CN105732872A - Narrow molecular weight distribution butyl rubber synthesis method - Google Patents
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Abstract
The invention belongs to the technical field of rubber synthesis and provides a narrow molecular weight distribution butyl rubber synthesis method. The method utilizes a haloalkane-C4-10 saturated alkane mixed solvent, the content of haloalkane is in a range of 1-55% by volume, a used main catalyst comprises R-Al-Cl2, R2-Al-Cl1 and vanadium trihalide oxide, water is added into the catalyst according to a certain ratio, benzopyrene and/or nitrosamine compound is added into the main catalyst so that an initiator aid is formed and a main initiator comprises R-Al-Cl2 and R2-Al-Cl1. The catalysis system is a homogeneous system and is convenient for charging. Through use of a trace amount of water, a stable complex initiation system is formed. The method solves the problem that butyl rubber molecular weight is reduced along with temperature increasing. The butyl rubber has number-average absolute molecular weight of 2000-550000 and molecular weight distribution of 1.1-2.0.
Description
Technical field
The present invention relates to a kind of synthesis butyl rubber new technique, particularly relate to the butyl rubber being monomer with isobutene. and isoprene with solwution method synthesis, and by method that the composition and proportioning changing catalyst controls molecular chain conformation.
Background technology
Butyl rubber is the product obtained by cationic copolymerization by isobutene. (94.5%～98.5%) and a small amount of isoprene (4.5%～1.5%), due to the feature in its structure, so having the air-tightness of brilliance, for instance air is about high 9 times.Butyl rubber is gone into operation from nineteen forty-three and is still taken turns the inner tube of a tyre or using it as seal coating in cover tire for synthesis so far, makes the glue kind that the tubeless tyre that Tire & Tube unites two into one is not replaced.It has excellent heat-proof aging, resistance to ozone and chemical stability, additionally, it also has distinctive damping capacity, it is possible to for occasions such as Shock-proof for building and suction radiant energy.
The industrial process of butyl rubber is divided into slurry process and solwution method two kinds.Use H2O·AlCl3Do initiator system and in chloromethanes, carry out the rubber of polyreaction generation insoluble in chloromethanes, but become paste-like granule or little blob of viscose to be suspended in chloromethanes, therefore named for slurry process.Slurry process is with H2O·A1Cl3For initiator system, chloromethanes is diluent, and isobutene. is prepared butyl rubber with a small amount of isoprene by cationic copolymerization by (about-100 DEG C) at low temperatures.Solwution method is that in varsol (such as isopentane) at-90～-70 DEG C, isobutene. and a small amount of isoprene copolymer form with the complex of alkyl aluminum chloride and water for initiator.
In butyl rubber polymerization technique, the method in general producing butyl rubber is known, and cationic polymerization generally adopts the Lewis such as metal and non-metallic halide acid as catalyst.Such as, see that UllmannsEncyclopediaofIndustrialChemistry, A roll up, 23 pages, 1993 years.Described slurry process is with dichloromethane for solvent, with aluminum chloride for initiator, is simultaneously introduced a small amount of water or hydrogen chloride, makes isobutene. react with isoprene generation cationic copolymerization.The polymeric reaction temperature of above-mentioned slurry process requires at-100 DEG C, in order to reach the sufficiently high molecular weight required by rubber processing industry, and therefore required energy consumption is very big.
Foreign literature widespread reports solwution method butyl rubber is isobutene. is the product obtained by cationic copolymerization under the catalysis such as ethyl chloride, isopentane and catalyst system and catalyzing ethyl aluminum dichloride at dicyandiamide solution with isoprene.Russ P RU2049795C1 adopts organo-aluminum compound to make catalyst, in varsol, at temperature-80 DEG C～-50 DEG C, comonomer and carry out the combined polymerization of isobutene. and isoprene when varsol volume ratio 37:41 and prepare butyl rubber.The control that its shortcoming is polyreaction has some limitations, and after improving polymeric reaction temperature, the molecular weight of product can significantly reduce.
It addition, it is aluminum alkyl halide that Canadian Patent 1,019,095 reports the catalyst system and catalyzing of employing, promoter is water or hydrogen sulfide, and solvent is the method for isopentane.US Patent No. 3,361,725 proposes the mixture adopting dialkyl aluminum halide and alkylaluminum dichlorides as catalyst, and the preferable temperature of this system is-79～-68 DEG C, and obtains satisfied result under atmospheric pressure when close-73 DEG C.
Chinese patent CN1253141A, discloses and a kind of adopts activation aluminum alkyl halide to prepare the improved method of butyl rubber, be actually one prepare weight average molecular weight at least about 400,000 the method for butyl polymer.The method comprises the following steps: to allow C4～C8Monoolefine monomer and C4～C14Multi-olefin monomer is the temperature range of about-100 DEG C～about+50 DEG C, contacting under aliphatic hydrocarbon diluent and a kind of catalyst mixture exist, this catalyst mixture comprises at least one accounting for major amount of aluminum dialkyl monohalide, a small amount of dihalide alkyl aluminum and minute quantity in water, aikyiaiurnirsoxan beta and mixture thereof.
This patented method can obtain isoprene content in higher polymerization rate, higher molecular weight rubber (particularly, weight average molecular weight) and higher rubber.Observing, when aikyiaiurnirsoxan beta is present in the reaction feed containing isobutene., polymerization rate and product molecular weight rubber all improve simultaneously.
Chinese patent CN102875716A discloses the method for a kind of solwution method synthesis butyl rubber, the method of described solwution method synthesis butyl rubber, specifically adopting halogenated alkane and carbon four to carbon ten saturated alkane mixed solvent, wherein the ratio of halogenated alkane is 1%～55%；The set of monomers of synthesis butyl rubber becomes isobutene. and isoprene, and isobutene. accounts for 15%～60% (V) of overall volume, and the addition of isoprene is 0.1%～5% (V) of isobutene. volume；
Catalyst composition is R-Al-Cl in molar ratio2:R2-Al-Cl1: three oxyhalogen vanadium=1:(0.1～30) (0.1～2.5)；R、R2For CH3-,CH3CH2-,CH3CH2CH2-,CH3CH2CH2CH2,CH3CH2(CH3)CH2-in any one alkyl；
Catalyst adds a certain proportion of water, and adding the total mole number of catalyst with the ratio of water is (0.1～10): 1；Add total mole number is reaction monomers total mole number the 0.05%～3% of catalyst.Polymeric reaction temperature is-45 DEG C～-80 DEG C；The system pressure of polyreaction is-0.05MPa～2.0MPa.
In the described alkane that carbon four to carbon ten saturated alkane is carbon four to carbon ten any component mixing, or by any component of corresponding monoolefine with arbitrary proportion mix after through be hydrogenated with saturated after obtain.
Described halogenated alkane is R-X, R is carbon one to carbon eight straight or branched alkyl, and X is F, Cl, Br or I.
In solwution method, use the complexation initiator system that three oxyhalogen vanadium of different ratio, aluminium diethyl monochloride and ethyl aluminum dichloride and water are formed that the molecular weight of synthesis butyl rubber is had regulating and controlling effect, and (-45 DEG C～-80 DEG C) alleviate the problem that molecular weight raises with temperature under higher polymerization temperature.
The main contents of this patent are the 3rd component three oxyhalogen vanadium added in catalyst system, and with the catalyst that aluminium diethyl monochloride and ethyl aluminum dichloride form in proportion, catalyst system and catalyzing is homogeneous system, it is simple to reinforced.By adding minor amount of water, form stable complex initiator system.The performance of butyl rubber will not be produced impact by solvent for use.The method is applied in the solution polymerization butyl rubber experiment that isobutene. and isoprene are monomer, the problem that can solve the problem that the molecular weight of butyl rubber to raise with temperature and to reduce, the equal absolute molecular weight of number of gained butyl rubber is 30,000～500,000, and molecular weight distribution is between 1.2～3.5.
The curability equal absolute molecular weight of number not high, gained butyl rubber that the deficiency that above patent exists is rubber is relatively low.
Summary of the invention
The technical scheme is that after improving polymeric reaction temperature, the molecular weight of product can significantly reduce, and the equal absolute molecular weight of number of gained butyl rubber is relatively fewer in order to overcome the control of the polyreaction existed in prior art to have some limitations；The shortcoming that required energy consumption is very big, and the method that a kind of efficient solwution method synthesis butyl rubber is provided, the problem that its objective is the molecular weight alleviating butyl rubber product to raise with temperature and to reduce rapidly, thus it is qualified to obtain molecular weight, the butyl rubber product of narrow molecular weight distribution, extending the continuous polymerization time of reactor, reduce wash number, this invention will obtain considerable economic benefit for producing.
Technical scheme:
The butyl rubber synthetic method of a kind of Narrow Molecular Weight Distribution, the method is in utilizing solwution method synthesis butyl rubber process, by changing the composition synthesis different molecular weight butyl rubber of catalyst；Wherein,
Adopting the solvent that halogenated alkane and carbon four to carbon ten saturated alkane are mixed to form, the volume ratio of wherein said halogenated alkane content is 1%～55%；
Use consists of R-Al-Cl2:R2-Al-Cl1: the major catalyst of three oxyhalogen vanadium, form network and thing initiator system as main initiator with minor amount of water；
Prepare in described major catalyst add using aluminum be quality base benchmark, mol ratio be 0.1%～30% benzopyrene and/or nitrosamine compound as aided initiating, prepare composite catalyst；
The set of monomers of described synthesis butyl rubber becomes isobutene. and isoprene, and wherein, isobutene. accounts for 15%～55% (V) of overall volume, and the addition of isoprene is 0.1%～6% (V) of isobutene. volume；
Being mixed with solvent with isoprene by described isobutene., isobutene. and isoprene than 15:85～45:55, after mixing under the water complex system catalysis of described composite catalyst, aggregated are obtained by reacting butyl rubber with solvent volume.
Described polymeric reaction temperature is-25 DEG C～-80 DEG C.
The system pressure of described polyreaction is-0.01MPa～2.5MPa.
The mol ratio of described major catalyst composition is: R-Al-Cl2:R2-Al-Cl1: three oxyhalogen vanadium=1:0.1～30:0.1～2.5.
Described major catalyst is additionally added a certain proportion of water, and it adds the mol ratio of water: major catalyst: water=0.1～10:1.
Described nitrosamines is any one or a few mixture in N-N-nitrosodimethylamine, nitroso-group methyl ethylamine, N-diethylnitrosamine, N-dipropyl nitrosamine, N-dibutyl nitrosamine, N-nitroso-piperidine, N-nitrosopyrolidine, N-nitrosomorpholine, N-methyl-N-nitroso aniline, N-ethyl-N-nitrosoaniline；Or, described benzopyrene is benzo (a) pyrene, benzo (b) pyrene, deuterated benzo (A) anthracene, benzo (b) fluoranthene, benzo (j) fluoranthene, benzo (k) fluoranthene, dibenzanthracene, bends (1,2-benzophenanthrene；Thick dinaphthyl) in any one or a few mixture,.
Described carbon four to carbon ten saturated alkane be in the alkane of carbon four to carbon ten any component mixing, or by any component of corresponding monoolefine with arbitrary proportion mix after through be hydrogenated with saturated after obtain.
Described halogenated alkane is R-X, R is carbon one to carbon eight straight or branched alkyl, and X can be F, Cl, Br or I.
Described R1-Al-Cl2And R2-Al-Cl1R represent CH3-, CH3CH2-, CH3CH2CH2-, CH3CH2CH2CH2-and CH3CH2(CH3)CH2-in any one alkyl.
The polyreaction of the present invention can continuously perform or interval carries out.In an embodiment of the present invention, polyreaction is intermittent reaction.
Beneficial effects of the present invention:
The present invention is a kind of solwution method butyl rubber new synthesis technology mainly.After being mixed with a certain amount of solvent with isoprene by isobutene., under the water complex system catalysis of composite catalyst, obtain a kind of butyl rubber.Wherein solvent is mainly the mixed solvent that halogenated alkane is formed with certain proportion proportioning with carbon four to carbon ten saturated alkane.The volume ratio of halogenated alkane and carbon four to carbon ten saturated alkane is 1-55%.This technology is a major advantage that and can solve the problem that molecular weight reduces with the raw height of temperature preferably.And the butyl rubber product of required Narrow Molecular Weight Distribution is realized producing by the composition and ratio of initiator system.
The present invention it is critical only that the 3rd affiliated component three oxyhalogen vanadium, and with the catalyst system and catalyzing that aluminium diethyl monochloride and dichloro one aluminium ethide form by a certain percentage, catalyst system and catalyzing is homogeneous system, it is simple to reinforced.By adding minor amount of water, form stable complex initiator system.The performance of butyl rubber will not be produced impact by solvent for use.Study discovery by experiment, the method is applied in the solution polymerization butyl rubber experiment that isobutene. and isoprene are monomer, the problem that can solve the problem that the molecular weight of butyl rubber raw high with temperature and to reduce, the equal absolute molecular weight of number of gained butyl rubber is 2,000～550,000, and molecular weight distribution is between 1.1～2.0.
The present invention improves the polymerization temperature of reaction, improves the molecular weight of polymer, improves the molecular weight distribution of polymerizate.Find by studying, in solwution method, if the network that use three oxyhalogen vanadium of different ratio, aluminium diethyl monochloride and ethyl aluminum dichloride and water are formed and initiator system are as main initiator, add aided initiating Benzpyrene and nitrosamine compound, the molecular weight of synthesis butyl rubber is had regulating and controlling effect, and (-25 DEG C～-80 DEG C) alleviate the problem that molecular weight raises with temperature under higher polymerization temperature.
Accompanying drawing explanation
Fig. 1 is the block diagram of the synthetic method of the present invention.
Detailed description of the invention
By the examples below the present invention is specifically described.Be necessary it is pointed out here that be that following example are served only for the present invention is further described; it is not intended that limiting the scope of the invention, the present invention can be made some nonessential improvement and adjustment according to the invention described above content by the person skilled in the art in this field.
As it is shown in figure 1, the butyl rubber synthetic method of a kind of Narrow Molecular Weight Distribution of the present invention, the method is in utilizing solwution method synthesis butyl rubber process, by changing the composition synthesis different molecular weight butyl rubber of catalyst；Wherein:
Adopting the solvent that halogenated alkane and carbon four to carbon ten saturated alkane are mixed to form, the volume ratio of wherein said halogenated alkane content is 1%～55%；
Use consists of R-Al-Cl2:R2-Al-Cl1: the major catalyst of three oxyhalogen vanadium, form network and thing initiator system as main initiator with minor amount of water；
Prepare in described major catalyst add using aluminum be quality base benchmark, mol ratio be 0.1%～30% benzopyrene and/or nitrosamine compound as aided initiating, prepare composite catalyst；
The set of monomers of described synthesis butyl rubber becomes isobutene. and isoprene, and wherein, isobutene. accounts for 15%～55% (V) of overall volume, and the addition of isoprene is 0.1%～6% (V) of isobutene. volume；
Being mixed with solvent with isoprene by described isobutene., isobutene. and isoprene than 15:85～45:55, after mixing under the water complex system catalysis of described composite catalyst, aggregated are obtained by reacting butyl rubber with solvent volume.
Described polymeric reaction temperature is-25 DEG C～-80 DEG C.
The system pressure of described polyreaction is-0.01MPa～2.5MPa.
The mol ratio of described major catalyst composition is: R-Al-Cl2:R2-Al-Cl1: three oxyhalogen vanadium=1:0.1～30:0.1～2.5.
Described major catalyst is additionally added a certain proportion of water, and it adds the mol ratio of water: major catalyst: water=0.1～10:1.
Described nitrosamines is any one or a few mixture in N-N-nitrosodimethylamine, nitroso-group methyl ethylamine, N-diethylnitrosamine, N-dipropyl nitrosamine, N-dibutyl nitrosamine, N-nitroso-piperidine, N-nitrosopyrolidine, N-nitrosomorpholine, N-methyl-N-nitroso aniline, N-ethyl-N-nitrosoaniline；Or, described benzopyrene is benzo (a) pyrene, benzo (b) pyrene, deuterated benzo (A) anthracene, benzo (b) fluoranthene, benzo (j) fluoranthene, benzo (k) fluoranthene, dibenzanthracene, bends (1,2-benzophenanthrene；Thick dinaphthyl) in any one or a few mixture.
Described carbon four to carbon ten saturated alkane be in the alkane of carbon four to carbon ten any component mixing, or by any component of corresponding monoolefine with arbitrary proportion mix after through be hydrogenated with saturated after obtain.
Described halogenated alkane is R-X, R is carbon one to carbon eight straight or branched alkyl, and X can be F, Cl, Br or I.
Described R1-Al-Cl2And R2-Al-Cl1R represent CH3-, CH3CH2-, CH3CH2CH2-, CH3CH2CH2CH2-and CH3CH2(CH3)CH2-in any one alkyl.
The polyreaction of the present invention can continuously perform or interval carries out.In an embodiment of the present invention, polyreaction is intermittent reaction.
In these embodiments, the molecular weight of butyl rubber multi-angle laser light scattering instrument detection molecules amount and distribution thereof, with polystyrene for standard specimen.Column temperature 30 DEG C, flow rates 1.000mL/min, flow rate accuracy 0.1%, solvent THF, refractive index: 1.402.
Monomer and solvent refining: solvent and isobutene. adoptMolecular sieve adsorption removes free water therein, makes water content be down to below 30ppm.Isoprene adoptsMolecular sieve adsorption removes free water therein, before use through polymerization inhibitor is distilled off.
Comparative example 1
Under the protection of high pure nitrogen, first the moisture in monomer is taken off to below 10ppm, by R1-Al-Cl2、R2-Al-Cl1(1:1) mixing by a certain percentage, then minor amount of water (m urges: m water=2:3) is added by the total mole number of catalyst, mixing also ageing is made into, after 5 minutes～400 hours, the major catalyst that concentration is 0.08M (in aluminum), add 5% (in aluminum, mol ratio) N-N-nitrosodimethylamine and 5% is (in aluminum, mol ratio) benzo (b) pyrene, it is configured to mixed initiator standby；300ml isobutene. and isoprene monomer are down to after mixing homogeneously with the solvent (chloromethanes containing 35% (v)) of 500ml after-75 DEG C, add the 40ml ageing complex catalyst of 30 minutes (concentration is 0.08M), add 60ml methanol after reacting 30 minutes and precipitate out butyl rubber.With the NaOH solution washing of 2% (m) to alkalescence, then it is washed till neutrality with distilled water.Drying 8 hours in 60 DEG C with vacuum drying oven, then detection obtains the absolute molecular weight of butyl rubber: 23.18 ten thousand, and molecular weight distribution is 1.45.Monomer conversion 40.3%.
Comparative example 2
Under the protection of high pure nitrogen, first the moisture in monomer is taken off to below 10ppm, by R1-Al-Cl2、R2-Al-Cl1(1:1) mixing by a certain percentage, then minor amount of water (m urges: m water=2:3) is added by the total mole number of catalyst, it is standby that mixing also ageing is made into, after 5 minutes-400 hours, the complex catalyst that concentration is 0.08M (in aluminum), 300ml isobutene. and isoprene monomer are down to after mixing homogeneously with the solvent (being not added with halogenated alkane) of 500ml after-60 DEG C, add the 60ml ageing complex catalyst of 30 minutes (concentration is 0.08M), add 60ml methanol after reacting 60 minutes and terminate reaction.NaOH solution washing with 2% is to alkalescence, then is washed till neutrality with distilled water.Drying 8 hours in 60 DEG C with vacuum drying oven, then detection obtains the molecular weight of butyl rubber is 9.2 ten thousand, and molecular weight distribution is 2.13, monomer conversion 34.7%.
Embodiment 1:
Under the protection of high pure nitrogen, first the moisture in monomer is taken off to below 10ppm, by R1-Al-Cl2、R2-Al-Cl1Certain mol proportion (1:1:0.5) mixing is pressed with vanadium oxytrichloride, then minor amount of water (m urges: m water=2:3) is added by the total mole number of catalyst, add 5% (in aluminum, mol ratio) N-N-nitrosodimethylamine and 5% is (in aluminum, mol ratio) benzo (b) pyrene, it is configured to mixed initiator, it is standby that mixing also ageing is made into, after 5 minutes-400 hours, the complex catalyst that concentration is 0.08M (in aluminum), 300ml isobutene. and isoprene monomer are down to after mixing homogeneously with the solvent (ethyl chloride containing 35% (v)) of 500ml after-70 DEG C, add the 60ml ageing complex catalyst of 30 minutes (concentration is 0.08M), add 60ml methanol after reacting 30 minutes and precipitate out butyl rubber.With the NaOH solution washing of 2% (m) to alkalescence, then it is washed till neutrality with distilled water.Drying 8 hours in 60 DEG C with vacuum drying oven, then detection obtains butyl rubber absolute molecular weight is 28.37 ten thousand, and molecular weight distribution is 1.28, monomer conversion 38.4%.
Embodiment 2
Under the protection of high pure nitrogen, first the moisture in monomer is taken off to below 10ppm, by R1-Al-Cl2、R2-Al-Cl1(1:1) mixing by a certain percentage, then minor amount of water (m urges: m water=2:3) is added by the total mole number of catalyst, it is standby that mixing also ageing is made into, after 5 minutes～400 hours, the complex catalyst that concentration is 0.08M (in aluminum), 300ml isobutene. and isoprene monomer are down to after mixing homogeneously with the solvent (chloromethanes containing 35% (v)) of 500ml after-60 DEG C, add the 60ml ageing complex catalyst of 30 minutes (concentration is 0.08M), add 60ml methanol after reacting 60 minutes and terminate reaction.NaOH solution washing with 2% is to alkalescence, then is washed till neutrality with distilled water.Drying 8 hours in 60 DEG C with vacuum drying oven, then detection obtains the absolute molecular weight of butyl rubber is 12.32 ten thousand, and molecular weight distribution is 1.58, monomer conversion 35.4%.
Embodiment 3
Under the protection of high pure nitrogen, first the moisture in monomer is taken off to below 10ppm, by R1-Al-Cl2、R2-Al-Cl1Certain mol proportion (2:1:0.2) mixing is pressed with vanadium oxytrichloride, then minor amount of water (m urges: m water=4:1) is added by the total mole number of catalyst, add 5% (in aluminum, mol ratio) N-N-nitrosodimethylamine and 5% is (in aluminum, mol ratio) benzo (b) pyrene, it is configured to mixed initiator, it is standby that mixing also ageing is made into, after 5 minutes～400 hours, the complex catalyst that concentration is 0.08M (in aluminum), 300ml isobutene. and isoprene monomer are down to after mixing homogeneously with the solvent (chloromethanes containing 40% (v)) of 500ml after-80 DEG C, add the 65ml ageing complex catalyst of 15 minutes (concentration is 0.08M), add 60ml methanol after reacting 40 minutes and precipitate out butyl rubber.With the NaOH solution washing of 2% (m) to alkalescence, then it is washed till neutrality with distilled water.Drying 8 hours in 60 DEG C with vacuum drying oven, then detection obtains butyl rubber absolute molecular weight is 32.3 ten thousand, and molecular weight distribution is 1.2, monomer conversion 35.3%.
Embodiment 4
Under the protection of high pure nitrogen, first the moisture in monomer is taken off to below 10ppm, by R1-Al-Cl2、R2-Al-Cl1Certain mol proportion (1:0.1:0.4) mixing is pressed with vanadium oxytrichloride, then minor amount of water (m urges: m water=3:5) is added by the total mole number of catalyst, add 5% (in aluminum, mol ratio) N-N-nitrosodimethylamine and 5% is (in aluminum, mol ratio) benzo (b) pyrene, it is configured to mixed initiator, it is standby that mixing also ageing is made into, after 5 minutes～400 hours, the complex catalyst that concentration is 0.08M (in aluminum), 300ml isobutene. and isoprene monomer are down to after mixing homogeneously with the solvent (chloromethanes containing 12% (v)) of 500ml after-55 DEG C, add the 60ml ageing complex catalyst of 90 minutes (concentration is 0.08M), add 60ml methanol after reacting 40 minutes and precipitate out butyl rubber.With the NaOH solution washing of 2% (m) to alkalescence, then it is washed till neutrality with distilled water.Drying 8 hours in 60 DEG C with vacuum drying oven, then detection obtains butyl rubber absolute molecular weight is 16.5 ten thousand, and molecular weight distribution is 1.36.Monomer conversion 36.2%.
Embodiment and comparative example data analysis in the present invention:
From table, comparative example 2 and embodiment 2 can be seen that, it is added without N-N-nitrosodimethylamine and benzo (b) pyrene, the molecular weight of butyl rubber is low, and distribution width, after addition, molecular weight N-N-nitrosodimethylamine and benzo (b) pyrene post-consumer polymer molecular weight substantially uprise, molecular weight distribution sharp, yield slightly improves.Remain to reach more than 16.5 ten thousand improving reaction temperature to-55 DEG C of post polymerization molecular weight of product.Illustrate that the addition effect of N-N-nitrosodimethylamine and benzo (b) pyrene is obvious.N-N-nitrosodimethylamine and benzo (b) pyrene form complex with initiator, participate in catalytic reaction, the amount existed with monomer in the polymer after the completion of reaction cannot detect, it should is washed with water or is combined with polymer formation segment, do not have polymer other influences.
Consumption for N-N-nitrosodimethylamine: 60 milliliters of (initiator) × 0.08M (concentration) × 5%=0.00024mol
The quality of N-N-nitrosodimethylamine: 0.00024mol × 74.08g/mol (molecular weight)=0.0178g
Generate polymer quality: 300 milliliters × 0.7g/ milliliter (isobutene. density)=210g
Theoretical content=0.0178/210g=84.8ppm in the polymer in N-N-nitrosodimethylamine not conversion situation
After alkali cleaning, washing, can't detect N-N-nitrosodimethylamine monomer in the polymer after real reaction, produce toxic effect thus without to polymer.Benzo (b) pyrene is also same.
Rubber processing process may be used benzo (b) pyrene or N-N-nitrosodimethylamine use as age resistor or rubber chemicals, but its consumption is far above consumption in the present invention, and its effect is not improve polymer molecular weight, therefore the present invention adopts N-N-nitrosodimethylamine or benzo (b) pyrene and R1-Al-Cl2、R2-Al-Cl1And vanadium oxytrichloride forms complex, as aided initiating, there is novelty.
N, N-N-nitrosodimethylamine physicochemical property: yellow liquid, in neutrality, has weak stink, and adhesive tape degree is low.Molecular weight 74.08.Density 1.015g/cm3(20℃).Boiling point 151～153 DEG C.Flash-point 61 DEG C.It is dissolved in water, ethanol, ether, dichloromethane.Stable with in highly basic in physiological conditions, unstable in an acidic solution.
N-N-nitrosodimethylamine and benzo (b) pyrene can use during difference in the present invention, it is also possible to reach the raising polymer molecular weight when higher polymerization temperature, reduce the result of molecular weight distribution.
The catalyst system and catalyzing of the present invention is homogeneous system, it is simple to reinforced；By adding minor amount of water, form stable complex initiator system；The method can solve the problem that the problem that the molecular weight of butyl rubber reduces with temperature rising, and the equal absolute molecular weight of number of gained butyl rubber is 2,000～550,000, and molecular weight distribution is between 1.1～2.0.
Claims (9)
1. the butyl rubber synthetic method of a Narrow Molecular Weight Distribution, it is characterised in that:
In utilizing solwution method synthesis butyl rubber process, by changing the composition synthesis different molecular weight butyl rubber of catalyst；Wherein:
Adopting the solvent that halogenated alkane and carbon four to carbon ten saturated alkane are mixed to form, the volume ratio of wherein said halogenated alkane content is 1%～55%；
Use consists of R-Al-Cl2:R2-Al-Cl1: the major catalyst of three oxyhalogen vanadium, form network and thing initiator system as main initiator with minor amount of water；
Prepare in described major catalyst add using aluminum be quality base benchmark, mol ratio be 0.1%～30% benzopyrene and/or nitrosamine compound as aided initiating, prepare composite catalyst；
The set of monomers of described synthesis butyl rubber becomes isobutene. and isoprene, and wherein, isobutene. accounts for 15%～55% (V) of overall volume, and the addition of isoprene is 0.1%～6% (V) of isobutene. volume；
Being mixed with solvent with isoprene by described isobutene., isobutene. and isoprene than 15:85～45:55, after mixing under the water complex system catalysis of described composite catalyst, aggregated are obtained by reacting butyl rubber with solvent volume.
2. the butyl rubber synthetic method of a kind of Narrow Molecular Weight Distribution according to claim 1, it is characterised in that: described polymeric reaction temperature is-25 DEG C～-80 DEG C.
3. the butyl rubber synthetic method of a kind of Narrow Molecular Weight Distribution according to claim 1, it is characterised in that: the system pressure of described polyreaction is-0.01MPa～2.5MPa.
4. the butyl rubber synthetic method of a kind of Narrow Molecular Weight Distribution according to claim 1, it is characterised in that: the mol ratio of described major catalyst composition is: R-Al-Cl2:R2-Al-Cl1: three oxyhalogen vanadium=1:0.1～30:0.1～2.5.
5. the butyl rubber synthetic method of a kind of Narrow Molecular Weight Distribution according to claim 1, it is characterised in that: described major catalyst is additionally added a certain proportion of water, and it adds the mol ratio of water: major catalyst: water=0.1～10:1.
6. the butyl rubber synthetic method of a kind of Narrow Molecular Weight Distribution according to claim 1, it is characterised in that: described nitrosamines is any one or a few mixture in N-N-nitrosodimethylamine, nitroso-group methyl ethylamine, N-diethylnitrosamine, N-dipropyl nitrosamine, N-dibutyl nitrosamine, N-nitroso-piperidine, N-nitrosopyrolidine, N-nitrosomorpholine, N-methyl-N-nitroso aniline, N-ethyl-N-nitrosoaniline；Or, described benzopyrene is benzo (a) pyrene, benzo (b) pyrene, deuterated benzo (A) anthracene, benzo (b) fluoranthene, benzo (j) fluoranthene, benzo (k) fluoranthene, dibenzanthracene, bends (1,2-benzophenanthrene；Thick dinaphthyl) in any one or a few mixture.
7. the butyl rubber synthetic method of a kind of Narrow Molecular Weight Distribution according to claim 1, it is characterized in that: described carbon four to carbon ten saturated alkane be in the alkane of carbon four to carbon ten any component mixing, or by any component of corresponding monoolefine with arbitrary proportion mix after through be hydrogenated with saturated after obtain.
8. the butyl rubber synthetic method of a kind of Narrow Molecular Weight Distribution according to claim 1, it is characterised in that: described halogenated alkane is R-X, R is carbon one to carbon eight straight or branched alkyl, and X can be F, Cl, Br or I.
9. the butyl rubber synthetic method of a kind of Narrow Molecular Weight Distribution according to claim 1, it is characterised in that: described R1-Al-Cl2And R2-Al-Cl1R represent CH3-, CH3CH2-, CH3CH2CH2-, CH3CH2CH2CH2-and CH3CH2(CH3)CH2-in any one alkyl.
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| CN102453183A (en) * | 2010-10-14 | 2012-05-16 | 中国石油天然气股份有限公司 | Method for preparing isoolefine copolymer |
| CN102875715A (en) * | 2011-07-15 | 2013-01-16 | 中国石油天然气股份有限公司 | Solution method for synthesizing butyl rubber |
| CN102875716A (en) * | 2011-07-15 | 2013-01-16 | 中国石油天然气股份有限公司 | Solution method for synthesizing butyl rubber |
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| CN102453183A (en) * | 2010-10-14 | 2012-05-16 | 中国石油天然气股份有限公司 | Method for preparing isoolefine copolymer |
| CN102875715A (en) * | 2011-07-15 | 2013-01-16 | 中国石油天然气股份有限公司 | Solution method for synthesizing butyl rubber |
| CN102875716A (en) * | 2011-07-15 | 2013-01-16 | 中国石油天然气股份有限公司 | Solution method for synthesizing butyl rubber |
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