adds 210 kilograms is in polymeric blends.Remaining step adds antioxidant, stripping, drying and other steps according to the mode of embodiment 1-3.The experimental result of different sorts coupler is as shown in table 3.Table 3: the coupling result and the effect of different couplers
| Comparative example | ???8 | ?9 |
| Coupler | Epoxy linseed oil (molecular weight～1000, the epoxy amount is more than 9%) | Epoxy soybean oil (molecular weight～1000, the epoxy amount is more than 9%) |
| The coupler consumption | 6.0parts/100parts whole monomers | 3.0parts/100parts whole monomers |
| The coupling rate | ???61.0 | ?60.8 |
| Molecular-weight average (* 10 after the coupling -4) | ???21.6 | ?7.9 |
| Molecular-weight average (* 10 before the coupling -4) | ???11.0 | ?15.4 |
| The coupling number | ???1.96 | ?1.95 |
| Tensile strength (kg/cm 2) | ???149 | ?160 |
| Elongation (%) | ???844 | ?844 |
| 300% modulus (kg/cm 2) | ???17.6 | ?18.1 |
| The transparency | ???33.6 | ?68.6 |
| The polymers soln color | Glassy yellow | Clear, colorless |
| Micelle color (yellow degree) | ???26.2 | ?8.9 |
Comparative example 10-12
Except 15% n-butyllithium solution consumption is promoted to 3.83 kilograms by 2.94 kilograms, remaining process is all identical with comparative example 8,9 with step.The gained result is as shown in table 4.Table 4: the coupling result and the effect of different couplers
| Comparative example | ?10 | ????11 | ??12 |
| Coupler | 3-ethyl-2, the 4-diacetylmethane | Anhydride phthalic acid | Terephthalic aldehyde |
| N-Butyl Lithium/coupler mol ratio | ?2.2 | ????2.2 | ??2.5 |
| Molecular-weight average (* 10 before the coupling -4) | ?6.67 | ????5.7 | ??6.9 |
| Molecular-weight average (* 10 after the coupling -4) | ?13.3 | ????11.7 | ??13.2 |
| The coupling number | ?1.99 | ????2.05 | ??1.91 |
| The coupling rate | ?34.2 | ????54.3 | ??70 |
| The transparency | ?48 | ????32 | ??52 |
Embodiment 4, comparative example 13
Except the vinylbenzene consumption is 72 kilograms, the divinyl consumption is 108 kilograms, and remaining manufacturing step is identical with comparative example 5-7, and the experimental result of different sorts coupler then is as shown in table 5:
Table 5
| Embodiment 4 | Comparative example 13 | |
| Coupler | 1,2,7,8-diepoxy octane | Silicon tetrachloride |
| N-Butyl Lithium consumption (kilogram) | 0.245 | ????0.344 |
| N-Butyl Lithium/coupler mol ratio | 2.2 | ????4.4 |
| Molecular weight (* 10 before the coupling -4) | 10.7 | ????5.4 |
| Molecular weight (* 10 after the coupling -4) | 19.0 | ????16.2 |
| The coupling number | 1.83 | ????3.0 |
| The coupling rate | 85 | ????90 |
| Tensile strength (kg/cm 2) | 282 | ????308 |
| Elongation (%) | 750 | ????695 |
| 300% modulus (kg/cm 2) | 36 | ????47.6 |
| The polymers soln color | Clear, colorless | Translucent vaporific |
| Wear resistant (Akron, 15 ° * 6lb * 3300rev) | 0.146 | ????0.541 |
| The transparency | 82 | ????23 |
As known from the above, coupling type polymer of the present invention (being embodiment 1-4 gained), not only coupling rate can reach more than 70%, and the product transparency that synthesizes is higher than more than 70%, and yellow degree is lower than 10, wear resistant also is better than tradition and uses the silicon tetrachloride coupling product.
Though the present invention with the preferred embodiment explanation as above; right its is not in order to qualification the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention; may make and changing and retouching, so protection scope of the present invention defines with claim and is as the criterion.
Claims (17)
1. a coupling type polymer is that alkali-metal polymkeric substance and coupler reaction get by a reactive terminal base,
Wherein this reactive terminal base is the chemical formula that alkali-metal polymkeric substance has P-M, wherein M is an alkali metal, P represents polymer molecular chain, be that one or more carbon numbers are the formed polymkeric substance carbonyl of the conjugated diolefine negatively charged ion of 4-12, perhaps one or more carbon numbers are the conjugated diolefine of 4-12 and the formed polymkeric substance carbonyl of the monovinyl aromatic hydrocarbon copolymerization negatively charged ion of one or more 8-18 carbon atoms
Wherein this coupler has following chemical formula:
R wherein
1, R
3Be aliphatic alkyl, thiazolinyl or hydrogen atom independently, R
2For alkylidene group (alkylene), alkenylene (alkenylene), divalent cycloalkyl, divalence aryl radical or have the ether of 1 or 1 above Sauerstoffatom or the C of ketone group
1-17Divalent radical.
2. coupling type polymer according to claim 1 is characterized in that: wherein this conjugated diolefine is selected from 1,3-butadiene, and 2,3-dimethyl-1, the 3-divinyl, 3-butyl-1,3-octadiene, isoprene, piperylene, 2-phenyl-1,3-butadiene, and composition thereof.
3. coupling type polymer according to claim 1 is characterized in that: wherein this monovinyl aromatic hydrocarbon is selected from vinylbenzene, vinyl toluene, propylstyrene, phenylcyclohexane ethene, contraposition tolyl vinylbenzene, 1-vinyl-5-hexyl naphthalene, vinylnaphthalene, and composition thereof.
4. coupling type polymer according to claim 1, it is characterized in that: wherein the foreign matter content in this coupler is lower than 0.1wt%, wherein this impurity is the epoxy compounds of water, peroxy acid, carboxylic acid, hydrogen halide, alkali halide metal, salt, halogenation terminal group, two alcohol, bis-phenol, and composition thereof.
5. coupling type polymer according to claim 1 is characterized in that: wherein this alkali metal is selected from lithium, sodium, potassium, rubidium, caesium.
6. coupling type polymer according to claim 5 is characterized in that: wherein this basic metal is elemental lithium.
7 coupling type polymers according to claim 1 is characterized in that: wherein this coupler and reactive terminal base are that the mol ratio of alkali-metal polymer loading is 0.05～3.5.
8. coupling type polymer according to claim 1 is characterized in that: wherein the coupling number of the coupling type polymer of gained is lower than 3.
9. coupling type polymer according to claim 1 is characterized in that: R wherein
1, R
2, R
3On do not have alcohol radical, ester group, halogen, functional groups such as carboxylic acid group.
10. coupling type polymer according to claim 1 is characterized in that: wherein P is the segmented copolymer of vinylbenzene and divinyl, perhaps the segmented copolymer of vinylbenzene and isoprene.
11. coupling type polymer according to claim 1, it is characterized in that: wherein this coupler is for containing alkyls, be selected from the methylpentane dioxide, the divinyl dioxide, dimethylpentane dioxide, pentane dioxide, the hexane dioxide, the heptane dioxide, octane dioxide, decane dioxide.
12. coupling type polymer according to claim 1 is characterized in that: wherein this coupler is selected from the vinyl cyclohexane dioxide for containing the cycloalkanes base class, dioxygen kautschin (limonenedioxide), the hexanaphthene dioxide, cyclooctane dioxide, Dicyclopentadiene (DCPD) dioxide.
13. coupling type polymer according to claim 1 is characterized in that: wherein this coupler is the divinylbenzene dioxide that contains the aromatic hydrocarbon base class.
14. coupling type polymer according to claim 1, it is characterized in that: wherein this coupler is selected from diglycidylether for containing the ether class, butanediol diglycidyl ether, ethylene glycol diglycidylether, hexanediol diglycidyl ether, Diethylene Glycol diglycidylether, two (2,3-oxirane ring amyl group) ether, the dihydroxy-benzene diglycidylether, 2-Racemic glycidol phenyl glycidyl ether, diepoxy saligenol (epoxidized saligenin), 3-(3,4-epoxy hexane)-8,9-epoxy-2,4-dioxy spiral shell-5,5-hendecene [3 (3,4-epoxy hexane)-8,9-epoxy-2,4-dioxaspiro-5,5-undecane), 4,4 '-isopropylidene diphenol (4,4 '-isopropylidenediphenol).
15. coupling type polymer according to claim 1 is characterized in that: wherein the R2 in this coupler has the ether of 1 or 1 above Sauerstoffatom or the C of ketone group
1-17Divalent radical.
16. coupling type polymer according to claim 15 is characterized in that: R wherein
2Can be-R
4-O-R
5-or
R wherein
4, R
5Be C independently
0-17Alkylidene group or inferior aryl radical.
17. a method for preparing coupling type polymer, it comprises that with a reactive terminal base be alkali-metal polymkeric substance and coupler reaction,
Wherein the very alkali-metal polymkeric substance of this reactive terminal has the chemical formula of P-M, wherein M is an alkali metal, P shows polymer molecular chain, be that one or more carbon numbers are the formed free polymer readical of conjugated diolefine of 4-12, perhaps one or more carbon numbers are the conjugated diolefine of 4-12 and the formed free polymer readical of monovinyl aromatic hydrocarbon copolymerization of one or more 8-18 carbon atoms;
Wherein this coupler has following chemical formula:
R wherein
1, R
3Be aliphatic alkyl, thiazolinyl or hydrogen atom independently, R
2For alkylidene group (alkylene), alkenylene (alkenylene), divalent cycloalkyl, divalence aryl radical or have the ether of 1 or 1 above Sauerstoffatom or the C of ketone group
1-17Divalent radical.
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| CNB981233473A CN1148384C (en) | 1998-12-14 | 1998-12-14 | Coupling type polymer and preparation process thereof |
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|---|---|---|---|
| CNB981233473A CN1148384C (en) | 1998-12-14 | 1998-12-14 | Coupling type polymer and preparation process thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326896C (en) * | 2002-09-12 | 2007-07-18 | 住友化学工业株式会社 | Process for producing modified polymer rubber |
| CN106008928A (en) * | 2010-05-21 | 2016-10-12 | 蓝立方知识产权有限责任公司 | Curable compositions |
-
1998
- 1998-12-14 CN CNB981233473A patent/CN1148384C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326896C (en) * | 2002-09-12 | 2007-07-18 | 住友化学工业株式会社 | Process for producing modified polymer rubber |
| CN106008928A (en) * | 2010-05-21 | 2016-10-12 | 蓝立方知识产权有限责任公司 | Curable compositions |
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| Publication number | Publication date |
|---|---|
| CN1148384C (en) | 2004-05-05 |
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