CN105085757A - Ethylene-alpha olefin-non-conjugated dialkene copolymer and preparation method thereof - Google Patents
Ethylene-alpha olefin-non-conjugated dialkene copolymer and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses an ethylene-alpha olefin-non-conjugated dialkene copolymer preparation method and an ethylene-alpha olefin-non-conjugated dialkene copolymer prepared through the preparation method. The preparation method comprises: (1) contacting non-conjugated dialkene or a dilution containing non-conjugated dialkene and a nanometer silica-alumina adsorbent to obtain a reaction material containing non-conjugated dialkene, wherein the impurity content in the reaction material is less than or equal to 5 ppm; and (2) in the presence of a polymerization catalyst, hydrogen gas and a solvent, carrying out a polymerization reaction of the reaction material obtained in the step (1), ethylene and alpha olefin. With the method of the present invention, the impurity content in the non-conjugated dialkene can be reduced, the conversion rate of the non-conjugated dialkene can e improved, the catalysis efficiency in the ethylene, alpha olefin and non-conjugated dialkene copolymerization reaction, and the gel content in the polymer solution can be reduced.
Description
Technical field
The present invention relates to a kind of ethylene-alpha-olefin-non-conjugated diene hydrocarbon copolymer and preparation method thereof, particularly, relate to a kind of ethylene-propylene-(5-ethylidene-2-norbornene) multipolymer and preparation method thereof.
Background technology
Terpolymer EP rubber (EPDM) normally by ethene, propylene and a small amount of non-conjugated diene monomers under ziegler-natta catalyzed system, the terpolymer prepared by solution or suspension polymerization copolymerization.In the structure of EPDM, ethylene-propylene monomer forms the saturated main chain of multipolymer, and this main chain is random rubber elastomer.In order to enable this rubber elastomer carry out sulfuration or crosslinked, this saturated main chain introducing non-conjugated diene hydrocarbon, EPDM being provided with and for the cross-linking set of sulfuration, elasticity and very strong heat-resisting, resistance to ozone, the cold-resistant and resistance to chemical attack ability of EPDM uniqueness can being given.Since EPDM realizes commercialization, its Application Areas is constantly expanded.
For the non-conjugated diene monomers in EPDM, once soundd out tens kinds of monomers, but commercial applications mainly contain dicyclopentadiene (DCPD) and ethylidene norbornene (being also called 5-ethylidene-2-norbornene, ENB).Wherein ENB is the non-conjugated diene that current EPDM first-selection uses, and its advantage is that vulcanization rate is fast, is the one that in all Third monomer, vulcanization rate is the fastest.Cross-linked rubber tensile strength obtained is thus high, and tension set is little.
Such as, but usually containing impurity in the non-conjugated diene monomers used in prior art, ethylidene norbornene chemical property is active, contacts at normal temperatures be easy to deterioration by oxidation occurs with air, generates oxide compound, superoxide, and during high temperature, reaction is more serious.Easily there is autohemagglutination in ethylidene norbornene itself simultaneously, generates dimerization and polymer.Therefore usually needing isolated air and cryopreservation when storing ethylidene norbornene, generally also needing to add phenolic inhibitor, as p-methyl phenol, tert-butyl catechol, Resorcinol etc.In addition, in the process of preparation ethylidene norbornene, the reaction product obtained is complicated, usually can contain the by products such as the dipolymer of unreacted monomer and monomer.
Non-conjugated diene hydrocarbon as ENB as important Third monomer in EPDM building-up process time, the quality standard that demand fulfillment is very strict, because the by product wherein contained, stopper and minor amount of water can reduce ziegler-natta catalyzed system catalytic efficiency, affect polyreaction, and easily cause polymerization process to produce gel, be unfavorable for the raising of ENB transformation efficiency, cause the cured properties obtained not good.
US20090312511A1 discloses the method for the mixture of a kind of polymerization containing ethene, at least one alpha-olefin and 5-vinyl-2-norbornylene, wherein 5-vinyl-2-norbornylene contains a small amount of impurity, can detect foreign matter content in ENB by UV absorption spectrum in the absorption intensity of 320nm and 343nm.Because the reactive behavior of oxygen is higher in ENB self and air, in actually operating, need starvation analysis.
Other method prior arts improving ENB transformation efficiency also disclose and can adopt staged reactor.US3629212 discloses a kind of polymerization process, and the method is implemented at least three continuous print reactors, and the method is carried out under Ziegler-Natta catalyst, promotor and sulfide exist.US4016342 discloses the continuous production method of the elastocopolymer of the alpha-olefin of ethene and C3-C10, wherein can have non-conjugated diene hydrocarbon, prepares in two tandem reactors.Product molecular weight distribution prepared by this method is wider, composition narrowly distributing.US4306041 discloses the preparation method of the elasticity terpolymer of ethene, alhpa olefin and non-conjugated diene hydrocarbon, adopts Ziegler-Natta catalyst to be polymerized in tandem reactor, then passes into the second reactor continuation polymerization to improve di-olefins rate.
CN1284051A discloses the method for murifying norbornene, and its crude product mixture comprises: light impurities, and its boiling point is lower than the boiling point of norbornylene; Middle heavy impurity, its boiling point is between norbornylene boiling point and ethyl norbornene boiling point; Heavy impurity, its boiling point is higher than the boiling point of ethyl norbornene; And ethyl norbornene is also included in described heavy impurity, it is characterized in that: the first time distillation of crude product mixture, completing in tailing column (C1), deviates from heavy impurity in part heavy impurity and part; Then its distillation of second time except the crude mixture after tail is completed in topping tower (C2), deviate from light impurities; The third time distillation of the mixture after topping, then completing in tailing column (C3), deviates from heavy and heavy impurity in remaining.This invention mainly passes through murifying norbornene by distillation.But the method processing speed is slow, treatment capacity is little, energy consumption is large, is difficult to meet needs in pilot scale or industrial production.
Also can adopt add can with the method for the material of impurity generation chemical reaction, but this method easily introduces new impurity, is unfavorable for ziegler-natta catalyzed polyreaction.
Can find out, prior art still can not reduce foreign matter content in non-conjugated diene hydrocarbon well, overcome in ethylene-alpha-olefin-non-conjugated diene hydrocarbon copolymer preparation process, the shortcoming that catalytic efficiency is low, non-conjugated diene hydrocarbon conversion rate is low, product gel content is high, therefore, the new method preparing ethylene-alpha-olefin-non-conjugated diene hydrocarbon copolymer is needed.
Summary of the invention
The object of the invention is, in order to overcome the shortcoming that above-mentioned prior art catalytic efficiency is low, non-conjugated diene hydrocarbon conversion rate is low, product gel content is high, to provide a kind of ethylene-alpha-olefin-non-conjugated diene hydrocarbon copolymer and preparation method thereof.
To achieve these goals, the invention provides the preparation method of a kind of ethylene-alpha-olefin-non-conjugated diene hydrocarbon copolymer, the method comprises: non-conjugated diene hydrocarbon or the diluent containing non-conjugated diene hydrocarbon contact with nano silicon-alumina adsorbant by (1), obtain the reaction material containing non-conjugated diene hydrocarbon, the foreign matter content in described reaction material is below 5ppm; (2) under polymerizing catalyst, hydrogen and solvent exist, step (1) is contacted the reaction material obtained and ethene, alhpa olefin carry out polyreaction.
Present invention also offers the ethylene-alpha-olefin-non-conjugated diene hydrocarbon copolymer obtained by preparation method provided by the invention, wherein, in this ethylene-alpha-olefin-non-conjugated diene hydrocarbon copolymer, with the gross weight of this multipolymer for benchmark, the content of ethylene unit unit is 25-85 % by weight, the content of alhpa olefin structural unit is 10-70 % by weight, and the content of non-conjugated diene hydrocarbon structure unit is 1-20 % by weight; The content of optimal ethylene structural unit is 40-75 % by weight, and the content of alhpa olefin structural unit is 20-45 % by weight, and the content of non-conjugated diene hydrocarbon structure unit is 1-10 % by weight.
The preparation method of ethylene-alpha-olefin provided by the invention-non-conjugated diene hydrocarbon copolymer, the foreign matter content in the non-conjugated diene hydrocarbon reaction material participating in polyreaction can be reduced, improve the transformation efficiency of non-conjugated diene hydrocarbon, improve the catalytic efficiency in ethene, alhpa olefin and the copolyreaction of non-conjugated diene hydrocarbon, reduce the gel content in polymers soln.
The present invention adopts nano silicon-alumina adsorbant, can realize the operate continuously of the impurity adsorbed in non-conjugated diene hydrocarbon, does not produce and needs waste liquid to be processed and solid waste, can meet economy and environmental requirement.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides the preparation method of a kind of ethylene-alpha-olefin-non-conjugated diene hydrocarbon copolymer, the method comprises: non-conjugated diene hydrocarbon or the diluent containing non-conjugated diene hydrocarbon contact with nano silicon-alumina adsorbant by (1), obtain the reaction material containing non-conjugated diene hydrocarbon, the foreign matter content in described reaction material is below 5ppm; (2) under polymerizing catalyst, hydrogen and solvent exist, the reaction material obtain step (1) and ethene, alhpa olefin carry out polyreaction.
In method provided by the invention, by using nano silicon-alumina adsorbant, the impurity in adsorbing and removing non-conjugated diene hydrocarbon.Under preferable case, with the gross weight of described nano silicon-alumina adsorbant for benchmark, described nano silicon-alumina adsorbant contains the silicon-dioxide of 5-15 % by weight, the aluminum oxide of 85-95 % by weight; The aperture of described nano silicon-alumina adsorbant is 2-8nm, and the inner ratio surface area of described nano silicon-alumina adsorbant accounts for the 75-90% of total specific surface area of described nano silicon-alumina adsorbant.
According to the present invention, under preferable case, described nano silicon-alumina adsorbant can be prepared by the following method: (a) is dry by activated alumina; B silicate, mineral acid and tensio-active agent are mixed to get nanosilica solution by (), the pH value of this solution is 7-9; C () in a heated condition, the activated alumina that step (a) is dry mixes with nanosilica solution prepared by step (b).
According to the present invention, under preferable case, the median size of described activated alumina is 3-5mm, and specific surface area is 280-360m
2/ g.Described particle diameter can be recorded by opticmicroscope.Specific surface area can pass through low-temperature physics loading capacity method method, adopt U.S. Micromeritics company PRISTAR-3000 type Determination of Specific Surface Area instrument, take high pure nitrogen as adsorbate, carry out the adsorptive capacity of working sample according to pressure balanced change, by BET Equation for Calculating specific surface area.The condition of described drying can be conventional condition of carrying out drying in this area, and such as temperature can be 150-300 DEG C, and the time can be 3-6 hour.
According to the present invention, in the preparation method of described nano silicon-alumina adsorbant, step (b) may be used for preparing nanosilica solution, under preferable case, described silicate can be selected from the silicate of basic metal and/or alkaline-earth metal, is preferably water glass; Described tensio-active agent can be nonionogenic tenside, and preferred described tensio-active agent is with general formula R-O-(CH
2cH
2o)
nthe fatty alcohol-polyoxyethylene ether that-H represents, wherein, R is the saturated of C12-C18 or undersaturated straight chain or branched alkyl, and n is 5-20, the fatty alcohol-polyoxyethylene ether (being commonly called as AEO) of preferred surfactant is R to be C12, n be 10-15; Described mineral acid is selected from least one in hydrochloric acid, sulfuric acid and nitric acid, is preferably hydrochloric acid.
In the present invention, in the preparation method of described nano silicon-alumina adsorbant, the median size of the nano silicon in nanosilica solution prepared by step (b) is recorded by Japanese JEOL company 6301F type field emission scanning electron microscope, test condition comprises: test voltage 20KV, operating distance 9mm, magnification 100,000 times.
According to the present invention, in the preparation method of described nano silicon-alumina adsorbant, under preferable case, the temperature of the described heating of step (c) is 100-140 DEG C.
In the present invention, after the preparation method of described nano silicon-alumina adsorbant can also be included in and mix described in step (c), the throw out be mixed to get is carried out centrifugal, washing, drying treatment, obtain nano silicon-alumina adsorbant.The sorbent material obtained adopts the field emission scanning electron microscope of Japanese JEOL company 6301F model at test voltage 20KV through scanning electron microscope method, and operating distance 9mm measures pore structure under magnification 100,000 times of conditions, can have the mean pore size of 2-8nm; U.S. Micromeritics company PRISTAR-3000 type Determination of Specific Surface Area instrument is adopted through BET nitrogen adsorption methods, take high pure nitrogen as adsorbate, the adsorptive capacity of working sample is carried out according to pressure balanced change, measure the inner ratio surface area of sorbent material and total specific surface area by BET equation, calculate the 75-90% that inner ratio surface area accounts for total specific surface area.
In aforesaid method provided by the invention, the content containing the impurity in the reaction material of non-conjugated diene hydrocarbon obtained through step (1) process can adopt ultraviolet-visible spectrophotometry, is that 320nm and 343nm place absorption intensity is determined by measuring wavelength.Also can by adopting gas chromatography determination containing the foreign matter content in the reaction material of non-conjugated diene hydrocarbon, preferably adopt vapor-phase chromatography, the method comprises the Ov-1 fused-silica capillary column that length is 30m, and internal diameter is 0.32nm, and thickness of liquid film is 0.25 μm.Also the chromatographic column of equal separating effect can be reached for other.Chromatographic condition: injector temperature is 250-290 DEG C; Detector temperature is 250-290 DEG C; Column temperature is 100-200 DEG C; Column flow rate is 1-2ml/min DEG C.External standard method is adopted to calculate the foreign matter content measured.
In the preparation method of ethylene-alpha-olefin provided by the invention-non-conjugated diene hydrocarbon copolymer, performing step (1), directly can contact non-conjugated diene hydrocarbon with nano silicon-alumina adsorbant, such as, contact with intermittent mode; Also non-conjugated diene hydrocarbon first can be carried out dilution process with diluting solvent, reduce the concentration of non-conjugated diene hydrocarbon, the diluent obtained can be in comparatively low viscosity scope, the mass transfer of diluent in the duct of this sorbent material is conducive to when contacting with nano silicon-alumina adsorbant, increase adsorption rate, such as, contact in a continuous manner.Under preferable case, the temperature of step (1) described contact is 0-30 DEG C, and the concentration of non-conjugated diene hydrocarbon described in described diluent is 20-80 volume %; The temperature of preferred described contact is 15-25 DEG C, and the concentration of non-conjugated diene hydrocarbon described in described diluent is 30-60 volume %.Under the concentration of above-mentioned diluent, the non-conjugated diene hydrocarbon in described diluent can have better adsorption effect, and the process of sorbent material regenerating easily.Described diluting solvent can be non-polar hydrocarbon solvent, such as can be selected from least one in benzene, toluene, ethylbenzene, dimethylbenzene, Skellysolve A, normal hexane, normal heptane, octane and hexanaphthene, preferably can be selected from least one in normal hexane, octane and normal heptane, more preferably described diluting solvent is normal hexane.
According to the present invention, described in step (1), the mode of contact can be intermittent mode, also can be continuous mode.When the mode of described contact is intermittent mode, non-conjugated diene hydrocarbon described in every ml uses the described nano silicon-oxygenant sorbent material of 0.2-1g.Described continuous mode can be piled up by nano silicon-alumina adsorbant to form nano silicon-alumina adsorption post, making diluent containing non-conjugated diene hydrocarbon by nano silicon-alumina adsorbant post, can be continuously by this adsorption column by diluent.Under preferable case, the mode of step (1) described contact is for making described diluent by nano silicon-alumina adsorbant post, and the volume space velocity of described diluent is 0.5-10h
-1, the volume space velocity of preferred described diluent is 1-5h
-1.Under this contact conditions, the diluent that can realize containing non-conjugated diene hydrocarbon carries out continuous adsorption, is conducive to realizing industrialization operate continuously.
According to the present invention, under preferable case, described non-conjugated diene hydrocarbon is 5-methyl-2,5-norbornylene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 1,4-hexadiene, 2-methyl isophthalic acid, at least one in 4-hexadiene, 1,6-octadiene and dicyclopentadiene; Preferred described non-conjugated diene hydrocarbon is 5-ethylidene-2-norbornene.
In the preparation method of ethylene-alpha-olefin provided by the invention-non-conjugated diene hydrocarbon copolymer, step (2) can realize the copolymerization of ethylene-alpha-olefin-non-conjugated diene hydrocarbon, wherein, under preferable case, described alhpa olefin is the alhpa olefin of C3-C12; Preferred alhpa olefin is the alhpa olefin of C3-C8, such as propylene, 1-butylene, 1-hexene or 1-octene; More preferably alhpa olefin is propylene.
According to the present invention, described polymerizing catalyst can be the various catalyzer that can be used for ziegler-natta catalyzed system of the prior art.Under preferable case, described polymerizing catalyst contains vanadium compound and organo-aluminium compound, described organo-aluminium compound is chlorinated organo-aluminium, can be selected from least one in a chlorine diethyl aluminum chloride, a Chlorodimethyl aluminium, ethyl aluminum dichloride, a chloro-di-isobutyl aluminum, ethyl aluminium sesquichloride and methylaluminum sesquichloride, preferred described organo-aluminium compound is at least one in aluminium diethyl monochloride, ethyl aluminum dichloride and ethyl aluminium sesquichloride.Described organo-aluminium compound is promotor.
According to the present invention, vanadium compound in described polymerizing catalyst can be various can the vanadium compound of polyreaction of completing steps (2), such as at " macromole " (D.L.Christman, G.I.Kein, Macromolecules, 1968,1,358) disclosed in various vanadium compound catalyzer.Under preferable case, described vanadium compound is at least one in vanadium trichloride, vanadium tetrachloride, vanadium oxytrichloride, vanadium triacetylacetonate, diacetyl acetone vanadyl, triethoxy vanadyl and two chloroethoxy vanadyl, and preferred described vanadium compound is vanadium oxytrichloride.Described vanadium compound is Primary Catalysts.
According to the present invention, although organo-aluminium compound and vanadium compound can realize polyreaction with various mol ratio in prior art, but under preferable case, in the described organo-aluminium compound of aluminium element with in the mol ratio of the described vanadium compound of v element for 1-1000:1, be preferably 2-300:1, be more preferably 5-80:1.
In the present invention, described organo-aluminium compound and vanadium compound can carry out polyreaction by being dissolved in adding after in aliphatics or aromatic hydrocarbon solvent again.This aliphatics or aromatic hydrocarbon solvent are inertia to described polymerizing catalyst usually, can preferably and the solvent phase of polyreaction with.Organo-aluminium compound and vanadium compound can be distinguished or the form of both mixtures is added.It can be organo-aluminium compound and vanadium compound are added with order successively that organo-aluminium compound and vanadium compound add respectively, also can be that organo-aluminium compound and vanadium compound add simultaneously.
According to the present invention, described polyreaction can be solution polymerization, can adopt the mode of batchwise polymerization, and the mode of successive polymerization also can be adopted to realize.Under preferable case, described in step (2), the condition of polyreaction comprises: based on the volume of described solvent, in the content of the vanadium compound of v element for 0.01-0.5mmol/L, is preferably 0.1-0.3mmol/L; The mol ratio of alhpa olefin and ethene is 1-5:1, is preferably 2-4:1; The mol ratio of non-conjugated diene hydrocarbon and ethene is 0.015-0.05:1.
According to the present invention, the consumption of described solvent can be the conventional amount used of carrying out solution polymerization, meets the requirement of polyreaction.Under preferable case, described in step (2), the condition of polyreaction also comprises: based on the gross weight of described solvent, and in ethene, alhpa olefin and described reaction material, the total concn of non-conjugated diene hydrocarbon is 5-30 % by weight, is preferably 8-10 % by weight.
Solvent described in the present invention can have chemical reaction effect for the polymkeric substance do not obtained with each component and polyreaction that participate in polyreaction.Described solvent can be solvent known in those skilled in the art.For the purpose of the present invention, described solvent can be non-polar hydrocarbon solvent, not restricted citing can be at least one in benzene, toluene, ethylbenzene, dimethylbenzene, Skellysolve A, normal hexane, normal heptane, octane and hexanaphthene, preferably can be selected from least one in normal hexane, octane and normal heptane, more preferably described solvent is normal hexane.
According to the present invention, described polyreaction can adopt hydrogen to control the molecular weight of multipolymer as molecular weight regulator, can adopt the hydrogen usage of this area routine.Under preferable case, described in step (2), the condition of polyreaction also comprises: based on the cumulative volume of non-conjugated diene hydrocarbon in ethene, alhpa olefin and described reaction material, and the consumption of described hydrogen is 0.01-10 volume %, is preferably 0.02-5 volume %.
According to the present invention, under preferable case, the temperature of polyreaction described in step (2) is-40 DEG C to 80 DEG C, and the temperature of preferred described polyreaction is 10-50 DEG C; The pressure of described polyreaction is 0.1-5MPa, and the pressure of preferred described polyreaction is 0.1-2MPa.
In the present invention, step (2) obtains in the solution of multipolymer under the above-mentioned conditions of polymerization, and the concentration of ethylene-alpha-olefin copolymer can be 5-15 % by weight, can be preferably 6-9 % by weight.
Present invention also offers the ethylene-alpha-olefin-non-conjugated diene hydrocarbon copolymer obtained by preparation method provided by the invention, wherein, in this ethylene-alpha-olefin-non-conjugated diene hydrocarbon copolymer, with the gross weight of this multipolymer for benchmark, the content of ethylene unit unit is 25-85 % by weight, the content of alhpa olefin structural unit is 10-70 % by weight, and the content of non-conjugated diene hydrocarbon structure unit is 1-20 % by weight; The content of optimal ethylene structural unit is 40-75 % by weight, and the content of alhpa olefin structural unit is 20-45 % by weight, and the content of non-conjugated diene hydrocarbon structure unit is 1-10 % by weight.
Below will be described the present invention by embodiment.
In following examples, non-conjugated diene hydrocarbon and the foreign matter content contained in the reaction material of non-conjugated diene hydrocarbon adopt Agilent company 6890 type gas chromatograph for determination.
The transformation efficiency of non-conjugated diene hydrocarbon adopts following methods analyst:
Get multipolymer glue sample, by its in vacuum drying oven with 50 DEG C of dryings, proton nmr spectra (Bruker company DRX400) is adopted by dry sample to measure the hydrocarbon content of the non-conjugated diene wherein combined, again divided by adding the non-conjugated diene hydrocarbon feed amount of carrying out polyreaction, obtain the transformation efficiency of non-conjugated diene hydrocarbon.
Gel content adopts following methods analyst:
Get multipolymer glue sample, by its in vacuum drying oven with 50 DEG C of dryings, weigh and count W
0.Then make solvent with perhydronaphthalene and shake dissolving at 135 DEG C.The lysate stainless (steel) wire of aperture (200 order) filters, and by the undissolved polymkeric substance that remains on stainless (steel) wire in vacuum drying oven at 100 DEG C dry 4 hours, weighs and counts W
1.Calculate W
1/ W
0× 100%, draw gel content.
Catalytic efficiency is calculated as follows:
Be polymerized in multipolymer dry glue weight (the g)/unit time obtained in add-on (g) × 100% of the vanadium compound of v element in catalytic efficiency=unit time.
In ethylene-alpha-olefin-non-conjugated diene hydrocarbon copolymer, the content of ethylene unit unit, alhpa olefin structural unit and non-conjugated diene hydrocarbon structure unit is by magnetic nuclear resonance method, adopts Bruker company DRX400 type nmr determination to obtain.
The pore structure of nano silicon-alumina adsorbant records mean pore size (test condition comprises: test voltage 20KV, operating distance 9mm, magnification 100,000 times) by Japanese JEOL company 6301F type field emission scanning electron microscope; Measure the inner ratio surface area of nano silicon-alumina adsorbant and total specific surface area by BET nitrogen adsorption methods (U.S. Micromeritics company PRISTAR-3000 type Determination of Specific Surface Area instrument), determine that inner ratio surface area accounts for the percentage ratio of total specific surface area.The composition of nano silicon-alumina adsorbant measures (test voltage 20KV, operating distance 9mm) by Japanese linkisis-300 type energy spectrometer.
Preparation example
This preparation example illustrates the preparation method of nano silicon-alumina adsorbant of the present invention.
(1) activated alumina that the BASF AG of getting 10g produces, median size is 4mm after measured, and specific surface area is 320m
2/ g.By this activated alumina at 200 DEG C dry 5 hours, be DB-1 for subsequent use.
(2) Na that 150ml concentration is 10% is got
2siO
2solution, wherein drip concentration be 1 % by weight hydrochloric acid soln and concentration be 5 % by weight fatty alcohol-polyoxyethylene ether AEO (Hai'an, Jiangsu petroleum chemical plant produce, trade mark AEO-3), to mix and the pH controlling this mixture is 8, obtain nanosilica solution.The median size being measured nano silicon in this solution by scanning electron microscope is 5nm.
(3) at Heating temperature is 120 DEG C, activated alumina DB-1 in (1) is added (2) obtain fully being uniformly mixed in nanosilica solution, and centrifugal for the throw out be mixed to get, washing, dry heat process are obtained nano silicon-alumina adsorbant, be sorbent material S-1.
The mean pore size being measured sorbent material S-1 by scanning electron microscope is 3nm, adopts BET nitrogen adsorption methods to measure the inner ratio surface area of sorbent material S-1 and total specific surface area, and calculating inner ratio surface area, to account for total specific surface area be 80%.
The content consisting of silicon-dioxide measuring sorbent material S-1 is 10 % by weight, and the content of aluminum oxide is 90 % by weight.
Absorption test case 1
This absorption test case illustrates the method that non-conjugated diene hydrocarbon provided by the invention contacts with nano silicon-alumina adsorbant provided by the invention.
Measure with the effect of intermittent mode absorption.
At temperature is 25 DEG C, the sorbent material S-1 of 50g is added in the 5-ethylidene-2-norbornene of 100ml and contacts, and under adopting gas chromatography determination different duration of contact, the content of impurity in 5-ethylidene-2-norbornene.The results are shown in Table 1.
Contrast absorption test case 1
According to the method for absorption test case 1, unlike, with " DB-1 of 50g ", substitute " the sorbent material S-1 of 50g ".
Under the different duration of contact measured, in 5-ethylidene-2-norbornene, the content results of impurity is in table 1.
Table 1
As can be seen from the data results of table 1, only adopt activated alumina DB-1 process 5-ethylidene-2-norbornene (ENB), within 4 days, rear impurity content is down to 40-50ppm, no longer continues to reduce; Adopt nano silicon-alumina adsorbant S-1 process ENB, after 4 days, foreign matter content is down to 24ppm, continues process and can not detect impurity to 7 days.Illustrate that nano silicon-alumina adsorbant can more effectively realize removing the impurity in ENB.
Absorption test case 2
This absorption test case illustrates the method that non-conjugated diene hydrocarbon provided by the invention contacts with nano silicon-alumina adsorbant provided by the invention.
Measure the effect contacted in a continuous manner.
The sorbent material S-1 of 100g is loaded adsorption column, and form the adsorption column of nano silicon-alumina adsorbant S-1, volume is about 0.2 liter.
By 5-ethylidene-2-norbornene and normal hexane solvent cut, the concentration obtaining 5-ethylidene-2-norbornene is the diluent of 20 % by weight.
At temperature is 25 DEG C, be 1h by the volume space velocity of diluent
-1, diluent is contacted with sorbent material S-1, and measures contact after 1 hour from the foreign matter content of liquid that adsorption column flows out, the results are shown in Table 2.
Absorption test case 3-5
According to the method for absorption test case 2, unlike, use " concentration of 5-ethylidene-2-norbornene is the diluent of 30 % by weight ", " concentration of 5-ethylidene-2-norbornene is the diluent of 40 % by weight " and " concentration of 5-ethylidene-2-norbornene is the diluent of 50 % by weight " respectively, substitute " concentration of 5-ethylidene-2-norbornene is the diluent of 20 % by weight ".Carry out the absorption of diluent.
Measurement result is in table 2.
Contrast absorption test case 2-5
According to the method for absorption test case 2-5, unlike, with " DB-1 of 100g ", substitute " the sorbent material S-1 of 100g ".Carry out the absorption of diluent.
Measurement result is in table 2.
Table 2
As can be seen from Table 2, employing nano silicon-alumina adsorbant S-1 carries out the adsorption effect that continuous adsorption successful is better than adopting aluminum oxide.Compared with the result of table 1, and adopt the continuous adsorption better effects if of diluent.
Embodiment 1
The present embodiment illustrates the preparation method of ethylene-alpha-olefin of the present invention-non-conjugated diene hydrocarbon copolymer.
(1) adsorbing contaminant.According to the method for absorption test case 2, obtain the refining 5-ethylidene-2-norbornene reaction material A that foreign matter content is 3ppm.
(2) intermittent polyreaction.The 5-ethylidene-2-norbornene reaction material A of 200mL normal hexane solvent and 10ml is added in 0.5L polymeric kettle, add ethene, propylene, the hydrogen gas mixture of 1:1.5:0.4 composition by volume continuously, mixing 20 minutes at temperature 20 DEG C and pressure 0.5MPa.Add vanadium oxytrichloride 0.04mmol, then add sesquialter ethylmercury chloride aluminium 0.8mmol.Control temperature of reaction in polymeric kettle constant in 20 DEG C, reaction pressure is 0.5MPa, and in polymeric kettle, adds mixed gas with 2 marks liter/min.Polyreaction, after 30 minutes, stops conveying mixed gas and stirring, removes ethene and propylene.Add ethanol 10ml and stop polyreaction, then add multipolymer weight (by the calculating that feeds intake) 0.1 % by weight the hexane solution of anti-aging agent Irganox1520.The polymers soln obtained is obtained polymerisate EPDM-1 through cohesion, drying.
Experimental result is in table 3.
Embodiment 2
The present embodiment illustrates the preparation method of ethylene-alpha-olefin of the present invention-non-conjugated diene hydrocarbon copolymer.
(1) adsorbing contaminant.According to the method for absorption test case 2, obtain the refining 5-ethylidene-2-norbornene reaction material A that foreign matter content is 3ppm.
(2) successive polymerization reaction.By passing into normal hexane solvent (6kg/h), ethene (0.2kg/h), propylene (0.35kg/h), 5-ethylidene-2-norbornene reaction material A (0.02kg/h) and hydrogen (0.001g/h) bottom 5L polymeric kettle in polymeric kettle continuously.Vanadium oxytrichloride solution and sesquialter ethylmercury chloride aluminum solutions are added polymeric kettle with 0.5L/h speed respectively simultaneously, and wherein vanadium oxytrichloride is 0.6g/h, and sesquialter ethylmercury chloride aluminium is 2.5g/h, starts polyreaction.Controlling temperature of reaction is 30 DEG C, and pressure is 0.5MPa.From the upper outlet of polymeric kettle.
The polymers soln of discharging is carried out termination reaction, cohesion, drying, obtains polymerisate EPDM-2.
Experimental result is in table 3.
Comparative example 1
(1) according to the method for embodiment 1, unlike, according to the method for contrast absorption test case 2, obtain the refining 5-ethylidene-2-norbornene reaction material B that foreign matter content is 20ppm.
(2) according to the method for embodiment 1, unlike, substitute " the 5-ethylidene-2-norbornene reaction material A of 10ml " with " the 5-ethylidene-2-norbornene reaction material B of 10ml ".
Experimental result is in table 3.
Comparative example 2
According to the method for embodiment 1, unlike, there is no step (1).
Substitute " the 5-ethylidene-2-norbornene reaction material A of 10ml " with " 10ml does not have the 5-ethylidene-2-norbornene of adsorbing contaminant ".
Experimental result is in table 3.
Comparative example 3
(1) according to the method for embodiment 2, unlike, according to the method for contrast absorption test case 2, obtain the refining 5-ethylidene-2-norbornene reaction material B that foreign matter content is 20ppm.
(2) according to the method for embodiment 2, unlike, substitute " 5-ethylidene-2-norbornene reaction material A " with " 5-ethylidene-2-norbornene reaction material B ".
Experimental result is in table 3.
Comparative example 4
According to the method for embodiment 2, unlike, there is no step (1).
Substitute " 5-ethylidene-2-norbornene reaction material A " with " there is no the 5-ethylidene-2-norbornene of adsorbing contaminant ".
Experimental result is in table 3.
As can be seen from the data results of table 3, the preparation method of ethylene-alpha-olefin provided by the invention-non-conjugated diene hydrocarbon copolymer, can reduce containing the foreign matter content in the reaction material of non-conjugated diene hydrocarbon, improve the transformation efficiency of non-conjugated diene hydrocarbon, improve the catalytic efficiency in ethene, alhpa olefin and the copolyreaction of non-conjugated diene hydrocarbon, reduce the gel content in polymers soln.
Embodiment 3
Polymerisate EPDM-1 and EPDM-2 embodiment 1 and 2 obtained carries out sulfuration respectively and obtains cross-linked rubber ER-1 and ER-2, and sulfurizing formula is in table 4.Cure conditions comprises: curing temperature 160 DEG C, pressure 15MPa, curing time 10-30min.Cured properties test result is in table 5.
Table 4
| Formula | Content (weight part) | Formula | Content (weight part) |
| EPDM-1 | 100 | EPDM-2 | 100 |
| Zinc oxide | 5 | Zinc oxide | 5 |
| Stearic acid | 1.0 | Stearic acid | 1.0 |
| Carbon black | 110 | Carbon black | 110 |
| Calcium carbonate | 55 | Calcium carbonate | 55 |
| Paraffin oil | 60 | Paraffin oil | 60 |
| Polyoxyethylene glycol | 2 | Polyoxyethylene glycol | 2 |
| Accelerant B Z | 1.8 | Accelerant B Z | 1.8 |
| Altax | 0.8 | Altax | 0.8 |
| Vulcanization accelerator TMTD | 1 | Vulcanization accelerator TMTD | 1 |
| Sulfur | 1.5 | Sulfur | 1.5 |
Table 5
| Performance | ER-1 | ER-2 |
| Mooney 1+4,125 DEG C | 80 | 82 |
| Tensile strength/MPa | 10.6 | 10.8 |
| 100% tensile modulus/MPa | 4.9 | 5.1 |
| Tensile yield/% | 350 | 380 |
| Compression set/% | 16 | 13 |
| Hardness (Shao Er A) | 66 | 66 |
As can be seen from Table 5, adopt the multipolymer prepared by the present invention, strength and extension property is good, and compression set is low, extrudes smooth surface smooth, is especially applicable to extruding sealing article.
Claims (12)
1. a preparation method for ethylene-alpha-olefin-non-conjugated diene hydrocarbon copolymer, the method comprises:
(1) non-conjugated diene hydrocarbon or the diluent containing non-conjugated diene hydrocarbon are contacted with nano silicon-alumina adsorbant, obtain the reaction material containing non-conjugated diene hydrocarbon, the foreign matter content in described reaction material is below 5ppm;
(2) under polymerizing catalyst, hydrogen and solvent exist, the reaction material obtain step (1) and ethene, alhpa olefin carry out polyreaction.
2. preparation method according to claim 1, wherein, with the gross weight of described nano silicon-alumina adsorbant for benchmark, described nano silicon-alumina adsorbant contains the silicon-dioxide of 5-15 % by weight, the aluminum oxide of 85-95 % by weight; The aperture of described nano silicon-alumina adsorbant is 2-8nm, and the inner ratio surface area of described nano silicon-alumina adsorbant accounts for the 75-90% of total specific surface area of described nano silicon-alumina adsorbant.
3. preparation method according to claim 1 and 2, wherein, described nano silicon-alumina adsorbant is prepared by the following method: (a) is dry by activated alumina; B silicate, mineral acid and tensio-active agent are mixed to get nanosilica solution by (), the pH value of this solution is 7-9; C () in a heated condition, the activated alumina that step (a) is dry mixes with nanosilica solution prepared by step (b).
4. preparation method according to claim 3, wherein, the particle diameter of described activated alumina is 3-5mm, and specific surface area is 280-360m
2/ g; Described silicate is selected from the silicate of basic metal and/or alkaline-earth metal, is preferably water glass; Described tensio-active agent is with general formula R-O-(CH
2cH
2o)
nthe fatty alcohol-polyoxyethylene ether that-H represents, wherein, R is the saturated of C12-C18 or undersaturated straight chain or branched alkyl, and n is 5-20; Described mineral acid is selected from least one in hydrochloric acid, sulfuric acid and nitric acid.
5. preparation method according to claim 3, wherein, the temperature of the described heating of step (c) is 100-140 DEG C.
6. preparation method according to claim 1, wherein, the temperature of step (1) described contact is 0-30 DEG C, and the concentration of non-conjugated diene hydrocarbon described in described diluent is 20-80 volume %; The temperature of preferred described contact is 15-25 DEG C, and the concentration of non-conjugated diene hydrocarbon described in described diluent is 30-60 volume %.
7. the preparation method according to claim 1 or 6, wherein, the mode of step (1) described contact is for making described diluent by nano silicon-alumina adsorbant post, and the volume space velocity of described diluent is 0.5-10h
-1, the volume space velocity of preferred described diluent is 1-5h
-1.
8. the preparation method according to claim 1 or 6, wherein, described non-conjugated diene hydrocarbon is 5-methyl-2,5-norbornylene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 1,4-hexadiene, 2-methyl isophthalic acid, at least one in 4-hexadiene, 1,6-octadiene and dicyclopentadiene; Preferred described non-conjugated diene hydrocarbon is 5-ethylidene-2-norbornene.
9. preparation method according to claim 1, wherein, described alhpa olefin is the alhpa olefin of C3-C12; Preferred alhpa olefin is the alhpa olefin of C3-C8.
10. preparation method according to claim 1, wherein, described polymerizing catalyst contains vanadium compound and organo-aluminium compound, described vanadium compound is at least one in vanadium trichloride, vanadium tetrachloride, vanadium oxytrichloride, vanadium triacetylacetonate, diacetyl acetone vanadyl, triethoxy vanadyl and two chloroethoxy vanadyl, and preferred described vanadium compound is vanadium oxytrichloride; Described organo-aluminium compound is at least one in a chlorine diethyl aluminum chloride, a Chlorodimethyl aluminium, ethyl aluminum dichloride, a chloro-di-isobutyl aluminum, ethyl aluminium sesquichloride and methylaluminum sesquichloride, and preferred described organo-aluminium compound is at least one in aluminium diethyl monochloride, ethyl aluminum dichloride and ethyl aluminium sesquichloride; In the described organo-aluminium compound of aluminium element with in the mol ratio of the described vanadium compound of v element for 2-300:1, be preferably 5-80:1.
11. preparation methods according to claim 1, wherein, described in step (2), the condition of polyreaction comprises: based on the volume of described solvent, in the content of the described vanadium compound of v element for 0.01-0.5mmol/L, is preferably 0.1-0.3mmol/L; Based on the gross weight of described solvent, in ethene, alhpa olefin and described reaction material, the total concn of non-conjugated diene hydrocarbon is 5-30 % by weight, is preferably 8-10 % by weight; The mol ratio of alhpa olefin and ethene is 1-5:1, is preferably 2-4:1; In described reaction material, the mol ratio of non-conjugated diene hydrocarbon and ethene is 0.015-0.05:1; Based on the cumulative volume of non-conjugated diene hydrocarbon in ethene, alhpa olefin and described reaction material, the consumption of described hydrogen is 0.01-10 volume %, is preferably 0.02-5 volume %; The temperature of polyreaction is-40 DEG C to 80 DEG C, and the temperature of preferred polymeric reaction is 10-50 DEG C; The pressure of polyreaction is 0.1-5MPa, and the pressure of preferred polymeric reaction is 0.1-2MPa.
12. ethylene-alpha-olefin obtained by the preparation method in claim 1-11 described in any one-non-conjugated diene hydrocarbon copolymers, it is characterized in that, in this ethylene-alpha-olefin-non-conjugated diene hydrocarbon copolymer, with the gross weight of this multipolymer for benchmark, the content of ethylene unit unit is 25-85 % by weight, the content of alhpa olefin structural unit is 10-70 % by weight, and the content of non-conjugated diene hydrocarbon structure unit is 1-20 % by weight; The content of optimal ethylene structural unit is 40-75 % by weight, and the content of alhpa olefin structural unit is 20-45 % by weight, and the content of non-conjugated diene hydrocarbon structure unit is 1-10 % by weight.
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