CN1169738A - Catalysts and synthesis of high molecular weight amorphous polyolefins and recovery method thereof - Google Patents
Catalysts and synthesis of high molecular weight amorphous polyolefins and recovery method thereof Download PDFInfo
- Publication number
- CN1169738A CN1169738A CN 95196738 CN95196738A CN1169738A CN 1169738 A CN1169738 A CN 1169738A CN 95196738 CN95196738 CN 95196738 CN 95196738 A CN95196738 A CN 95196738A CN 1169738 A CN1169738 A CN 1169738A
- Authority
- CN
- China
- Prior art keywords
- reactor
- catalyzer
- olefin
- alpha
- solid matter
- 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.)
- Pending
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention discloses a process for the production of amorphous polyolefins. The process entails contacting the olefin monomer, in an unreactive hydrocarbon solvent, with a catalyst in a recirculated, stirred reactor thereby producing amorphous polyolefin. The reactor is capable of recirculating contents that are very viscous.
Description
Invention field
The present invention relates to the synthetic of high molecular amorphous polyolefin.More particularly, the present invention relates to synthetic high molecular amorphous polyolefin with fabulous color and luster and viscosity.The invention still further relates to and use the high solids solution method to produce amorphous polyolefin.
Background of invention
With the synthetic lower molecular weight amorphous polyolefin of Z-N (Ziegler-Natta) type catalyzer, as poly-octene, method be known.But the commercial run of production high molecular amorphous polyolefin, the method for especially producing polyhexene or poly-octene then is not reported.
The open report of great majority be used for alpha-olefine polymerizing based on TiCl
3Classical Ziegler-Natta catalyst or based on MgCl
2Load TiCl
4The third generation or the 4th generation the loading type Ziegler-Natta catalyst publication, usually only openly report C
2-C
10The polymerization process of alpha-olefin.Yet in these publications, both, do not have about producing with high alpha-olefin (C not about the open report of high molecular amorphous polyolefin yet
4More than) be the polyolefine of the principal constituent open report of (comprising polyhexene and poly-octene).In addition, there is not the patent application of relevant high molecular amorphous polyolefin or high alpha-olefin polymkeric substance (as polyhexene and poly-octene) yet.
People wish to find the purposes of high molecular amorphous polyolefin and high alpha-olefin polymkeric substance very much.People also wish to produce the high molecular amorphous polyolefin, include the amorphous polymer of the high alpha-olefin of economic worth, and can produce a kind of polyolefine with good color and luster and premium properties.
Summary of the invention
Method according to the synthetic amorphous polyolefin of the present invention comprises following content: allow C
3-C
10The inert hydrocarbon solvent of alpha-olefin and 0-50 weight percentage (such as ore deposit essential oil) in the recirculation reactor of belt stirrer, in the presence of catalyzer, 25 ℃ in the temperature range of alpha-olefin boiling point, the contact certain hour is to produce amorphous polyolefin; The stirring of the recirculation reactor of wherein said belt stirrer should be able to make the material thorough mixing in the reactor, use high-viscosity pump from this reactor, to extract the material that a part contains alpha-olefin, ore deposit essential oil and amorphous polyolefin continuously out simultaneously, so that reclaim described polyolefine; Wherein said catalyzer is the Ziegler-natta catalyst that contains trialkylaluminium and halogenated titanium; And the viscosity of material is 100,000 to 500,000 centipoises in the wherein said reactor.
The accompanying drawing summary
Fig. 1. this figure is illustrated in amorphous polyolefin polymeric preferred method in the stirred reactor that contains viscous soln.Monomer and catalyzer are imported reactor, extract product continuously out, and part loops back reactor.
The detailed description of invention
The applicant be surprised to find that a kind of method of producing the HMW amorphous polyolefin and Produce the method for amorphous polyolefin in the high solids solution method. The applicant also is surprised to find that A kind of production have the changing of heavy polymer of the high alpha-olefin of fabulous color and luster and viscosity Advance technology and catalyst system.
Method according to the synthetic amorphous polyolefin of the present invention comprises following content: allow C
3-C
10The inert hydrocarbon solvent of alpha-olefin and 0-50 weight percentage in the recirculation reactor of belt stirrer, in the presence of catalyzer, 25 ℃ to the temperature range of alpha-olefin boiling point, the contact certain hour is to produce amorphous polyolefin; The stirring of the recirculation reactor of wherein said belt stirrer should be able to make the material thorough mixing in the reactor, use high-viscosity pump from this reactor, to extract the material that a part contains alpha-olefin, solvent and amorphous polyolefin continuously out simultaneously, so that reclaim described amorphous polyolefin; Wherein said catalyzer is the Ziegler-natta catalyst that contains halogenated titanium and be selected from trialkylaluminium and dialkyl monohalide aluminum cocatalyst; And the material viscosity in the wherein said reactor is 100,000 to 500,000 centipoises.
According to method of the present invention, C
3-C
10The preferred C of alpha-olefin
4-C
10Alpha-olefin, more preferably hexene and octene.In according to method of the present invention, C
3-C
10Alpha-olefin can react with the extra alpha-olefin that reaches 10% weight.
In according to method of the present invention, the most handy ore deposit of inert hydrocarbon solvent essential oil.
In according to method of the present invention, catalyzer is to be the Ziegler-Natta catalyst of principal constituent with the titanium chloride, preferably with TiCl
3For principal constituent or with MgCl
2Load TiCl
4Ziegler-Natta catalyst for principal constituent.
In according to method of the present invention, temperature of reaction is 50 ℃ to 100 ℃, and be 0.5 to 10 hour the duration of contact of main material in the described reactor, preferred 3 to 5 hours.
In according to method of the present invention, make the better method of the partial material recirculation in the recirculation reactor of described belt stirrer be: material to be extracted out with pump from a certain exit of reactor continuously, and annotate back reactor from another ingress, be more preferably in 5 minutes to 2 hours time range, the inventory that accounts for this reactor volume 10% to 100% is carried out recirculation.
In addition, a part of material in the described reactor can be continuously removed by from recycle stock, taking out one slip-stream.According to method of the present invention, the part of described material can adopt above-mentioned high-viscosity pump (such as toothed gear pump) that it is extracted out from this reactor bottom, and then the method for injecting from the top of this reactor is carried out recirculation.
According to method of the present invention, stir described reactor with revolving stirrer, this agitator has centre rotational axis, and its blade is vertically connected on this turning axle.
In according to method of the present invention, described C
3-C
10Alpha-olefin preferably is dissolved in the octene in the essential oil of ore deposit, and its concentration is 20 to 60 weight percentage, and contains the catalyzer of 0.009 to 0.02 weight percentage.
Contain the poly-octene of high-molecular weight according to composition of the present invention, its intrinsic viscosity adopts the ASTM method, is at least 2 when measuring in 25 ℃ toluene solution, and more preferably intrinsic viscosity is at least 2.5, (Garadner) color that adds nail (unit of length) is 1 to 3 poly-octene.
According to the present invention's batch solution method, the operate continuously (see figure 1) is produced when gathering octene, preferably undertaken by following condition: temperature is 50 to 100 ℃, under the atmospheric pressure, the residence time is 3 to 5 hours, and transformation efficiency is 65% to 85%, the concentration of octene is 20 to 60% in the essential oil of ore deposit, contain 0.7 to 1.58 gram solid catalyst in the mixture of 3 gallons of ore deposit essential oils and octene, organoaluminum/titanium mol ratio is 5/1 to 20/1, and the mol ratio of organoaluminum/silicon compound is 5/1 to 20/1.
The high-molecular-weight poly octene of producing according to the present invention after catalyst deactivation and stabilization, possesses the overall characteristic of good color and luster that the high-efficiency binder application facet requires, aggressive tack and fabulous bond strength.Because high-molecular-weight poly octene (intrinsic viscosity 2.6) has good color and luster, aggressive tack and fabulous overall characteristics such as bond strength concurrently, therefore in various high-efficiency binders and seal gum application, caused people's interest, the tackiness agent of disposable product (as diaper and woman article) usefulness for example, label is with hot melt pressure sensitive adhesive, the tackiness agent that is used for the composite product of polyolefin plastics and timber, floor tile tackiness agent, adhesive of medical, automobile usefulness tackiness agent and carpet seam band tackiness agent.
Fig. 1 has described the selection process that the present invention produces amorphous polyolefin.Heat exchanger 4 is being overlapped in the outside of reactor 2, so that keep the temperature that is suitable for polyreaction in the reactor 2.Unreacted alkene monomer and solvent (such as ore deposit essential oil) are through pipeline 18 injecting reactors.Flowable slurried catalyst is through pipeline 16 injecting reactors.Be equipped with in the reactor 2 and stir or whipping appts 14 and recirculation unit 6, to guarantee the thorough mixing of reactant and amorphous polyolefin product.The amorphous polyolefin product and the unreacted reactant that will come out from stirred reactor 2 bottoms with high-viscosity pump 6 (such as toothed gear pump) pump into pipeline 8.By pipeline 20, the material that will contain product and unreacted reactant takes out from reaction system.The part of this material is recycled to heat exchanger 12 continuously, and annotates back reactor 2 by pipeline 10.Product in the pipeline 20 and unreacted reactant can be stored in container or the basin 22, in order to reclaiming the usefulness of product subsequently.
Alternative a kind of method that reclaims product is to introduce wet air and oxidation inhibitor by pipeline 24, so that make catalyst failure or inactivation.Adopt the vacuum extraction method to remove reactant and all kinds of SOLVENTS or thinner.
Another kind of recovery product also makes the preferred method of catalyst deactivation require by pipeline 24 oxidation inhibitor and sour remover to be introduced basin, and make it and mixing of materials with the recycle pump (not shown), then material is introduced the screw extrusion press (not shown), vacuumize to remove most of volatile matter, purifying is after pipeline 18 loops back reactor 2.For example, be used in two and mediate the twin screw extruder that interblock has counterscrew, after making material carry out forward and reverse thorough mixing, vacuumize the catalyst deactivation product of removing remaining unreacted monomer, volatile matter and generation after importing empty G﹠W (both all import in the back of second vacuum port, and are not shown) again.Product comes out from forcing machine, contains 99.5% solid usually.
Be used to produce C
4-C
10Polyolefinic preferred new catalyst system comprises:
(A) ingredient of solid catalyst for preparing by the following method:
(a) in organic solvent, and in the presence of organic acyl chlorides, make the magnesium chemical combination of suspension
Thing and titanium tetrachloride reaction generate a kind of solid matter, and this solid matter contains
Generated in-situ strong interior electron donor(ED), the general formula of wherein said magnesium compound
For:
MgQ
2-nX
n
In the formula, Q is selected from alkoxide group (alkoxide), phenates base respectively
(aryloxide) or carboxylate radical, X is a halogen, n=0 or 1;
(b) drain solid matter, then with the organic solvent that does not dissolve described solid matter
Wash this solid matter;
(c) make described described solid matter and the titanium tetrachloride that is suspended in the organic solvent connect
Touch; With
(d) drain described solid matter after, with not dissolving the organic molten of described solid matter
Described solid matter is washed in agent;
(B) the following silicon compound of a kind of general formula:
SiR
m(OR′)
4-m
In the formula, R is selected from alkyl, cycloalkyl, aryl and vinyl, and R ' is an alkyl, m
Be the integer of zero or 1-3, its condition is when m is 2 or 3, several R bases
Group can be identical or different; Perhaps, when m is 0,1 or 2, several R ' bases
Group can be identical or different; And/or when R was alkyl, R ' can be identical with R
Or it is different; With
(C) the following organo-aluminium compound of a kind of general formula:
R
n″AlX
3-n
In the formula, R " be alkyl, X is halogen or hydrogen atom, and n is the integer of 1-3,
Its condition is that when n was 2 or 3, " group can be identical or different for several R.
Before carrying out (a) step reaction, the magnesium compound that preferably will be used for producing ingredient of solid catalyst (A) is suspended in organic solvent.Before making organic acyl chlorides and titanium tetrachloride contacts, magnesium compound is suspended in guarantees in the solvent that reaction is more complete.Be suspended in preferred 2% to 20% (weight) of magnesium compound content in the organic solvent, more preferably 5% to 15% (weight), most preferably 10% (weight).
Can use any organic solvent that does not dissolve magnesium chloride.Appropriate organic solvent comprises aromatics or aliphatics organic solvent, and aromatics or aliphatic halogenated hydrocarbons solvent are preferably selected aromatic solvent or halogenated aromatic hydrocarbon solvent for use.Suitable concrete example with solvent has benzene, chlorobenzene and toluene, and is wherein best with toluene.
In the above-mentioned general formula preferably magnesium compound be selected from next the group compound: alkoxyl group and aralkoxy magnesium halide; Dialkoxy magnesium; Two aryloxy magnesium; The alkoxyl magnesium carboxylate salt; The alkoxyl group aryloxy thing of aryloxy magnesium carboxylate salt and magnesium.The specific examples of the magnesium compound that is suitable for has: isobutoxy magnesium chloride, oxyethyl group magnesium bromide, phenoxy group magnesium iodide, isopropyl benzene oxygen base magnesium bromide, naphthyloxy magnesium chloride, diisopropoxy magnesium, diethoxy magnesium, dibutoxy magnesium, two phenoxy group magnesium, two naphthyloxy magnesium, oxyethyl group isobutoxy magnesium, two sad magnesium, dipropionic acid magnesium, ethoxy phenoxy magnesium, naphthyloxy isopentyloxy magnesium, the sad magnesium of oxyethyl group, phenoxy propionic acid magnesium and laurostearic acid magnesium chloride, wherein inexpensive because the diethoxy magnesium compound is easy to get, so the most desirable.When in (a) step reaction, when organic acyl chlorides precursor makes the strong electron donor(ED) of (a), to discuss as bottom, this magnesium compound should contain an OR base at least, preferably alkoxyl magnesium or alkoxyl group magnesium halide.
(a) the strong interior electron donor(ED) in is ester preferably, and original position makes from corresponding organic acyl chlorides.By organic acyl chlorides precursor and magnesium compound, as alkoxyl magnesium, reaction promptly makes strong interior electron donor(ED) in position.The preferred organic acyl chlorides precursor that is used for electron donor(ED) in preparation (a) strong can be selected from Benzoyl chloride and phthalyl chloride, they can with the diethoxy reactive magnesium generate optimal strong in electron donor(ED), i.e. ethyl benzoate and diethyl phthalate.The term of Shi Yonging " strong electron donor(ED) " means Louis (lewis) alkali herein, and it has strong electron donation, thus can with active catalyst (as titanous chloride) be subjected to the strong complexing in electronics position.
Catalyst system according to the present invention's preparation and use, in ingredient of solid catalyst (A), electron donor(ED) is present in (a) step reaction process with the form of organic acyl chlorides precursor in strong, its content is that every mole of magnesium compound is equivalent to 0.1 to 2 mole, and more preferably every mole of magnesium compound is corresponding to 0.2 to 0.4 mole.
When preparation ingredient of solid catalyst (A), the titanium tetrachloride consumption is preferably every mole of magnesium compound corresponding to 2 to 6 moles in the reactions steps (a), and more preferably every mole of magnesium compound is corresponding to 3 to 4 moles.In the reaction of (a) step, if use the titanium tetrachloride that surpasses 6 moles far away corresponding to every mole of magnesium compound, then surpass the required effective level of preparation magnesium chloride, and if corresponding to the titanium tetrachloride of every mole of magnesium compound use far below 2 moles, then in the reaction of (c) step, need more titanium tetrachloride, or need repeatedly to repeat the operation of (c) step.
(a) solid matter for preparing in the step need take out from solvent with the decantation method, and washing then is to remove unreacted component.Wash with the organic solvent that does not dissolve this solid matter.The example of this class organic solvent that is suitable for comprises employed those solvents in above-mentioned (a) step.This washing step (b) can repeat repeatedly as required, so that fully remove by product, impurity or unreacted component.
Solid matter resuspending through preparing, washing and drain is handled once at least again with titanium tetrachloride in organic solvent.This treating processes can be carried out once or several times, and is just passable as long as the titanium tetrachloride that has the magnesium compound of capacity to change into magnesium chloride and capacity deposits on the magnesium chloride surface in the solid matter.After handling with titanium tetrachloride at every turn, or after final the processing, again solid matter is drained, and use organic solvent washing.Each washing step all need carry out several, and preferably at least three times, so that remove unwanted material.At washing step (d) afterwards, preferably repeat a titanium tetrachloride treatment step (c) at least again, and then washing once.
Begin and follow-up reactions steps in, the concentration of titanium tetrachloride is: contain titanium tetrachloride 200 to 600 mmoles in per 100 milliliters of organic solvents, the mol ratio that is titanium tetrachloride and magnesium compound is 2 to 6, preferably in per 100 milliliters of organic solvents, contain titanium tetrachloride 400 to 500 mmoles, make the mol ratio of titanium tetrachloride and magnesium compound reach 4 to 5.
The preparation ingredient of solid catalyst (A) reaction preferably under agitation carry out at 80 to 100 ℃, the reaction times is 30 minutes to 8 hours, under 100 to 110 ℃ of temperature the reaction 2 to 3 hours then better.If temperature of reaction is during far below 80 ℃, then the preparation feedback of ingredient of solid catalyst begins quite slowly, and temperature of reaction then can make solvent evaporates during far above 125 ℃ under normal pressure.Reaction times, perhaps not enough so that reaction is carried out fully, the reaction times then was unnecessary more than 8 hours during far fewer than 30 minutes.
According to needing to exist a kind of silicon compound in the catalyst system of the present invention with above-mentioned general formula.An eka-silicon examples for compounds that is fit to comprises: tetraalkoxysilane, alkylalkoxy silane, octadecyloxy phenyl TMOS, phenylalkyl organoalkoxysilane, cycloalkyl alkoxy silane, cycloalkylalkyl organoalkoxysilane, cycloalkyl octadecyloxy phenyl TMOS and cycloalkylalkyl octadecyloxy phenyl TMOS.The example of concrete silicon compound comprises: tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane and four butoxy silanes, the trimethoxy ethylsilane, trimethoxymethylsila,e, dimethyldimethoxysil,ne, the triethyl methoxy silane, the trimethylammonium methoxy silane, the diethyl diethoxy silane, second, isobutyl dimethoxy silane, propyl trimethoxy silicane, ethyl trimethoxy silane, ethyl three isopropoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl tripropoxy silane, phenyl three isopropoxy silane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, the triphenyl methoxy silane, the cyclohexyl triethoxyl silane, cyclohexyl methyl dimethoxy silane, dicyclopentyl dimethoxyl silane, the thricyclohexyl Ethoxysilane, phenyl (methyl) dimethoxy silane, cyclohexyl (ethyl) phenyl methoxy silane, the dicyclohexyl diethoxy silane, vinyltrimethoxy silane, vinyl (dimethyl) methoxy silane, and vinyl (cyclohexyl) methyl methoxy base silane, preferably cyclohexyl methyl dimethoxy silane and phenyl triethoxysilane.
In catalyst system of the present invention, the consumption of silicon compound (B) should make the mol ratio of organo-aluminium compound and silicon compound reach 1 to 100, and with 5 to 30 better, 10 to 20 best.When the mol ratio of organoaluminum/silicon compound far below 1 the time, can reduce activity of such catalysts, and when its mol ratio far above 100 the time, can produce the poly-octene of nonconforming lower molecular weight.
Organo-aluminium compound (C) preferably is selected from the compound of trialkylaluminium, dialkyl aluminum halide and dialkyl aluminum hydride one class.Preferred organo-aluminium compound is selected from the compound that contains trimethyl aluminium, triethyl aluminum, triisobutyl aluminium and diisobutyl alanate one class, preferably selects triethyl aluminum (TEAL) for use, because of it is convenient to acquisition and inexpensive.
The selection of organo-aluminium compound consumption should make the mol ratio of organo-aluminium compound/titanium reach 1 to 50 and be advisable, and its mol ratio is 5 to 20 better, and best consumption is that to make the mol ratio of organo-aluminium compound/titanium be 10 to 15.In catalyst system, the mol ratio of organo-aluminium compound/titanium is crossed and is lower than 1, can make catalyst activity very low, and mol ratio is crossed and is higher than at 50 o'clock, then produces the poly-octene of nonconforming lower molecular weight.
Following embodiment is used to illustrate the present invention, and does not constitute the restriction to zone of reasonableness of the present invention.
The embodiment solution method
In the following embodiments, use the small test chamber device that constitutes by 3 gallons of glass reactors of jacketed type, heat exchanger and LCI22/13 recycle pump (a kind of high viscosity solution pump) to carry out the octene polyreaction, substantially as shown in Figure 1.
A typical polymerization flow process is: under nitrogen protection octene/ore deposit essential oil raw mix of 1 gallon 50/50 joined in one 3 gallons the reactor, and be heated to 50 ℃ of whiles and make reaction mixture cycle through heat exchanger with 200 rev/mins speed (0.2 gallon of per minute circulation).Catalyzer is joined in the described reactor of present embodiment then.Usually after adding catalyzer, temperature begins to rise and begin to form foam.In case temperature reaches 60 ℃, append raw material immediately and make temperature maintenance between 60 and 65 ℃, in reactor, add till the full with substance (3 gallons or 8000 gram solution).This operation need be carried out 20 to 30 minutes usually.Temperature of reaction is controlled at 65 ℃ ± 2 ℃, makes polyreaction proceed 3 hours.Adopt the method for reactor jacket circulating hot water or cold water, or with the method for heat exchanger circulating water, or with the method for electric heating cooker reheat heat exchanger, all can reach the reactor medium is heated or cooling purpose.After polyreaction was carried out 3.25 hours to 3.5 hours, the weight percent solids in the reaction medium generally reached 30% to 33%.The polymers soln that will still contain active catalyst this moment is discharged in one 5 gallons the batch can, in solution, import wet air so that the catalyst deactivation in the polymkeric substance with Bubbling method, simultaneously 6.5 gram Irganox1010 (by a kind of oxidation inhibitor of 0.25% weight fraction of solid polymer) are joined in the solution, stirred 30 minutes, and made polymer stabilising.Get the 10ml polymers soln and place test tube, 230 ℃ of following vacuum extraction 30 minutes.Measure the intrinsic viscosity of the finished product (poly-octene) in the toluene solution under 25 ℃.Classical Ziegler-Natta catalyst
The classical Ziegler-Natta catalyst that uses among the relatively poor embodiment of effect is Lynx 900, and this is a kind of preactivated TiCl
3Catalyzer.
Be used to prepare pre-activation TiCl
3TiCl
3Be the TiCl that makes with chemical reduction method
3At this TiCl
3Exist down, make the TiCl of propylene prepolymerization to the polypropylene that contains 50% (weight) and 50% (weight)
3Thereby, make TiCl
3Pre-activation.The commercially available pre-activated catalyst that uses in the relatively poor embodiment of effect (is the TiCl that is made by chemical reduction method as Lynx 900
3), can buy from the Catalyst Resorces company of Texas Houston.Loaded catalyst
The loaded catalyst that uses in the relatively poor embodiment of effect is with TiCl with polishing
4Be carried on MgCl
2On.This TiCl
4At MgCl
2Charge capacity on the carrier is 10% (weight), and contains the organic ester (right-the ethoxyethyl group benzoic ether) of 20% (weight).Employed commercially available loaded catalyst is Lynx 705 in the relatively poor embodiment of these effects, can buy from the Catalyst Resorces company of Texas Houston.This class catalyzer also often is referred to as third generation catalyzer.Embodiment 1-10 (effect is relatively poor)
Usually be used for the commercially available Ziegler-Natta catalyst of octene polymeric with two kinds of small test chamber device evaluations.Working method is identical with above-mentioned solution method basically, and different is, is 2.6 poly-octene in order to produce intrinsic viscosity, needs to change the mol ratio of monomer consumption, temperature, catalyzer and catalyzer.Shown in the following Table I of its reaction conditions and result.
Table I reaction condition embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 ore deposit essential oil/octenes 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 injection rates, gallon octene concentration 20 30 40 50 50 50 50 50 50 50 % by weight catalyst type LYNX LYNX LYNX LYNX LYNX LYNX LYNX LYNX LYNX LYNX
705 705 705 705 705 705 705 705 900 900 solid catalysts, 1.0 1.0 1.0 1.0 1.0 1.0 1.5 1.5 2.7 2.7 consumptions, titanium 1.87 1.87 1.87 1.87 1.89 1.87 1.87 1.87 15.5 15.5 content in the gram catalyzer, weight %AlEt
3/ Ti mol ratio 75 75 75 75 50 25 75 75 1.0 1.0AlEt
3/ CHMDS------20 10--molar ratio reaction temperature ℃ 60 ± 2 60 ± 2 60 ± 2 60 ± 2 60 ± 2 60 ± 2 60 ± 2 60 ± 2 60 ± 2 80 ± 2 residence times, 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 hours solids as a result, weight % 14.4 16.8 28.6 32.0 26.2 15.5 24.0 21.0 26.4 27.5 transformation efficiencys, % 72 56 71.5 64 52 31 48 42 53 55 catalyzer output capacities, 1,152 1,344 2,288 2,560 2,096 1,240 1, the faint yellow faint yellow deep yellow deep yellow of 280 1,120 782 815 gram/gram polymkeric substance I..V., 1.63 1.69 1.71 1.73 1.85 1.89 2.03 1.97 3.78 2.51 polymkeric substance tint lemon yellows white white white white
The result shows that monomer content has a significant effect to the output capacity of Lynx 705 catalyzer in the material of adding.When the monomer consumption when 20% increases to 50%, the output capacity of catalyzer is brought up to the poly-octene (seeing embodiment 1-4) of every gram catalyzer output 2,560 grams from the poly-octene of every gram catalyzer output 1,150 gram.See from the result of evaluate catalysts Lynx 705, at AlEt
3/ Ti mol ratio is the poly-octene molecular weight ratio expected value low (intrinsic viscosity is 1.7) that 75/1 and 60 ℃ lesser temps is produced down, (every gram catalyzer output is gathered octene 2 but the catalyzer output capacity is very high, 600 restrain), and the catalyst deactivation after product has fabulous color and luster (white).Work as AlEt
3/ Ti catalyst molar ratio drops at 25/1 o'clock from 75/1, or adds cyclohexyl methyl dimethoxy silane (CHMDS) and make AlEt in catalyzer
3/ CHMDS mol ratio is 20/1 and 10/1 o'clock, all the catalyzer output capacity is produced utmost point injurious effects, makes it from 2,600 gram/grams reduce to 1,200 gram/grams, and the intrinsic viscosity of polymkeric substance increases to 2.0 from 1.7, still is lower than the intrinsic viscosity target value 2.5 to 2.6 (seeing embodiment 5-8) of expection.
Evaluation to catalyzer Lynx 900 shows that this catalyzer is at AlEt
3/ Ti mol ratio is 1/1, when temperature of reaction is 80 ℃, can produce only high-molecular-weight poly octene (intrinsic viscosity is 2.5), but catalyzer output capacity low (the poly-octene of every gram catalyzer output 800 grams), and at the color and luster of catalyst deactivation after product bad (deep yellow).Also can obtain the more poly-octene (seeing embodiment 9 and 10) of high-molecular weight when under 60 ℃ lesser temps, reacting with this catalyzer.In a word, use those catalyzer among the embodiment 1-10, none can reach produces the poly-octene that not only has higher molecular weight (intrinsic viscosity 2.5-2.6) but also have good color and luster, and the effect of high catalyzer output capacity is arranged again.Embodiment 11-18
With the appraisal of equipment the present invention of small test chamber best the 4th generation catalyzer.Working method is identical with above-mentioned solution method basically, different is used the 4th generation catalyzer be by TiCl
4Be carried on MgCl
2(titanium of 2.5% (weight)) and interior electron donor(ED) (phthalic ester) upward constitute, and regulate the mol ratio and the temperature of catalyzer, make the intrinsic viscosity of the poly-octene that is produced reach 2.5 to 2.6.Reaction conditions and the results are shown in Table II.
Table II reaction condition embodiment 11 embodiment 12 embodiment 13 examples 14 embodiment 15 embodiment 16 embodiment 17 embodiment 18 ore deposit essential oil/octenes 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 injection rates, gallon octene concentration 50 50 50 50 50 50 50 50 % by weight catalyst types are of the present invention
Catalyst agent catalyst agent catalyst agent catalyst agent solid catalyst 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 consumptions, titanium 2.58 2.58 2.58 2.58 2.58 2.58 2.58 2.58 content in the gram catalyzer, weight %AlET
3/ Ti mol ratio 125 125 20 15 10 15 15 15AIET
310 molar ratio reaction temperature ℃ 60 60 60 60 60 65 70 75 residence times of/CHMDS 2,5/1 5/1----20,3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 hours solids as a result, weight % 45.2 41.6 39.5 37.1 35.4 37.0 36.0 35.5 transformation efficiencys, % 90 83 79 74 71 74 72 71 catalyzer output capacities, 3,620 3,330 3,160 2,970 2,880 2,960 2,880 2,840 gram/gram polymkeric substance I.V., 1.57 1.68 2.25 2.75 3.20 2.6 2.75 2.58 polymkeric substance color and lusters white white white white white white white white
Use as the 4th generation of catalyzer of the present invention during catalyzer synthesing isotactic polypropylene, common Al/Ti mol ratio is 100-150/1, and the Al/CHMDS mol ratio is 5-25/1, and temperature of reaction is 65-70 ℃.The poly-octene that under this condition, makes, its intrinsic viscosity very low (1.57-1.68) (seeing embodiment 11 and 12).What do not expected is, when the Al/Ti mol ratio when 125/1 reduces to 20/1, obtained the desired high intrinsic viscosity and the poly-octene of good color and luster unexpectedly, and good catalyzer output capacity can have been arranged.Mol ratio to catalyzer has further been done small adjusting, obtains the poly-octene that three kinds shown in the following Table III can be produced desired characteristic viscosity number 2.6 and good color and luster, and the alternative plan of high catalyzer output capacity is arranged again simultaneously.
Table III
Temperature ℃ 2 70 ℃ 1,5/1 20/1 scheme of Al/Ti mol ratio Al/CHMDS mol ratio scheme 1 65 15/1-scheme the results are shown in embodiment 13-18 for 3 75 ℃ 1,5/1 10/1.
Claims (20)
1. the method for a synthetic amorphous polyolefin comprises: allow C
3-C
10The inert hydrocarbon solvent of alpha-olefin and 0-50 weight percentage in the recirculation reactor of belt stirrer, in the presence of catalyzer, 25 ℃ to the temperature range of alpha-olefin boiling point, the contact certain hour is to produce amorphous polyolefin; The stirring of the recirculation reactor of wherein said belt stirrer should be able to make the material thorough mixing in the reactor, use high-viscosity pump from this reactor, to extract the material that a part contains alpha-olefin, solvent and amorphous polyolefin continuously out simultaneously, so that reclaim described amorphous polyolefin; Wherein said catalyzer is the Ziegler-natta catalyst that contains halogenated titanium and be selected from trialkylaluminium and dialkyl monohalide aluminum cocatalyst; And the material viscosity in the wherein said reactor is 100,000 to 500,000 centipoises.
2. according to the process of claim 1 wherein described C
3-C
10Alpha-olefin is C
4-C
10Alpha-olefin.
3. according to the method for claim 2, wherein said C
3-C
10Alpha-olefin is selected from hexene and octene.
4. according to the process of claim 1 wherein described C
3-C
10Alpha-olefin can react with the extra alpha-olefin up to 10% (weight).
5. according to the process of claim 1 wherein that described unreactive hydrocarbons solvent is the ore deposit essential oil.
6. according to the process of claim 1 wherein that described catalyzer is that titanium chloride is main Ziegler-Natta catalyst.
7. according to the method for claim 6, wherein said catalyzer is selected from TiCl
3Be main Ziegler-Natta catalyst and be stated from MgCl
2On TiCl
4It is main Ziegler-Natta catalyst.
8. according to the method for claim 7, wherein said catalyzer comprises:
(A) ingredient of solid catalyst for preparing by the following method:
(a) in organic solvent, and in the presence of organic acyl chlorides, make the magnesium chemical combination of suspension
Thing and titanium tetrachloride reaction generate a kind of solid matter, and this solid matter contains
Generated in-situ strong interior electron donor(ED), the general formula of wherein said magnesium compound
For:
MgQ
2-nX
n
In the formula, Q is selected from alkoxide group (alkoxide), phenates base respectively
(aryloxide) or carboxylate radical, X is a halogen, n=0 or 1;
(b) drain solid matter, then with the organic solvent that does not dissolve described solid matter
Wash this solid matter;
(c) make described described solid matter and the titanium tetrachloride that is suspended in the organic solvent connect
Touch; With
(d) drain described solid matter after, with not dissolving the organic molten of described solid matter
Described solid matter is washed in agent;
(B) the following silicon compound of a kind of general formula:
SiR
m(OR′)
4-m
In the formula, R is selected from alkyl, cycloalkyl, aryl and vinyl, and R ' is an alkyl, m
Be the integer of zero or 1-3, its condition is when m is 2 or 3, several R bases
Group can be identical or different; Perhaps, when m is 0,1 or 2, several R ' bases
Group can be identical or different; And/or when R was alkyl, R ' can be identical with R
Or it is different; With
(C) the following organo-aluminium compound of a kind of general formula:
R
n″AlX
3-n
In the formula, R " be alkyl, X is halogen or hydrogen atom, and n is the integer of 1-3,
Its condition is that when n was 2 or 3, " group can be identical or different for several R.
9. according to the process of claim 1 wherein that described temperature is 50 ℃ to 100 ℃.
10. according to the process of claim 1 wherein that reaction (contact) time of most of material is 0.5 to 10 hour in the described reactor.
11. according to the method for claim 10, the wherein said reaction times is 3 to 5 hours.
12. according to the process of claim 1 wherein that the partial material in the described recirculation stirred reactor extracts out by an outlet from reactor continuously, send reactor back to from another inlet of reactor again, be achieved recirculation.
13. according to the method for claim .12, the partial material of wherein said reactor is constantly to shift out by taking out one slip-stream the material of from recirculation.
14., wherein saidly make that material recirculation is meant that the material that the 10-100% volume is arranged in the described reactor has carried out recirculation in 5 minutes to 2 hours time in the reactor according to the method for claim 12.
15. according to the method for claim 12, wherein said partial material is to extract out from this reactor bottom with described high-viscosity pump, and injects and carry out recirculation from this reactor head.
16. according to the method for claim 15, wherein said high-viscosity pump is a toothed gear pump.
17. according to the process of claim 1 wherein that described reactor stirs with revolving stirrer, this agitator has centre rotational axis, its blade is vertically connected on this axle.
18. according to the process of claim 1 wherein described C
3-C
10Alpha-olefin is the octene that is dissolved in the essential oil of ore deposit, and its concentration is 20% to 60% (weight), and contains the catalyzer of 0.009% to 0.02% (weight).
19. a composition that contains the high-molecular-weight poly octene, the intrinsic viscosity of described poly-octene is at least 2, and this is to record with the ASTM method in 25 ℃ toluene solution.
20. according to the composition of claim 19, the intrinsic viscosity of wherein said poly-octene is 2.5 at least, adding the nail (unit of length) color is 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95196738 CN1169738A (en) | 1994-10-18 | 1995-10-10 | Catalysts and synthesis of high molecular weight amorphous polyolefins and recovery method thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/332,306 | 1994-10-18 | ||
| CN 95196738 CN1169738A (en) | 1994-10-18 | 1995-10-10 | Catalysts and synthesis of high molecular weight amorphous polyolefins and recovery method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1169738A true CN1169738A (en) | 1998-01-07 |
Family
ID=5083241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95196738 Pending CN1169738A (en) | 1994-10-18 | 1995-10-10 | Catalysts and synthesis of high molecular weight amorphous polyolefins and recovery method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1169738A (en) |
-
1995
- 1995-10-10 CN CN 95196738 patent/CN1169738A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1726080A (en) | Magnesium dichloride-based adducts and catalyst components obtained therefrom | |
| CN1976959A (en) | High activity and good hydrogen response ziegler-natta polyethylene catalyst | |
| CN1008907B (en) | Catalyst components, a catalyst and a process for the polymerization alpha-olefins | |
| CN1026003C (en) | Process for manufacturing of catalyst composition used in olefin polymerization | |
| CN1681853A (en) | Components and catalysts for the polymerization of olefins | |
| CN1035301A (en) | The novel method of propylene polymerization | |
| EP0787155B1 (en) | Catalysts and synthesis of high molecular weight amorphous polyolefins and recovery thereof | |
| CN1948351A (en) | Polymer carrier Ziegler-Natta catalyst for olefin hydrocarbon polymerization and its preparation method | |
| CN1050360C (en) | Organoaluminoxy product, catalyst systems, preparation, and use | |
| CN1029234C (en) | Supported polymerization catalyst | |
| CN1207312C (en) | Catalyst obtained by prepolymerization of polyolefin and olefin polymerization method using the same | |
| CN1230451C (en) | Catalyst for olefin polymerization and method of olefin polymerization using same | |
| CN1188432C (en) | A multi-stage process for the preparation of alpha-olefin polymers having controlled stereoregularity and products prepared thereof | |
| US7414095B2 (en) | Liquid phase process for polymerizing olefins | |
| CN1290874C (en) | Magnesium dichloride-alcohol adducts and catalyst components obtained therefrom | |
| CN1169738A (en) | Catalysts and synthesis of high molecular weight amorphous polyolefins and recovery method thereof | |
| CN1107682C (en) | alpha-olefin polymerization catalyst and process for producing alpha-olefin polymer | |
| CN1152063C (en) | Solid catalyst for polymerization of olefin and its preparing process | |
| CN1241955C (en) | Catalyst composition for olefine polymerization or copolymerization | |
| CN1282669C (en) | Compound catalyst for olefin polymerization | |
| CN1185443A (en) | Olefin polymerization catalyst and method for preparing polyolefin using said catalyst | |
| CN1492882A (en) | Zieger Natta catalyst for polymerization of olefins | |
| CN1272349C (en) | Polyolefine catalyst, its making method, using method, and polymer made from said catalyst | |
| CN1122047C (en) | Preparation of catalyst for ethylene polymerization | |
| CN1849342A (en) | Process for producing polyolefin and vapor phase polymerization apparatus therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |