CN105585646A - Linear poly(1,3-pentadiene) having low allyl content and narrow molecular weight distribution and preparing method thereof - Google Patents
Linear poly(1,3-pentadiene) having low allyl content and narrow molecular weight distribution and preparing method thereof Download PDFInfo
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Abstract
Linear poly(1,3-pentadiene) having a low allyl content and narrow molecular weight distribution and a preparing method thereof are disclosed. The poly(1,3-pentadiene) is characterized in that linearity is high, a content of a 1,4- structure is 70-90%, the number-average molecular weight is adjustable in a range of 10<3>-10<6> g/mol, the narrow molecular weight distribution is 1.05-1.18 and the glass transition temperature Tg ranges from -55 DEG C to -33 DEG C. The poly(1,3-pentadiene) is prepared by adopting an active controllable anionic polymerization manner and adopting an organic alkali metal initiator as a catalyst. The organic alkali metal initiator comprises an A component and a B component in a mole ratio of 1:(0.1-100), wherein the A component is an organic alkali metal and the B component is an organic ether or an organic amine compound. Active controllable polymerization of 1,3-pentadiene can be achieved through the initiator at reference polymerization temperature. The method is characterized by a wide polymerization temperature range, a simple, convenient and mild reaction, a high reaction speed, a high monomer conversion ratio, and controllable linearity of a polymer microstructure.
Description
Technical field
The present invention relates to macromolecule synthesising technology field, particularly a kind of low acrylic content, Narrow Molecular Weight DistributionLinear poly-1,3-pentadiene and preparation method thereof.
Background technology
1,3-pentadiene claims again pentadiene, is oil C5One of main component in cut, its content is only second to isoamylDiene and cyclopentadiene are the industrial chemicals of rich content. In 1,3-pentadiene molecular structure owing to there being cis-trans isomerism,Can obtain by polymerisation the poly-1,3-pentadiene that various structures is complicated and changeable, this polymer has class in theoryLike the feature of polyisoprene, but rare its application in synthetic rubber field.
1,3-pentadiene is mainly used in synthesizing petroleum resin at present, because the feature of cationic polymerization mechanism causes polymerMolecular weight is lower, and molecular weight distribution is very wide, has condensed ring structure in strand, directly affects its properties of product, soAdded value of product is not high.
Preparing the method that linear poly-1,3-pentadiene mainly adopts is coordination polymerization and anionic polymerisation. Wherein coordination catalysisAgent mainly contains Fe-series catalyst, cobalt series catalyst, chromium-based catalysts, vanadium series catalyst and rare-earth catalysis system, as public affairsThe Chinese patent that the number of opening is CN102190745 discloses the method for the poly-1,3-pentadiene of a kind of Fe-series catalyst preparation,The poly-1,3-pentadiene molecular weight distribution obtaining by the method is wide, and acrylic content is high; US Patent No. 4048418Disclose a kind of polymerization of Fe-series catalyst catalysis 1,3-pentadiene, but polymer is crystalline state, can not directly useDo rubber; The patent No. is that to disclose employing DIFFERENT Cr be ternary to the United States Patent (USP) of US4148983 and US4168357The method of the poly-1,3-pentadiene of catalyst system and catalyzing preparation, having synthesized a series of cis Isosorbide-5-Nitraes is to lead (70% left and right), TgLow (40 DEG C of left and right) and high by 3, the poly-1,3-pentadiene of 4-structure, high Tg (20 DEG C of left and right); The patent No. is US5066754United States Patent (USP) disclose that to utilize vanadium be the method for the poly-1,3-pentadiene of binary catalyst system preparation, low temperature (78 DEG C～-20 DEG C) under synthesized molecular weight 2000-500000g/mol, have lower molecular weight distribute (PDI=1.4～2.4)Poly-1,3-pentadiene; Publication number is that the Chinese patent of CN103709295 discloses a kind of rare-earth catalysis system system of usingThe method of standby poly-1,3-pentadiene, preparation has been synthesized suitable Isosorbide-5-Nitrae-structural content 40～60%, acrylic content 30～40% poly-1,3-pentadiene, but the highest yield of this system is 60.1% left and right; The patent No. is the U.S. of US4482771Patent discloses a kind of method with the poly-1,3-pentadiene of anionic polymerisation preparation, but in this system, has synthesized high acrylicThe poly-1,3-pentadiene of content, molecular weight distribution PDI > 2.0.
To sum up, adopt Fe-series catalyst, cobalt series catalyst, chromium-based catalysts, vanadium series catalyst and rare-earth catalysis systemCarry out coordination polymerization, or adopt the poly-1,3-pentadiene of anionic polymerization preparation, molecular weight distribution is wider, and product producesRate is limited, condition harshness, and in synthetic micmstructure of polymer, acrylic content is higher, is not too suitable as synthetic rubberGlue (low Tg); In the preparation process of complex catalyst, catalyst preparation process complexity, preparation time is longer, to insteadAnswer the technical parameter requirement such as temperature, time harshness, synthetic cost is high.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of low acrylic content, narrow molecular-weightPoly-1,3-pentadiene of linearity distributing and preparation method thereof. The present invention adopts active controlled anionic polymerisation process, and it closesOne-tenth method is simple, conversion ratio high (reaching as high as 99%); The poly-1,3-pentadiene of linearity obtaining has Narrow Molecular Weight Distribution1.05～1.18, low acrylic content (10%～30%) and lower glass transition temperatures Tg (55 DEG C～-33 DEG C).
The invention provides the preparation method of the poly-1,3-pentadiene of linearity of a kind of low acrylic content, Narrow Molecular Weight Distribution,Concrete steps are as follows: under the condition of anhydrous and oxygen-free, add aprotic solvent in polymer reactor, 1,3-penta 2Alkene monomer and organic alkali metal initator, polymerisation 1h～24h at 0～120 DEG C of temperature afterwards, finally with anti-oldThe alcoholic solution cessation reaction of agent, and separate out polymer with excessive methanol or ethanol, washing, dry, obtain low propyleneThe poly-1,3-pentadiene of linearity of base content, Narrow Molecular Weight Distribution; Wherein: described 1,3-pentadiene monomer and organic baseThe mol ratio of metal initiator is 1:(10-3～10-6); Described organic alkali metal initator comprises that mol ratio is 1:The A of (0.1～100), B two components, component A is organic alkali metal, B component is organic ethers or organic amineCompound.
In the present invention, described organic alkali metal is selected from organo-lithium compound, organosiloxane compound, organic potassium compoundOr in organocesium compounds any; It is organic that described organo-lithium compound is selected from lithium alkylide, nitrogen lithium or large molecular activityIn lithium any; Described organosiloxane compound is selected from sodium alkyl, nitrogen sodium or the large organic sodium of molecular activity any;Described organic potassium compound is selected from potassium alkyl, nitrogen potassium or large molecular activity organic potassium any; Described organic caesiumCompound is selected from alkyl caesium, nitrogen caesium or the large organic caesium of molecular activity any; Wherein: described lithium alkylide is normal-butylLithium, s-butyl lithium, tert-butyl lithium, benzene lithium or benzyl lithium; Described nitrogen lithium is dimethylamino lithium, diethylamino lithiumOr lithium diisopropylamine; Described large molecular activity organolithium is polystyryl lithium, polybutadiene lithium, poly-isoamyl twoAlkene lithium or poly-1,3-cyclohexadiene lithium; Described potassium alkyl is naphthalene potassium; Preferably, in the present invention, organic alkali metal is just selected fromButyl lithium, tert-butyl lithium, benzyl lithium, lithium diisopropylamine, polystyryl lithium, polymethylstyrene base lithium,In polyisopreneyl lithium, naphthalene sodium, naphthalene potassium, butyl potassium or benzyl potassium any.
In the present invention, described organic ether compounds is selected from ether, diethylene glycol dimethyl ether (2G), diisopropylEther, many glycol dialkyl ethers, oxolane, 1, appoint in 3-dioxane, oxolane alkyl ether and derivative thereofA kind of; Described organic amine compound is selected from triethylamine, tetramethylethylenediamine (TMEDA), pentamethyl divinylIn triamine, tetrahydrofurfuryl amine, dipiperidinoethane, tetrahydrofurfuryl amine methyl ether and derivative thereof any; Preferably, haveMachine ethers or aminated compounds are oxolane, tetramethylethylenediamine, diethylene glycol dimethyl ether, diisopropyl ether, tetrahydrochyseneA kind of in furfuryl alcohol ether or tetrahydrofurfuryl amine methyl ether.
In the present invention, described aprotic solvent is selected from cyclohexane, hexane, pentane, isopentane, toluene, tetrahydrochyseneOne or more in furans, ether, diethylene glycol dimethyl ether, triethylamine or tetramethylethylenediamine; 1,3-penta 2The volumetric concentration of alkene monomer in aprotic solvent is 5～40%; Preferably, volumetric concentration is 10～20%; Due toConsider the problem of rate of polymerization, cis-1,3 pentadiene rates of polymerization are less than trans-1,3 pentadienes, suggestion different monomers is adoptedWith the initator of different activities.
In the present invention, described 1,3-pentadiene monomer comprises the cis-1 that is selected from polymer grade, 3-pentadiene, trans-1,3-penta 2The cis/trans-1 of alkene, any proportioning, 3-pentadiene mix monomer, or in 1,3-pentadiene derivative, as 2-Methyl 1,3-pentadiene, 2,3-dimethyl 1,3-pentadiene etc. any.
In the present invention, polymerization 2～4 hours at 60～80 DEG C of temperature.
The alcoholic solution of the age resistor adopting in the present invention, preferred mass mark is 0.5～1.5% 2,6-di-t-butyl pairThe methyl alcohol of methylphenol or ethanolic solution.
The present invention proposes a kind of low acrylic content obtaining according to above-mentioned preparation method, the linearity of Narrow Molecular Weight DistributionPoly-1,3-pentadiene, the high Isosorbide-5-Nitrae-structural content of this poly-1,3-pentadiene between 70～90%, acrylic content 10～Between 30%, number-average molecular weight Mn103～106Between g/mol, the PDI value of Narrow Molecular Weight Distribution, i.e. Mw/MnBetween 1.05～1.18, vitrification point Tg is between-55 DEG C～-30 DEG C; Wherein: in its Isosorbide-5-Nitrae-structure, trans-Isosorbide-5-NitraeThe content of structure is in 50～70% scopes; Mw represents weight average molecular weight.
Beneficial effect of the present invention is: its synthetic method is simple, and polymerization temperature wider range reacts easy, gentle,Reaction rate is fast, conversion ratio high (reaching as high as 99%); The poly-1,3-pentadiene of linearity obtaining has Narrow Molecular Weight Distribution(PDI value 1.05～1.18), low acrylic content (10%～30%) and low polymer glass transition temperatureTg(-55℃～-33℃)。
Brief description of the drawings
Fig. 1 is the poly-1,3-pentadiene prepared of the embodiment of the present invention 11HNMR figure.
Fig. 2 is the poly-1,3-pentadiene prepared of the embodiment of the present invention 513CNMR figure.
Fig. 3 is the DSC figure of the poly-1,3-pentadiene prepared of embodiment of the present invention 1-4 and embodiment 10.
Fig. 4 is the GPC figure of the poly-1,3-pentadiene prepared of the embodiment of the present invention 1 and embodiment 11.
Detailed description of the invention
In the present invention, the model that the microstructure of synthetic poly-1,3-pentadiene adopts Varian company of the U.S. to produce isThe nuclear magnetic resonance spectrometer of INOVA-400 is measured, and frequency is 400MHz, taking tetramethylsilane (TMS) as interior mark, moltenAgent is CDCl3. The infrared instrument that the model that infrared analysis uses Shimadzu company to produce is IRAffinity-1 is measured,With CS2For solvent, resolution ratio is 2cm-1, transmissivity T% is between 30-50%. Molecular weight and molecualr weight distribution is adoptedThe gel permeation chromatograph that is GPC-220 by the model that PL company of Britain produces is measured, and leacheate is THF, flow velocityFor 1.0mL/min, probe temperature is 40 DEG C. The DSC200F3 differential amount that Nai Chi Instrument Ltd. of Germany producesThermal scanner carries out the mensuration of glass transition temperature Tg. Cooling: 25 DEG C～(100 DEG C), 5 DEG C/min; Heat up:-100 DEG C～25 DEG C, 10 DEG C/min; Sweep gas: nitrogen, 50mL/min; Protection gas: nitrogen, 50mL/min.
Solvent, monomer and the terminators etc. that use in polymerisation in the present invention all operate through the strict deoxygenation that dewaters,Water oxygen content is all lower than 20ppm.
Organic alkali metal initator in the present invention, by under anhydrous and oxygen-free condition, at room temperature, by B component andComponent A is according to mol ratio (0.1-100): 1 ratio is uniformly mixed, and set aside for use obtains. Wherein: component AFor organic alkali metal, B component is organic ethers or organic amine compound.
Concrete, in the initator a～h in embodiment, formula and the mol ratio of B component and component A are as follows:
Initator a:THF:n-BuLi=1.0
Initator b:TMEDA:s-BuLi=0.2
Initator c:2G:t-BuLi=0.2
Initator d:THF: lithium diisopropylamine=50
Initator e: dipiperidinoethane: n-BuLi=0.2
Initator f: tetrahydrofurfuryl alcohol ethylether: n-BuLi=0.2
Initator g: tetrahydrofurfuryl amine methyl ether: s-BuLi=0.2
Initator h:THF: naphthalene potassium=0.2
While preparing initator, said n-BuLi, s-BuLi, t-BuLi and lithium diisopropylamine are all Aladdin examinationsAgent company or An Naiji reagent company provide.
Embodiment 1
Under anhydrous and oxygen-free atmosphere, in the polymer reactor of processing through super-dry, add the volume fraction of 10ml to be10% trans-1,3-pentadiene cyclohexane solution, (Mn is designed to 20000 to add the initator a of specific meteringG/mol), at 80 DEG C, react 2h. Cooling rear use is whole containing the methanol solution of the BHT of 1wt%Only reaction, then use excessive methanol solution precipitating polymer, cyclic washing 4-5 time, finally vacuum drying at 40 DEG C24h, obtains polymer. Its1HNMR schemes as shown in Figure 1, and DSC schemes as shown in Figure 3, and GPC schemes as Fig. 4 instituteShow.
Calculating polymer yield through weighing is 98%, and in polymer, Isosorbide-5-Nitrae-structural content is 85%, wherein trans Isosorbide-5-Nitrae-knotStructure content is 74.5%, and acrylic content (1,2-content) is only 14%, essentially no 3,4-structure. The equal molecule of numberAmount Mn=26000g/mol, molecular weight distribution PDI=1.16, glass transition temperature Tg=-43.71 DEG C of polymer(mid point), initial Tg=-46.08 DEG C.
Embodiment 2
As organic alkali metal initator and polymerizing condition in embodiment 1, only replace cyclohexane give polymerization list with pentaneThe solvent of body carries out trans-1, the living polymerization of 3-pentadiene. The DSC of the polymer preparing schemes as shown in Figure 3.
The analysis result of resulting polymers is as follows: polymerisation conversion 95%, and in polymer, Isosorbide-5-Nitrae-structural content is 87%,Wherein trans Isosorbide-5-Nitrae-structural content is 68%, and acrylic content (1,2-content) is only 13%, essentially no 3,4-Structure. Number-average molecular weight Mn=18600g/mol, molecular weight distribution PDI=1.10, the vitrifying of polymer turnTemperature Tg=-48.08 DEG C (mid point), initial Tg=-50.52 DEG C.
Embodiment 3
As organic alkali metal initator and polymerizing condition in embodiment 1, only replace cyclohexane give as polymerization taking isopentaneThe solvent of monomer carries out trans-1, the living polymerization of 3-pentadiene. The DSC of the polymer preparing schemes as Fig. 3 instituteShow.
The analysis result of resulting polymers is as follows: polymerisation conversion 90%, and in polymer, Isosorbide-5-Nitrae-structural content is 90%,Wherein trans Isosorbide-5-Nitrae-structural content is 68%, and acrylic content (1,2-content) is only 10%, essentially no 3,4-Structure. Number-average molecular weight Mn=19400g/mol, molecular weight distribution PDI=1.09, the vitrifying of polymer turnTemperature Tg=-46.77 DEG C (mid point), initial Tg=-49.28 DEG C.
Embodiment 4
As organic alkali metal initator and polymerizing condition in embodiment 1, only replace cyclohexane give polymerization single polymerization monomer with tolueneSolvent carry out trans-1, the living polymerization of 3-pentadiene. The DSC of the polymer preparing schemes as shown in Figure 3.
The analysis result of resulting polymers is as follows: polymerisation conversion 60%, and in polymer, Isosorbide-5-Nitrae-structural content is 86%,Wherein trans Isosorbide-5-Nitrae-structural content is 69%, and acrylic content (1,2-content) is only 14%, essentially no 3,4-Structure. Number-average molecular weight Mn=5300g/mol, molecular weight distribution PDI=1.55, the glass transition of polymerTemperature T g=-49.35 DEG C (mid point), initial Tg=-51.39 DEG C. Toluene makees solvent and produces serious chain transfer, by brightShow and have influence on polymerization yield rate, polymer molecular weight and distribution.
Embodiment 5
As organic alkali metal initator and solvent in embodiment 1, only change temperature, reacting 6h at 60 DEG C carries outTrans-1, the living polymerization of 3-pentadiene. The poly-1,3-pentadiene that the present embodiment prepares13CNMR schemes as Fig. 2Shown in.
The analysis result of resulting polymers is as follows: polymerisation conversion 90%, and in polymer, Isosorbide-5-Nitrae-structural content is 86%,Wherein trans Isosorbide-5-Nitrae-structural content is 68%, and acrylic content (1,2-content) is only 14%, essentially no 3,4-Structure. Number-average molecular weight Mn=21200g/mol, molecular weight distribution PDI=1.17, the vitrifying of polymer turnTemperature Tg=-43.12 DEG C (mid point), initial Tg=-45.89 DEG C.
Embodiment 6
As the organic alkali metal initator in embodiment 1 and the solvent of polymerization single polymerization monomer, only change temperature, reaction at 40 DEG C12h carries out trans-1, the living polymerization of 3-pentadiene.
The analysis result of resulting polymers is as follows: polymerisation conversion 60%, and in polymer, Isosorbide-5-Nitrae-structural content is 86%,Wherein trans Isosorbide-5-Nitrae-structural content is 60%, and acrylic content (1,2-content) is only 14%, essentially no 3,4-Structure. Number-average molecular weight Mn=9400g/mol, molecular weight distribution PDI=1.13, the glass transition of polymerTemperature T g=-44.23 DEG C (mid point), initial Tg=-48.10 DEG C.
Embodiment 7
As the solvent of the polymerization single polymerization monomer in embodiment 1 and polymerizing condition, only change initiator type, with initator bCarry out trans-1, the living polymerization of 3-pentadiene.
The analysis result of resulting polymers is as follows: polymerisation conversion 98%, and in polymer, Isosorbide-5-Nitrae-structural content is 84%,Wherein trans Isosorbide-5-Nitrae-structural content is 67%, and acrylic content (1,2-content) is only 16%, essentially no 3,4-Structure. Number-average molecular weight Mn=32000g/mol, molecular weight distribution PDI=1.10, the vitrifying of polymer turnTemperature Tg=-48.11 DEG C (mid point), initial Tg=-50.46 DEG C.
Embodiment 8
As the solvent of the polymerization single polymerization monomer in embodiment 1 and polymerizing condition, only change initiator type, with initator, c entersRow trans-1, the living polymerization of 3-pentadiene.
The analysis result of resulting polymers is as follows: polymerisation conversion 97%, and in polymer, Isosorbide-5-Nitrae-structural content is 84%,Wherein trans Isosorbide-5-Nitrae-structural content is 67%, and acrylic content (1,2-content) is only 16%, essentially no 3,4-Structure. Number-average molecular weight Mn=23300g/mol, molecular weight distribution PDI=1.17, the vitrifying of polymer turnTemperature Tg=-52.83 DEG C (mid point), initial Tg=-53.64 DEG C.
Embodiment 9
As the solvent of the polymerization single polymerization monomer in embodiment 1 and polymerizing condition, only change initiator type, with initator dCarry out trans-1, the living polymerization of 3-pentadiene.
The analysis result of resulting polymers is as follows: polymerisation conversion 96%, and in polymer, Isosorbide-5-Nitrae-structural content is 85%,Wherein trans Isosorbide-5-Nitrae-structural content is 70%, and acrylic content (1,2-content) is only 15%, essentially no 3,4-Structure. Number-average molecular weight Mn=25100g/mol, molecular weight distribution PDI=1.16, the vitrifying of polymer turnTemperature Tg=-48.23 DEG C (mid point), initial Tg=-50.45 DEG C.
Embodiment 10
As polymerizing condition in embodiment 1, only change initiator type, in THF solvent, carry out with initator hTrans-1, the living polymerization of 3-pentadiene. The DSC of resulting polymers schemes as shown in Figure 3.
The analysis result of resulting polymers is as follows: polymerisation conversion 96%, and in polymer, Isosorbide-5-Nitrae-structural content is 71%,Wherein trans Isosorbide-5-Nitrae-structural content is 50%, and acrylic content (1,2-content) is only 3 of 25%, 4% content, 4-Structure. Number-average molecular weight Mn=21000g/mol, molecular weight distribution PDI=1.17, the vitrifying of polymer turnTemperature Tg=-32.23 DEG C (mid point), initial Tg=-35.15 DEG C.
Embodiment 11
As the solvent of the polymerization single polymerization monomer in embodiment 1 and polymerizing condition, only change initiator amount, regulate trans-pentaMole (Mn is designed to 90000g/mol) of the quality/initator of diene carried out the living polymerization of 1,3-pentadiene.The GPC of the poly-1,3-pentadiene preparing schemes as shown in Figure 4.
The analysis result of resulting polymers is as follows: polymerisation conversion 99%, and in polymer, Isosorbide-5-Nitrae-structural content is 84%,Wherein trans Isosorbide-5-Nitrae-structural content is 62%, and acrylic content (1,2-content) is only 16%, essentially no 3,4-Structure. Number-average molecular weight Mn=80600g/mol, molecular weight distribution PDI=1.17, the vitrifying of polymer turnTemperature Tg=-43.71 DEG C (mid point), initial Tg=-46.14 DEG C
Embodiment 12
As the solvent of the polymerization single polymerization monomer in embodiment 1 and polymerizing condition, only change monomer type, with mix-pentadieneFor polymerization single polymerization monomer carries out mix-1, the living polymerization of 3-pentadiene (trans:cis=67:33). The analysis of resulting polymersResult is as follows: polymerisation conversion 97%, in polymer, Isosorbide-5-Nitrae-structural content is 84%, wherein trans Isosorbide-5-Nitrae-structural contentBe 67%, acrylic content (1,2-content) is only 16%, essentially no 3,4-structure. Number-average molecular weightMn=31000g/mol, molecular weight distribution PDI=1.17, glass transition temperature Tg=-46.13 DEG C of polymer(mid point), initial Tg=-48.52 DEG C.
Embodiment 13
As the solvent of the polymerization single polymerization monomer in embodiment 1 and polymerization temperature, only change monomer type and polymerization time, withCis-pentadiene is polymerization single polymerization monomer, and the reaction time is 12h.
The analysis result of resulting polymers is as follows: polymerisation conversion 94%, and in polymer, Isosorbide-5-Nitrae-structural content is 83%,Wherein trans Isosorbide-5-Nitrae-structural content is 65%, and acrylic content (1,2-content) is only 17%, essentially no 3,4-Structure. Number-average molecular weight Mn=29000g/mol, molecular weight distribution PDI=1.18, the vitrifying of polymer turnTemperature Tg=-47.03 DEG C (mid point), initial Tg=-49.12 DEG C.
Embodiment 14
As organic alkali metal initator and polymerizing condition in embodiment 1, only replace cyclohexane give polymerization list with THFThe solvent of body carries out trans-1, the living polymerization of 3-pentadiene.
The analysis result of resulting polymers is as follows: polymerisation conversion 99%, and in polymer, Isosorbide-5-Nitrae-structural content is 68%,Wherein trans Isosorbide-5-Nitrae-structural content is 68%, and acrylic content (1,2-content) is 3 of 30%, 2% content, 4-Structure. Number-average molecular weight Mn=29600g/mol, molecular weight distribution PDI=1.14, the vitrifying of polymer turnTemperature Tg=-33.02 DEG C (mid point), initial Tg=-35.51 DEG C.
Embodiment 15
Under anhydrous and oxygen-free atmosphere, in the polymer reactor of processing through super-dry, add the volume fraction of 10ml to be1% cinnamic cyclohexane solution, adds specific metering initator e (Mn is designed to 2000g/mol), in 60 DEG CLower reaction 2h forms the polystyrene lithium macromole evocating agent with activated centre, adds specific metering after coolingTrans-1,3-pentadiene, makes monomer concentration remain on 15% (design molecular weight is 30000g/mol), anti-at 80 DEG CAnswer 2h, reaction finishes the methanol solution cessation reaction of rear use containing the BHT of 1wt%, then use excessiveMethanol solution precipitating polymer, cyclic washing 4-5 time, finally vacuum drying 24h at 40 DEG C, calculates poly-through weighingCompound conversion ratio is 99%, and in polymer, Isosorbide-5-Nitrae-structural content is 85%, and acrylic content (1,2-content) is only15%, essentially no 3,4-structure. Number-average molecular weight Mn=26000g/mol, molecular weight distribution PDI=1.16, instituteGlass transition temperature Tg=-43.71 DEG C (mid point) of polymer, initial Tg=-46.08 DEG C.
Embodiment 16
Under anhydrous and oxygen-free atmosphere, in the polymer reactor of processing through super-dry, add the volume fraction of 10ml to beThe cyclohexane solution of 1% isoprene, adds the initator f (Mn is designed to 2000g/mol) of specific metering,At 60 DEG C, react 2h and form the polyisoprene lithium macromole evocating agent with activated centre, add specific meter after coolingThe trans-1 of amount, 3-pentadiene, makes monomer concentration remain on 15% (design molecular weight is 30000g/mol), in 80 DEG CLower reaction 2h, reaction finishes the methanol solution cessation reaction of rear use containing 1% BHT, then usesAmount methanol solution precipitating polymer, cyclic washing 4-5 time, finally vacuum drying 24h at 40 DEG C, through the calculating of weighingPolymer conversion ratio is 98%, and in polymer, Isosorbide-5-Nitrae-structural content is 85%, and acrylic content (1,2-content) onlyBe 15%, essentially no 3,4-structure. Number-average molecular weight Mn=26000g/mol, molecular weight distribution PDI=1.16,Glass transition temperature Tg=-43.71 DEG C (mid point) of polymer, initial Tg=-46.08 DEG C.
Embodiment 17
Under anhydrous and oxygen-free atmosphere, in the polymer reactor of processing through super-dry, add the volume fraction of 10ml to beThe cyclohexane solution of 1% butadiene, adds the initator g (Mn is designed to 2000g/mol) of specific metering, inAt 60 DEG C, react 2h and form the polybutadiene lithium macromole evocating agent with activated centre, add specific metering after coolingTrans-1,3-pentadiene, makes monomer concentration remain on 15% (design molecular weight is 30000g/mol), anti-at 80 DEG CAnswer 2h, reaction finishes the methanol solution cessation reaction of rear use containing 1% BHT, then uses excessive firstAlcoholic solution precipitating polymer, cyclic washing 4-5 time, finally vacuum drying 24h at 40 DEG C, through the calculating polymerization of weighingThing conversion ratio is 98%, and in polymer, Isosorbide-5-Nitrae-structural content is 85%, and acrylic content (1,2-content) is only 15%,Essentially no 3,4-structure. Number-average molecular weight Mn=26000g/mol, molecular weight distribution PDI=1.16, polymerizationGlass transition temperature Tg=-43.71 of thing DEG C (mid point), initial Tg=-46.08 DEG C.
Claims (10)
1. a preparation method for the poly-1,3-pentadiene of the linearity of low acrylic content, Narrow Molecular Weight Distribution, is characterized in that,Concrete steps are as follows: under the condition of anhydrous and oxygen-free, add aprotic solvent, 1 in polymer reactor, 3-penta 2Alkene monomer and organic alkali metal initator, polymerisation 1h～24h at 0～120 DEG C of temperature afterwards, finally with anti-oldThe alcoholic solution cessation reaction of agent, and separate out polymer with excessive methanol or ethanol, washing, dry, obtain low propyleneThe poly-1,3-pentadiene of linearity of base content, Narrow Molecular Weight Distribution; Wherein: described 1,3-pentadiene monomer and organic baseThe mol ratio of metal initiator is 1:(10-3～10-6); Described organic alkali metal initator comprises that mol ratio is 1:The A of (0.1～100), B two components, component A is organic alkali metal, B component is organic ethers or organic amineCompound.
2. preparation method according to claim 1, is characterized in that, described organic alkali metal is selected from organolithium chemical combinationIn thing, organosiloxane compound, organic potassium compound or organocesium compounds any.
3. preparation method according to claim 2, is characterized in that, described organo-lithium compound be selected from lithium alkylide,
In nitrogen lithium or large molecular activity organolithium any; Described organosiloxane compound is selected from sodium alkyl, nitrogen sodium or divides greatlySon active organic sodium in any; Described organic potassium compound is selected from potassium alkyl, nitrogen potassium or large molecular activity organic potassiumIn any; Described organocesium compounds is selected from alkyl caesium, nitrogen caesium or the large organic caesium of molecular activity any.
4. preparation method according to claim 3, is characterized in that, described lithium alkylide is n-BuLi, sec-butylLithium, tert-butyl lithium, benzene lithium or benzyl lithium; Described nitrogen lithium is dimethylamino lithium, diethylamino lithium or diisopropylLithium amide; Described large molecular activity organolithium is polystyryl lithium, polybutadiene lithium, polyisoprene lithium or poly-1,3-cyclohexadiene lithium; Described sodium alkyl is butyl sodium or naphthalene sodium; Described potassium alkyl is butyl potassium, naphthalene potassium or benzyl potassium;Described alkyl caesium is butyl caesium.
5. preparation method according to claim 1, is characterized in that, described organic ether compounds be selected from ether,Diethylene glycol dimethyl ether, diisopropyl ether, many glycol dialkyl ethers, oxolane, 1,3-dioxane, tetrahydrochyseneIn furan alkyls ether and derivative thereof any; Described organic amine compound be selected from triethylamine, tetramethylethylenediamine,In PMDETA, tetrahydrofurfuryl amine, dipiperidinoethane, tetrahydrofurfuryl amine methyl ether and derivative thereof any.
6. preparation method according to claim 1, is characterized in that, described aprotic solvent is selected from cyclohexane, ownAlkane, pentane, isopentane, toluene, oxolane, ether, diethylene glycol dimethyl ether, triethylamine or tetramethyl secondOne or more in diamines; The volumetric concentration of 1,3-pentadiene monomer in aprotic solvent is 5～40%.
7. according to the preparation method described in claim 1 or 6, it is characterized in that, described 1,3-pentadiene monomer is in non-matterVolumetric concentration in sub-solvent is 10～20%.
8. according to the preparation method described in claim 1 or 6, it is characterized in that, described 1,3-pentadiene monomer comprises and being selected fromThe cis-1 of polymer grade, 3-pentadiene, trans-1, the cis/trans-1 of 3-pentadiene, any proportioning, 3-pentadiene mix monomer,Or in 1,3-pentadiene derivative any.
9. preparation method according to claim 1, is characterized in that, polymerization 2～4 hours at 60～80 DEG C of temperature.
10. the poly-1,3-pentadiene of linearity that preparation method according to claim 1 obtains, is characterized in that, poly-Isosorbide-5-Nitrae-the structural content of 1,3-pentadiene is between 70～90%, and acrylic content, between 10～30%, is counted equal moleculeMn is 10 for amount3～106Between g/mol, the PDI value of Narrow Molecular Weight Distribution, Mw/Mn between 1.05～1.18,Vitrification point Tg is between-55 DEG C～-30 DEG C; Wherein: in its Isosorbide-5-Nitrae-structure, the content of trans-Isosorbide-5-Nitrae structure 50～In 70% scope, Mw represents weight average molecular weight.
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| CN102134293A (en) * | 2011-02-23 | 2011-07-27 | 中国科学院长春应用化学研究所 | Preparation method of 1,3-pentadiene polymer |
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| US4482771A (en) * | 1983-01-03 | 1984-11-13 | The Dow Chemical Company | Anionic polymerization of cis- and trans-1,3-pentadiene from a mixture of saturated and unsaturated hydrocarbons |
| CN1293211A (en) * | 1999-10-14 | 2001-05-02 | 上海石油化工股份有限公司 | Process for polymerizing pentadiene resin |
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