CN103509141B - For composite carried catalyst that ultrahigh molecular weight polyethylene(UHMWPE) synthesizes and preparation method thereof - Google Patents
For composite carried catalyst that ultrahigh molecular weight polyethylene(UHMWPE) synthesizes and preparation method thereof Download PDFInfo
- Publication number
- CN103509141B CN103509141B CN201210213961.1A CN201210213961A CN103509141B CN 103509141 B CN103509141 B CN 103509141B CN 201210213961 A CN201210213961 A CN 201210213961A CN 103509141 B CN103509141 B CN 103509141B
- Authority
- CN
- China
- Prior art keywords
- molecular weight
- uhmwpe
- preparation
- 1molmg
- weight polyethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a kind of composite carried catalyst for ultrahigh molecular weight polyethylene(UHMWPE) synthesis and preparation method thereof, belong to catalyst preparation technical field.Described catalyzer by complex carrier, titanium compound, at least one Organic Alcohol and have at least the alkylaluminium cpd of a halogen substiuted react make, wherein: (1) complex carrier is the composition of silica gel, magnesium halide, and ratio is 0.3 ~ 10molSi/1molMg; (2) titanium compound is one or more in titanium tetrachloride, titanous chloride or tetrabutyl titanate, and consumption is 2 ~ 10molTi/1molMg; (3) Organic Alcohol is C
2~ C
20straight chain, side chain or cycloalkyl alcohol, consumption is 0.1 ~ 3molXOH/1molMg; (4) general formula of the alkylaluminium cpd of halogen substiuted is R
nalX
3-n, in formula, R is C
1~ C
10alkyl, X is halogen, and n is integer, 1≤n < 3, and consumption is 0.05 ~ 6molAl/1molMg.Catalyzer of the present invention is had a more substantial increase by ultrasonication activity, can effectively improve resin particle form, and has high reactivity and the stable feature of reaction kinetics.
Description
Technical field
The present invention relates to a kind of composite carried catalyst for ultrahigh molecular weight polyethylene(UHMWPE) synthesis and preparation method thereof, belong to catalyst preparation technical field.
Background technology
Ultrahigh molecular weight polyethylene(UHMWPE) (hereinafter referred to as UHMWPE) typically refers to viscosity-average molecular weight 1.5 × 10
6above linear structure polyethylene, because UHMWPE molecular weight is even millions of up to 1,000,000, thus has excellent stress cracking resistance, electrical insulating property, wear resistance etc.Be particularly suitable for the parts of need of production higher building rationality energy, as transmitting gear, joint prosthesis part etc.UHMWPE is compared with common high molecular polyolefine, and the excellences such as acoustic resistance, radiation resistance, thermotolerance, moistureproofness, tensile property, have caused the power of people's synthesizing super high molecular weight polyethylene thus.And research shows: in the synthesis of UHMWPE, there is the phenomenon of so-called " copying " with catalyzer in resin, thus, can be played the effect effectively controlling resin form and improve polymerization efficiency by the form controlling catalyzer.
Up to the present, the synthesis of UHMWPE has many technological processs, is generally only by inorganic magnesium compound, if magnesium halide, magnesium oxide or magnesium hydroxide are carrier loaded transistion metal compound (catalyzer that titanium or vanadium compound obtain).But these techniques have some problems, and such as product apparent density is low, and size-grade distribution is wide.
Mitsui company discloses a kind of preparation method of the catalyzer for vinyl polymerization and copolymerization in JP49-51378: the magnesium dichloride through grinding in mineral oil medium and ethanol synthesis generate alcohol adduct slurries, remove most of ethanol with aluminium diethyl monochloride generation esterification again, finally use TiCl
4carry out carrying Ti reaction, obtain Ti/MgCl
2the PZ catalyzer of carried catalyst and industrial widespread use.But find in the lab, the irregular platy shaped particle produced when carrier magnesium chloride exists former grinding in slurry reaction system, cause the solid catalyst particle form that obtains poor, thickness is uneven, and thus the form of UHMWPE is poor, and fine powder is many.
Hoechst Aktiengesellschaft in CN1097426A, CN1080933A, disclose a series of alkyl magnesium compound and halogenating agent, titanium compound, electron donor react the extra high-molecular polythene catalyst obtained, and is still with intermediate product MgCl in this catalyst series
2as carrier.The said firm refer to and other inorganicss can be utilized as carrier in extra high-molecular polythene catalyst disclosed in CN1116630A in addition, but the embodiment of having no, the main or MgCl generated with halogenating agent with alkyl magnesium compound
2as carrier, and and two or more complex carrier not mentioned.
Magnesium chloride load in silica gel (SiO
2), aluminum oxide (Al
2o
3), zinc chloride (ZnCl
2) on the higher inorganics of equal strength, making the catalyzer with complex carrier becomes one of current vinyl polymerization research direction.Wherein, CN1038593C is by MgCl
2dissolve and make solution in ethanol, then silica gel is dipped in wherein, evaporates unnecessary ethanol, make ethanol and magnesium chloride mol ratio in solids be 1.5-4.0:1, and then load active component titanium compound, obtain catalyzer.CN1050389A is by magnesium chloride and silicon-dioxide mixing, then adds appropriate alcohol, makes magnesium alkoxide mol ratio be 3-25:1, stirs lower fully reaction, then adds aluminum alkyls and electron donor, remove unnecessary alcohol and obtain catalyzer.Above two kinds of methods need to use a large amount of alcohol and carry out alcoholysis complexing in preparation process, reduce the polymerization efficiency of catalyzer to a certain extent, and the molecular weight of resin are not high.
CN1239520C provides a kind of and above-mentioned two kinds of equal diverse ways, only make activator with a small amount of alcohol, the magnesium chloride tetrahydrofuran (THF) adducts be carried on silica-gel carrier is activated, catalyzer is made again with wherein load active component titanium, application finds, use tetrahydrofuran (THF) can reduce the polymerization efficiency of catalyzer equally, and the molecular weight of resin is not high.
Invention applies ultrasonic technology, both can avoid using alcohol in a large number, also do not need to use generation magnesium chloride tetrahydrofuran (THF) adducts and carry out load, high polymerization efficiency can be ensured, and may be used for synthesizing UHMWPE.
Ultrasonic wave refers to that frequency is higher than produced the in media as well elastic wave of the object of 20kHz.The applicable field of ultrasonic wave is very extensive, and in chemical industry, hyperacoustic application also more and more comes into one's own, and thereby produces an emerging cross discipline--sonochemistry.Hyperacoustic chemokinesis, is mainly derived from its cavitation phenomenon.So-called ultrasonic cavitation refers to that be present in the micro-bubble in liquid phase vibrates, grows, collapses closed process under the effect of ultrasonic field, is acoustochemical energy derive.The focus of research has been become, the activity of the catalyzer that especially in catalyst preparation process, by ultrasonication, the specific surface area of catalyzer can be increased, active ingredient is disperseed better, thus improve in catalytic field sonochemistry.
CN1861650A discloses a kind of preparation method that can be used for the Ziegler-Natta catalyst of ethylene thick liquid polymerizing, and the method carries out ultrasonication by support-activated, active centre load two step, improves the Ti content of this catalyzer.CN1506384A discloses a kind of preparation method ultrasonic technology being used for polypropylene catalyst, and the method, by using hyperacoustic treatment technology in support of the catalyst reactivation process, improves polypropylene catalyst activity and polymer stacks density.Although above two kinds of methods apply ultrasonic technology, carrier is single carrier, there is the shortcoming that bulk density is low.
Summary of the invention
The object of the present invention is to provide that a kind of polymerization efficiency is high, reaction kinetics steadily, composite carried catalyst for ultrahigh molecular weight polyethylene(UHMWPE) synthesis that can improve polymer stacks density and preparation method thereof.
Of the present invention for ultrahigh molecular weight polyethylene(UHMWPE) synthesis composite carried catalyst, by complex carrier, titanium compound, at least one Organic Alcohol and have at least the alkylaluminium cpd of a halogen substiuted react make, wherein:
(1) complex carrier is the composition of silica gel, magnesium halide, and ratio is 0.3 ~ 10molSi/1molMg; Magnesium halide is one or more in magnesium chloride, methylmagnesium-chloride, methoxyl group magnesium chloride, oxyethyl group magnesium chloride or butoxy magnesium chloride;
(2) titanium compound is one or more in titanium tetrachloride, titanous chloride or tetrabutyl titanate, and consumption is 2 ~ 10molTi/1molMg;
(3) Organic Alcohol is C
2~ C
20straight chain, side chain or cycloalkyl alcohol, consumption is 0.1 ~ 3molXOH/1molMg;
(4) general formula of the alkylaluminium cpd of halogen substiuted is R
nalX
3-n, in formula, R is C
1~ C
10alkyl, X is halogen, and n is integer, 1≤n < 3, and consumption is 0.05 ~ 6molAl/1molMg.
The preferred magnesium chloride of described magnesium halide.
The preferred titanous chloride of described titanium compound or titanium tetrachloride.
The preferred C of described Organic Alcohol
2~ C
8alcohol, more preferably ethanol, n-propyl alcohol, propyl carbinol, isopropylcarbinol or isooctyl alcohol, most preferably propyl carbinol.Few and the better propyl carbinol of solute effect of preferable amount of the present invention.
One or more in the preferred aluminium diethyl monochloride of alkylaluminium cpd of described halogen substiuted, dichloro one aluminium triethyl or chlorination dipropyl aluminium, most preferably aluminium diethyl monochloride.
The preparation method of the described composite carried catalyst for ultrahigh molecular weight polyethylene(UHMWPE) synthesis, comprises the steps:
(1) under nitrogen protection, magnesium halide, silica gel are added in there-necked flask, adds inert solvent, there-necked flask is placed in the oil bath that temperature is 40 ~ 80 DEG C;
(2) add Organic Alcohol, react 0.1 ~ 1 hour at 20 ~ 120 DEG C, the material now in system is the composition of magnesium alkoxide compound silica gel, and the consumption of Organic Alcohol is 0.1 ~ 3molXOH/1molMg;
(3) in magnesium alkoxide compound, drip the alkylaluminium cpd of halogen substiuted, at 20 ~ 120 DEG C, react 0.5 ~ 6 hour, obtain the aaerosol solution of magnesium halide, the consumption of the alkylaluminium cpd of halogen substiuted is 0.05 ~ 6molAl/1molMg;
(4) obtained to step (3) solution carries out supersound process: ultrasonic frequency 20 ~ 80KHz, ultrasonic power 30 ~ 500W, and sonication treatment time is 0.5 ~ 30min;
(5) drip titanium compound in aaerosol solution after ultrasound exposure, at 20 ~ 120 DEG C, react 0.5 ~ 12 hour, the consumption of titanium compound is 2 ~ 10molTi/1molMg;
(6) reaction terminates, and leaves standstill 3 ~ 120 minutes, treats granules of catalyst sedimentation, layering, by supernatant liquid sucking-off, adds hydrocarbon solvent washing solid particulate, repetitive scrubbing like this 3 times; Obtained after dry at 70 ~ 150 DEG C.The preferred C of inert solvent described in step (1)
5~ C
15alkane, preferred C
5~ C
10alkane, further preferably normal hexane.Sonification power preferably 40 ~ 150W described in step (4), sonication treatment time preferably 1 ~ 15 minute, preferably 3 ~ 6 minutes further.
Composite carried catalyst of the present invention need with promotor together for polyreaction, may be used for synthesizing super high molecular weight polyvinyl resin, described promotor is alkylaluminium cpd: one or more of trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, aluminium diethyl monochloride or methylaluminoxane, preferred triethyl aluminum.
Complex carrier provided by the invention is magnesium halide silica gel, then using ultrasonic technology carries out complex carrier activation treatment, and the complex carrier of activation directly carries out active constituent loading.The present invention in extra high-molecular polythene catalyst complex carrier reactivation process by carrying out the ultrasonication of certain hour to complex carrier, through overload titanium step, highly active extra high-molecular polythene catalyst can be obtained, and the molecular weight of gained ultrahigh molecular weight polyethylene(UHMWPE), bulk density obtain effective raising, this polymerization catalyst reaction kinetics is steady simultaneously, is easy to polymerization technique and controls.
Using ultrasonic technology of the present invention, reduces and uses alcohol amount in support-activated process, and avoids application tetrahydrofuran (THF) polar solvent, can ensure to maintain higher polymerization efficiency, application finds, complex carrier can improve the bulk density of resin, and obtains the higher resin of molecular weight.The present invention adopts ultrasonic technology to effectively prevent a large amount of alcohol or needs other polar solvents to carry out the step of vehicle treated in complex carrier reactivation process, and catalyst activity is had a more substantial increase, and the polymerization efficiency in enforcement is up to 210000gPE(gCat)
-1h
-1.It should be noted that, ultrasonic treatment time is too short by limited to the action effect of carrier magnesium halide crystal, be difficult to the activity effectively improving catalyzer, but ultrasonic treatment time is long by the crystal habit of havoc carrier magnesium halide, this directly will affect morphology.
Ultrasonic unit of the present invention is high frequency electrical signal power frequency electric being transformed into more than 20KHz, is transported on transverter by high frequency cable, and transverter can convert electric energy to strong ultrasonic vibration.In catalyst formulation process, the high energy " cavitation effect " utilizing ultrasonic wave to produce, effectively Control granularity distribution can more be tending towards even, the specific surface area of further raising complex carrier, the raising of the active and polymericular weight of final promoting catalyst, bulk density, simultaneously obtained polymerization catalyst reaction kinetics is steady, is easy to polymerization reactor control.
Ultrasonic unit of the present invention can be that form of popping one's head in is inserted in glass reaction vessel and directly acted on reaction system, also can act on reaction system in reaction vessels outside by liquid phase.
The present invention's ultrahigh molecular weight polyethylene(UHMWPE) composite carried catalyst used is applicable to ethylene homo or ethene and alpha-olefin copolymer as Primary Catalysts.Need take aluminum alkyls as promotor during polymerization, suitable promotor be one or more of trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, aluminium diethyl monochloride or methylaluminoxane, preferred triethyl aluminum.Al/Ti mol ratio suitable during polymerization is 20 ~ 400, preferably 50 ~ 200.
Described polymerization can be slurry polymerization or gas phase mass polymerization.Slurry polymerization polymerizing condition is, ethylene partial pressure 0.1 ~ 1.2MPa, polymerization temperature 40 ~ 120 DEG C, and the medium that slurry polymerization adopts can be C
5~ C
15alkane, preferred C
5~ C
10one or more of alkane, polymerization reactor can be stirred-tank reactor or annular-pipe reactor.Gas phase polymerisation conditions is, ethylene partial pressure 0.6 ~ 2.4MPa, polymerization temperature 60 ~ 120 DEG C, and polymerization reactor can be gas-phase fluidized-bed or gas phase strong stirring still.
Beneficial effect of the present invention is as follows:
1. the present invention is in composite carried catalyst preparation process, a large amount of alcohol can be effectively prevent by ultrasonication or need other polar solvents to carry out the step of vehicle treated, catalyst activity is had a more substantial increase, under 0.6MPa, 60 DEG C of slurry polymerization conditions, with promotor triethyl aluminum with the use of, carry out ethene slurry polymerization 1 hour, the polymerization activity of catalyzer reaches as high as 210000gPE(gCat)
-1, resulting polymers molecular weight can reach 400 × 10
4above.
2. the present invention applies complex carrier in catalyst preparation process, can effectively improve resin particle form, and with the resin-phase ratio adopting single carried catalyst to prepare, its bulk density improves 30 ~ 50%.
3. catalyzer of the present invention has high reactivity and the stable feature of reaction kinetics, can simultaneously for one or more series polymerizations of gas phase, slurry polymerization, be easier to the control of polyreaction in the course of the polymerization process, in the polymerization process of 1 hour, catalyst activity has no obvious decay.
Accompanying drawing explanation
Fig. 1 is kinetics of polymerization reaction curve.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
In embodiment, the salient features test of catalyst performance and polymerisate adopts following methods to carry out:
(1) polymerization efficiency: the ratio of certain hour inner catalyst polymerization gained resin quality and Primary Catalysts quality, that is:
(2) molecular weight determination: undertaken by ASTM-D4020-2005.Make solvent with perhydronaphthalene, temperature 135 DEG C, adopt Ubbelohde viscometer to measure the polyethylene solution elution time, then calculate the intrinsic viscosity η of polymkeric substance.Calculation formula is as follows:
M
γ=5.37×10
4×[η]
1.37
M in formula
γfor the molecular weight of polymkeric substance.
(3) titanium content: adopt spectrophotometer method
1. titanium Specification Curve of Increasing: add respectively in the volumetric flask of 100ml the titanium standardized solution 10 of 100mg/L, 20,30,40,50,60ml, be diluted to scale with acid extract liquid; Use spectrophotometer under 420nm wavelength, record the absorbancy of each mark liquid; Take absorbancy as ordinate zou, titanium content is that X-coordinate draws out titanium typical curve.
2. titanium content measures: accurately take 0.200-0.300g catalyst sample W, be settled to 100ml with acid extract liquid; Get 0 respectively, sample, in 25ml volumetric flask, adds 3%H after 10ml extraction
2o
215ml, with distilled water diluting to scale; Point luminosity of blank sample and catalyzer sample is recorded in 30min; Titanium typical curve is found corresponding titanium content T.
Titanium content (wt%) in catalyzer is as shown in the formula calculating:
Embodiment 1
Catalyst preparing:
First by with heating system and the there-necked flask nitrogen replacement being furnished with the 250ml of whipping appts and reflux condensation mode system is no less than three times, then 60ml normal hexane is added, 1g Magnesium Chloride Anhydrous, 1g silica gel (through 600 DEG C of high-temperature activation 4h) stirs and heats up (temperature sets 65 DEG C); Add propyl carbinol 2ml subsequently, stir 0.3 hour; Slowly 1.1 × 10 are dripped after being cooled to room temperature
-2mol aluminium diethyl monochloride, refluxes 1 hour at 65 DEG C; Open ultrasonic unit, adjust frequency as 40KHz, rating of set is 50W, maintains 1min, closes after ultrasonic unit, still keeps reaction system isothermal reaction 0.5 hour at 70 DEG C; Slowly 4 × 10 are dripped again after being cooled to room temperature
-2mol titanium tetrachloride, isothermal reaction 2 hours at 70 DEG C; Finally stop stirring, upper strata mother liquor is separated out, with hexane repetitive scrubbing three times, after drying, obtain catalyzer.Described ultrasonic unit is that reaction vessels outside acts on reaction system by liquid phase.
Vinyl polymerization is tested
2L stainless steel polymeric kettle is vacuumized and is no less than three times with high pure nitrogen displacement, then in polymeric kettle, add 1.2L normal hexane, add 2.4 × 10
-3mol triethyl aluminum and the above-mentioned solid catalyst of 1.5mg, open after stirring and raise system temperature to 60 DEG C, being filled with ethene to polymeric kettle pressure is 0.6MPa, holding temperature, constant pressure carry out polyreaction, reaction to be polymerized was lowered the temperature after 1 hour, discharging is also dry, obtains polyvinyl resin with super-high molecular weight.The molecular weight of polymerization catalyst efficiency and resin is in table 1, and kinetics of polymerization reaction curve is shown in Fig. 1.
Embodiment 2
First by with heating system and the there-necked flask nitrogen replacement being furnished with the 250ml of whipping appts and reflux condensation mode system is no less than three times, then 60ml normal hexane is added, 1g Magnesium Chloride Anhydrous, 1g silica gel (through 200 DEG C of high-temperature activation 2h) stirs and heats up (temperature sets 65 DEG C); Add propyl carbinol 2ml subsequently, stir 0.3 hour; Slowly 1.4 × 10 are dripped after being cooled to room temperature
-2mol aluminium diethyl monochloride, refluxes 1 hour at 65 DEG C; Open ultrasonic unit, adjust frequency as 40KHz, rating of set is 50W, maintains 10min, closes after ultrasonic unit, still keeps reaction system isothermal reaction 0.5 hour at 70 DEG C; Slowly 6 × 10 are dripped again after being cooled to room temperature
-2mol titanium tetrachloride, isothermal reaction 12 hours at 70 DEG C; Finally stop stirring, upper strata mother liquor is separated out, with hexane repetitive scrubbing three times, after drying, obtain catalyzer.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1.
Embodiment 3
The preparation method of catalyst component with embodiment 1, but in Kaolinite Preparation of Catalyst process, changes hyperacoustic treatment time into 5min.Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1.
Embodiment 4
First by with heating system and the there-necked flask nitrogen replacement being furnished with the 250ml of whipping appts and reflux condensation mode system is no less than three times, then 60ml normal hexane is added, 1g Magnesium Chloride Anhydrous, 0.2g silica gel (through 200 DEG C of high-temperature activation 2h) stirs and heats up (temperature sets 65 DEG C); Add propyl carbinol 2ml subsequently, stir 0.3 hour; Slowly 2.0 × 10 are dripped after being cooled to room temperature
-2mol aluminium diethyl monochloride, refluxes 2 hours at 65 DEG C; Open ultrasonic unit, adjust frequency as 40KHz, rating of set is 50W, maintains 2min, closes after ultrasonic unit, still keeps reaction system isothermal reaction 0.5 hour at 70 DEG C; Slowly 6 × 10 are dripped again after being cooled to room temperature
-2mol titanium tetrachloride, isothermal reaction 12 hours at 70 DEG C; Finally stop stirring, upper strata mother liquor is separated out, with hexane repetitive scrubbing three times, after drying, obtain catalyzer.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1.
Embodiment 5
First by with heating system and the there-necked flask nitrogen replacement being furnished with the 250ml of whipping appts and reflux condensation mode system is no less than three times, then 60ml normal hexane is added, 1g Magnesium Chloride Anhydrous, 0.5g silica gel (through 200 DEG C of high-temperature activation 2h) stirs and heats up (temperature sets 65 DEG C); Add propyl carbinol 2ml subsequently, stir 0.3 hour; Slowly 1.1 × 10 are dripped after being cooled to room temperature
-2mol aluminium diethyl monochloride, refluxes 1 hour at 65 DEG C; Open ultrasonic unit, adjust frequency as 40KHz, rating of set is 50W, maintains 2min, closes after ultrasonic unit, still keeps reaction system isothermal reaction 0.5 hour at 70 DEG C; Slowly 4 × 10 are dripped again after being cooled to room temperature
-2mol titanium tetrachloride, isothermal reaction 2 hours at 70 DEG C; Finally stop stirring, separated out by upper strata mother liquor, with hexane repetitive scrubbing three times, obtain catalyzer after drying, kinetics of polymerization reaction curve is shown in Fig. 1.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1.
Embodiment 6
Catalyst component preparation method is with embodiment 5, but in Kaolinite Preparation of Catalyst process, ultrasonic unit power changes 80W into by 50W.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1.
Embodiment 7
Catalyst component preparation method is with embodiment 5, but in Kaolinite Preparation of Catalyst process, ultrasonic unit power changes 150W into by 50W.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1.
Embodiment 8
Propyl carbinol in embodiment 5 changes ethanol into, and dosage is 3ml, and other catalyst components preparation method is with embodiment 5.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1.
Embodiment 9
Titanium tetrachloride in embodiment 5 changes tetrabutyl titanate into, and dosage is same, and other catalyst components preparation method is with embodiment 5.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1.
Embodiment 10
Titanium tetrachloride in embodiment 5 changes titanous chloride into, and dosage is same, and other catalyst components preparation method is with embodiment 5.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1.
Embodiment 11
Propyl carbinol in embodiment 5 changes Virahol into, and dosage is same, and other catalyst components preparation method is with embodiment 5.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1.
Embodiment 12
Propyl carbinol consumption in embodiment 5 is 5ml, and other catalyst components preparation method is with embodiment 5.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1.
Embodiment 13
First by with heating system and the there-necked flask nitrogen replacement being furnished with the 250ml of whipping appts and reflux condensation mode system is no less than three times, then 60ml normal hexane is added, 1g Magnesium Chloride Anhydrous, 1.5g silica gel (through 200 DEG C of high-temperature activation 2h) stirs and heats up (temperature sets 65 DEG C); Add propyl carbinol 3ml subsequently, stir 0.3 hour; Slowly 1.5 × 10 are dripped after being cooled to room temperature
-2mol aluminium diethyl monochloride, refluxes 1 hour at 65 DEG C; Open ultrasonic unit, adjust frequency as 40KHz, rating of set is 50W, maintains 2min, closes after ultrasonic unit, still keeps reaction system isothermal reaction 0.5 hour at 70 DEG C; Slowly 4 × 10 are dripped again after being cooled to room temperature
-2mol titanium tetrachloride, isothermal reaction 2 hours at 70 DEG C; Finally stop stirring, upper strata mother liquor is separated out, with hexane repetitive scrubbing three times, after drying, obtain catalyzer.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1.
Embodiment 14
First by with heating system and the there-necked flask nitrogen replacement being furnished with the 250ml of whipping appts and reflux condensation mode system is no less than three times, then 60ml normal hexane is added, 1g Magnesium Chloride Anhydrous, 2.0g silica gel (through 200 DEG C of high-temperature activation 2h) stirs and heats up (temperature sets 65 DEG C); Add propyl carbinol 5ml subsequently, stir 0.3 hour; Slowly 2.8 × 10 are dripped after being cooled to room temperature
-2mol aluminium diethyl monochloride, refluxes 1 hour at 65 DEG C; Open ultrasonic unit, adjust frequency as 40KHz, rating of set is 50W, maintains 2min, closes after ultrasonic unit, still keeps reaction system isothermal reaction 0.5 hour at 70 DEG C; Slowly 4 × 10 are dripped again after being cooled to room temperature
-2mol titanium tetrachloride, isothermal reaction 2 hours at 70 DEG C; Finally stop stirring, upper strata mother liquor is separated out, with hexane repetitive scrubbing three times, after drying, obtain catalyzer.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1, and kinetics of polymerization reaction curve is shown in Fig. 1.
Embodiment 15
First by with heating system and the there-necked flask nitrogen replacement being furnished with the 250ml of whipping appts and reflux condensation mode system is no less than three times, then 60ml normal hexane is added, 1g Magnesium Chloride Anhydrous, 2.5g silica gel (through 200 DEG C of high-temperature activation 2h) stirs and heats up (temperature sets 65 DEG C); Add propyl carbinol 2ml subsequently, stir 0.3 hour; Slowly 1.4 × 10 are dripped after being cooled to room temperature
-2mol aluminium diethyl monochloride, refluxes 2.5 hours at 65 DEG C; Open ultrasonic unit, adjust frequency as 40KHz, rating of set is 300W, maintains 2min, closes after ultrasonic unit, still keeps reaction system isothermal reaction 0.5 hour at 70 DEG C; Slowly 4 × 10 are dripped again after being cooled to room temperature
-2mol titanium tetrachloride, isothermal reaction 12 hours at 70 DEG C; Finally stop stirring, upper strata mother liquor is separated out, with hexane repetitive scrubbing three times, after drying, obtain catalyzer.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1.
Embodiment 16
First by with heating system and the there-necked flask nitrogen replacement being furnished with the 250ml of whipping appts and reflux condensation mode system is no less than three times, then 60ml normal hexane is added, 1g Magnesium Chloride Anhydrous, 1.5g silica gel (without high-temperature activation) stirs and heats up (temperature sets 65 DEG C); Add propyl carbinol 0.5ml subsequently, stir 0.3 hour; Slowly 2.0 × 10 are dripped after being cooled to room temperature
-3mol aluminium diethyl monochloride, refluxes 1 hour at 65 DEG C; Open ultrasonic unit, adjust frequency as 40KHz, rating of set is 50W, maintains 2min, closes after ultrasonic unit, still keeps reaction system isothermal reaction 0.5 hour at 70 DEG C; Slowly 4 × 10 are dripped again after being cooled to room temperature
-2mol titanium tetrachloride, isothermal reaction 2 hours at 70 DEG C; Finally stop stirring, upper strata mother liquor is separated out, with hexane repetitive scrubbing three times, after drying, obtain catalyzer.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1.
Embodiment 17
First by with heating system and the there-necked flask nitrogen replacement being furnished with the 250ml of whipping appts and reflux condensation mode system is no less than three times, then 60ml normal hexane is added, 1g Magnesium Chloride Anhydrous, 1.5g silica gel (without high-temperature activation) stirs and heats up (temperature sets 65 DEG C); Add propyl carbinol 2ml subsequently, stir 0.3 hour; Slowly 1.4 × 10 are dripped after being cooled to room temperature
-2mol dichloro one aluminium triethyl, refluxes 4 hours at 65 DEG C; Open ultrasonic unit, adjust frequency as 40KHz, rating of set is 50W, maintains 2min, closes after ultrasonic unit, still keeps reaction system isothermal reaction 0.5 hour at 70 DEG C; Slowly 4 × 10 are dripped again after being cooled to room temperature
-4mol titanium tetrachloride, at 70 DEG C during isothermal reaction 0.5; Finally stop stirring, upper strata mother liquor is separated out, with hexane repetitive scrubbing three times, after drying, obtain catalyzer.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1.
Comparative example 1
First by with heating system and the there-necked flask nitrogen replacement being furnished with the 250ml of whipping appts and reflux condensation mode system is no less than three times, then add 60ml normal hexane, 1g Magnesium Chloride Anhydrous stirs and heats up (temperature sets 65 DEG C); Add propyl carbinol 1ml subsequently, stir 0.3 hour; Slowly 1.0 × 10 are dripped after being cooled to room temperature
-4mol aluminium diethyl monochloride, refluxes 1 hour at 65 DEG C; Open ultrasonic unit, adjust frequency as 40KHz, rating of set is 50W, maintains 2min, closes after ultrasonic unit, still keeps reaction system isothermal reaction 0.5 hour at 70 DEG C; Slowly 3 × 10 are dripped again after being cooled to room temperature
-4mol titanium tetrachloride, isothermal reaction 2 hours at 70 DEG C; Finally stop stirring, upper strata mother liquor is separated out, with hexane repetitive scrubbing three times, after drying, obtain catalyzer.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1, and kinetics of polymerization reaction curve is shown in Fig. 1.
Comparative example 2
First by with heating system and the there-necked flask nitrogen replacement being furnished with the 250ml of whipping appts and reflux condensation mode system is no less than three times, then 60ml normal hexane is added, 1g Magnesium Chloride Anhydrous, 0.5g silica gel (through 200 DEG C of high-temperature activation 2h) stirs and heats up (temperature sets 65 DEG C); Add propyl carbinol 1ml subsequently, stir 0.3 hour; Slowly 1.0 × 10 are dripped after being cooled to room temperature
-4mol aluminium diethyl monochloride, refluxes 1 hour at 65 DEG C; Slowly 3 × 10 are dripped again after being cooled to room temperature
-4mol titanium tetrachloride, isothermal reaction 3 hours at 70 DEG C, finally stops stirring, is separated out by upper strata mother liquor, with hexane repetitive scrubbing three times, obtain catalyzer after drying.
Vinyl polymerization test is with embodiment 1, and it the results are shown in Table 1, and kinetics of polymerization reaction curve is shown in Fig. 1.
Table 1 resin detects analytical table
Claims (8)
1. for the preparation method of composite carried catalyst for ultrahigh molecular weight polyethylene(UHMWPE) synthesis, it is characterized in that by complex carrier, titanium compound, at least one Organic Alcohol and have at least the alkylaluminium cpd of a halogen substiuted to react to make, wherein:
(1) complex carrier is the composition of silica gel, magnesium halide, and ratio is 0.3 ~ 10molSi/1molMg; Magnesium halide is one or more in magnesium chloride, methylmagnesium-chloride, methoxyl group magnesium chloride, oxyethyl group magnesium chloride or butoxy magnesium chloride;
(2) titanium compound is one or more in titanium tetrachloride, titanous chloride or tetrabutyl titanate, and consumption is 2 ~ 10molTi/1molMg;
(3) Organic Alcohol is C
2~ C
20straight chain, side chain or cycloalkyl alcohol, consumption is 0.1 ~ 3molXOH/1molMg;
(4) general formula of the alkylaluminium cpd of halogen substiuted is R
nalX
3-n, in formula, R is C
1~ C
10alkyl, X is halogen, and n is integer, 1≤n < 3, and consumption is 0.05 ~ 6molAl/1molMg;
The preparation method of the described composite carried catalyst for ultrahigh molecular weight polyethylene(UHMWPE) synthesis, comprises the steps:
(1) under nitrogen protection, magnesium halide, silica gel are added in there-necked flask, adds inert solvent, there-necked flask is placed in the oil bath that temperature is 40 ~ 80 DEG C;
(2) add Organic Alcohol, react 0.1 ~ 1 hour at 20 ~ 120 DEG C, the material now in system is the composition of magnesium alkoxide compound silica gel, and the consumption of Organic Alcohol is 0.1 ~ 3molXOH/1molMg;
(3) in magnesium alkoxide compound, drip the alkylaluminium cpd of halogen substiuted, at 20 ~ 120 DEG C, react 0.5 ~ 6 hour, obtain the aaerosol solution of magnesium halide, the consumption of the alkylaluminium cpd of halogen substiuted is 0.05 ~ 6molAl/1molMg;
(4) obtained to step (3) solution carries out supersound process: ultrasonic frequency 20 ~ 80KHz, ultrasonic power 30 ~ 500W, and sonication treatment time is 0.5 ~ 30min;
(5) drip titanium compound in aaerosol solution after ultrasound exposure, at 20 ~ 120 DEG C, react 0.5 ~ 12 hour, the consumption of titanium compound is 2 ~ 10molTi/1molMg;
(6) reaction terminates, and leaves standstill 3 ~ 120 minutes, treats granules of catalyst sedimentation, layering, by supernatant liquid sucking-off, adds hydrocarbon solvent washing solid particulate 3 times, obtained after dry at 70 ~ 150 DEG C.
2. the preparation method of the composite carried catalyst for ultrahigh molecular weight polyethylene(UHMWPE) synthesis according to claim 1, is characterized in that described magnesium halide is magnesium chloride.
3. the preparation method of the composite carried catalyst for ultrahigh molecular weight polyethylene(UHMWPE) synthesis according to claim 1, is characterized in that described titanium compound is titanous chloride or titanium tetrachloride.
4. the preparation method of the composite carried catalyst for ultrahigh molecular weight polyethylene(UHMWPE) synthesis according to claim 1, is characterized in that described Organic Alcohol is C
2~ C
8alcohol.
5. the preparation method of the composite carried catalyst for ultrahigh molecular weight polyethylene(UHMWPE) synthesis according to claim 4, is characterized in that described Organic Alcohol is ethanol, n-propyl alcohol, propyl carbinol, isopropylcarbinol or isooctyl alcohol.
6. the preparation method of composite carried catalyst for ultrahigh molecular weight polyethylene(UHMWPE) synthesis according to claim 1, is characterized in that the alkylaluminium cpd of described halogen substiuted is one or more in aluminium diethyl monochloride, dichloro one aluminium triethyl or chlorination dipropyl aluminium.
7. the preparation method of the composite carried catalyst for ultrahigh molecular weight polyethylene(UHMWPE) synthesis according to claim 1, is characterized in that the inert solvent described in step (1) is C
5~ C
15alkane.
8. the preparation method of the composite carried catalyst for ultrahigh molecular weight polyethylene(UHMWPE) synthesis according to claim 1, it is characterized in that the sonification power described in step (4) is 40 ~ 150W, sonication treatment time is 3 ~ 6 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210213961.1A CN103509141B (en) | 2012-06-27 | 2012-06-27 | For composite carried catalyst that ultrahigh molecular weight polyethylene(UHMWPE) synthesizes and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210213961.1A CN103509141B (en) | 2012-06-27 | 2012-06-27 | For composite carried catalyst that ultrahigh molecular weight polyethylene(UHMWPE) synthesizes and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103509141A CN103509141A (en) | 2014-01-15 |
| CN103509141B true CN103509141B (en) | 2016-01-06 |
Family
ID=49892608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210213961.1A Active CN103509141B (en) | 2012-06-27 | 2012-06-27 | For composite carried catalyst that ultrahigh molecular weight polyethylene(UHMWPE) synthesizes and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103509141B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034124A (en) * | 2017-12-28 | 2018-05-15 | 宁波俐辰新能源有限公司 | A kind of super high molecular weight porous polyethylene foamed plastics and its manufacture method |
| CN110283281A (en) * | 2019-06-26 | 2019-09-27 | 深圳聚石新材料科技有限公司 | A kind of preparation method of ultra-high molecular weight polyethylene and polypropylene in-situ blending object |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1861650A (en) * | 2005-05-12 | 2006-11-15 | 北京燕化高新催化剂有限公司 | Preparation process of catalyst for ethylene polymerization |
| CN1958623A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Catalyst in use for polymerization or combined polymerization of ethylene, preparation and application |
-
2012
- 2012-06-27 CN CN201210213961.1A patent/CN103509141B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1861650A (en) * | 2005-05-12 | 2006-11-15 | 北京燕化高新催化剂有限公司 | Preparation process of catalyst for ethylene polymerization |
| CN1958623A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Catalyst in use for polymerization or combined polymerization of ethylene, preparation and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103509141A (en) | 2014-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102952222B (en) | Ultra-high molecular weight polyethylene resin and preparation method thereof | |
| JP3237711B2 (en) | Solid component of catalyst for (co) polymerization of ethylene | |
| EP0416928A2 (en) | New carrier catalyst for the polymerization of ethylene | |
| EP2922880A1 (en) | High performance ziegler-natta catalyst systems, process for producing such supported catalysts and use thereof | |
| CN102453154B (en) | Organic chromium catalyst for ethylene polymerization and preparation method thereof | |
| CN105199021A (en) | Titanium fluoride modified load type chrome alum double-active center catalyst and preparation method thereof | |
| CN102264772A (en) | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst | |
| CN102863563B (en) | Ultrahigh molecular polyethylene catalyst and preparation method | |
| CN103509141B (en) | For composite carried catalyst that ultrahigh molecular weight polyethylene(UHMWPE) synthesizes and preparation method thereof | |
| WO2003068830A1 (en) | Solid catalytic component and catalytic system of the ziegler-natta type, process for their preparation and their use in the polymerisation of alk-1-enes | |
| JPH01247405A (en) | Catalyst composition for production high density alpha-olefin polymer having wide molecular weight distribution | |
| CN102863564B (en) | High activity catalyst used for synthesizing ultrahigh molecular weight polyethylene and preparation method | |
| JPH02107605A (en) | Catalyst component | |
| CN107840910B (en) | Catalyst component for ethylene polymerization reaction, preparation method thereof, catalyst and application thereof | |
| JPH0410486B2 (en) | ||
| CZ281952B6 (en) | Catalyst for ethylene homopolymerization and copolymerization and process for preparing a solid component thereof | |
| CN104558294B (en) | Ultrahigh-molecular weight polyethylene catalyst and preparation method thereof | |
| CN101029101B (en) | Diviny polymerization or copolymer catalyst | |
| JP5405172B2 (en) | Olefin polymerization catalyst, polyolefin production method, and polyolefin resin composition | |
| CN103509139B (en) | The preparation method of extra high-molecular polythene catalyst | |
| RU2809186C1 (en) | Catalyst component for polymerization or copolymerization of olefins, method of its preparation and its use | |
| KR20150006856A (en) | A process for the polymerisation of ethylene | |
| WO2004050723A1 (en) | A catalyst for polymerization of ethylene, preparation thereof and use of the same | |
| CZ35098A3 (en) | Process for preparing solid carrier for olefin polymerization catalysts | |
| CZ34998A3 (en) | Process for preparing solid carrier for olefin polymerization catalysts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |