CN86107933A - The manufacture method of alfon or multipolymer - Google Patents
The manufacture method of alfon or multipolymer Download PDFInfo
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- CN86107933A CN86107933A CN198686107933A CN86107933A CN86107933A CN 86107933 A CN86107933 A CN 86107933A CN 198686107933 A CN198686107933 A CN 198686107933A CN 86107933 A CN86107933 A CN 86107933A CN 86107933 A CN86107933 A CN 86107933A
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 74
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 74
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 64
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 48
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 39
- 238000010992 reflux Methods 0.000 claims abstract description 26
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 10
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 10
- 239000004711 α-olefin Substances 0.000 claims abstract description 9
- 238000012662 bulk polymerization Methods 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 29
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 11
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- -1 polypropylene Polymers 0.000 abstract description 18
- 239000004743 Polypropylene Substances 0.000 abstract description 17
- 229920001155 polypropylene Polymers 0.000 abstract description 17
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 238000004260 weight control Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 22
- 239000012071 phase Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000029305 taxis Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 210000004916 vomit Anatomy 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Abstract
Make alfon or molecular weight of copolymer control constant method.Separately with propylene or with propylene with can with the alpha-olefin of copolymerization of propylene, in the presence of hydrogen, mass polymerization in the reactor that reflux exchanger is housed.Constantly measure the heat of from reactor, removing, constantly calculate the hydrogen volume (X) that consumes in the reactor by the hydrogen volume of removing heat and the consumption of Board Lot polypropylene, and then the hydrogen of the suitable volume of variation of adding and volume calculated, just can make alfon and multipolymer continuously molecular weight control in the expection level.X is that the relational expression ln η=lnX+A by the hydrogen volume of polyacrylic intrinsic viscosity η and the consumption of Board Lot polypropylene obtains.
Description
The present invention relates to the method for equal polymerization of propylene or copolymerization.Particularly, the present invention relates to control the method for alfon or molecular weight of copolymer.These polymkeric substance are to use propylene separately, or use propylene and other can with the mixture of the alpha-olefin of copolymerization of propylene, in the presence of molecular weight regulator hydrogen, in the reactor that reflux exchanger is housed and with propylene or mix monomer self, carry out mass polymerization as liquid medium and make.
As everyone knows, when propylene carried out polymerization in the presence of Ziegler-Natta catalyst, the volume that is adjusted in the hydrogen that adds in the polymerization process just can be controlled the polyacrylic molecular weight of product (for example referring to J.Polymer Sci., C2,109(1974)).Because certain substantial connection (for example referring to J.Pol-mer Sci., Part Al, vol.8,2717(1970)) is arranged between the polyacrylic molecular weight of the concentration of hydrogen and product in gas phase.Generally, the concentration of hydrogen in the gas phase is controlled at the constant level makes polypropylene, just can make the polyacrylic molecular weight of product have the numerical value of expection.
When in large-size reactor, adopting mass polymerization to make polypropylene,, be difficult to remove heat of polymerization if just dispel the heat by the reactor wall or by means of the interchanger that is contained in reactor inside.Therefore, people use and utilize the reflux exchanger of liquid medium latent heat to solve, and this is also known.
When propylene carried out mass polymerization in the above-mentioned reactor that reflux exchanger is housed, along with the load difference of reflux exchanger, the concentration of hydrogen had obvious variation in the gas phase.Thereby, must repeat frequently in reactor to add or from reactor, discharge hydrogen with the concentration of keeping hydrogen in the gas phase in constant level, that is to say the molecular weight of having controlled polymerisate.This means to bleed off a large amount of hydrogen that in addition, along with the hydrogen that bleeds off so also will bleed off a large amount of propylene simultaneously, this has just produced the very not rational economically problem of above-mentioned technology.
The present inventor has carried out long research, and purpose is to find out solution to the problems described above.Now, a kind of method has been found in research work, and it can well controllability be regulated polyacrylic molecular weight and not lose hydrogen and/or propylene, and this has just finished the present invention.
Thereby, an object of the present invention is to propose a kind of method of making alfon or multipolymer, its molecular weight of may command and do not lose raw material.
The present invention summarizes in fact, be to have proposed a kind of method of making alfon or multipolymer, Here it is, use propylene separately, or use propylene and other can with the mixture of the alpha-olefin of copolymerization of propylene as monomer or mix monomer, in the presence of molecular weight regulator hydrogen, in constant temp, in being housed, the reactor of reflux exchanger carries out mass polymerization, and with propylene or mix monomer self as liquid medium, the steam of this class medium of condensation can shift out partially polymerized heat at least in reflux exchanger.
Present method comprises:
According to the thermal value that the heat that shifts out artificially from reactor in the unit time and the heat sum of distributing naturally are calculated, calculate the interior polymerization of same unit time monomer or the amount of monomer mixture;
According to the relational expression between the volume (X) of the intrinsic viscosity η of following predetermined alfon that in 135 ℃ tetraline solution, records or multipolymer and the alfon of Board Lot or the hydrogen that multipolymer consumes respectively, determine to have the Board Lot homopolymer of expection molecular weight or the volume of the required hydrogen of multipolymer:
lnη＝lnX+A
A is a constant in the formula;
Volume and the monomer of previous calculations or the product of monomer mixture quantity from top definite hydrogen, add the volume that is accompanied by the hydrogen that slurry leads out from reactor, from itself and deduct the volume that is accompanied by slurry and enters the hydrogen in the reactor, just can calculate the volume of used up hydrogen in reactor, must add the volume of hydrogen in the reactor according to the volume change situation control that consumes hydrogen.
Fig. 1 is an example that is applicable to the equipment of implementing the inventive method;
Fig. 2 is the diagram that concerns between the volume of used up hydrogen in the typical polymerization technology of carrying out under constant temperature and the polymerisate intrinsic viscosity that records in tetraline solution;
Fig. 3 is concentration, the intrinsic viscosity of polymerisate and the diagram that concerns between the reaction times of hydrogen in the reaction vessel in the example.
" other can with the alpha-olefin of copolymerization of propylene " used herein this term means it is wherein a kind of such as ethene, 1-butylene, 1-hexene at least, also can be described as " but alpha-olefin of copolymerization " later on.When making propylene copolymer according to method of the present invention, as long as the product polypropylene keeps slurry state, but there is no particular limitation to the consumption of the alpha-olefin of copolymerization.Yet, but the percentage ratio upper limit of the copolymerization alpha-olefin except that propylene generally can be a 40%(weight in every kind of polymerisate) about.When of the present invention, for simplicity, " propylene " this term that uses in the part of the narration except example is interpreted as not only comprising simple propylene in this manual in narration, also comprise propylene with other can with the mixture of the alpha-olefin of copolymerization of propylene.Correspondingly used " polypropylene " this term of the narration part except example in this manual not only means alfon, also means the multipolymer of monomer mixture.
Because following reason, when propylene in the presence of molecular weight regulator hydrogen, during polymerization, the inventive method has epochmaking purposes in the reactor of reflux exchanger is housed.
In the reactor that does not reinstall flow condenser, gas phase and liquid phase are to be in the vapor liquid equilibrium state, and gas phase is in basically in the uniform state.Thereby, if the concentration of hydrogen in the sample is measured in the gas sampling from gas phase, just can accurately determine the concentration of hydrogen in the gas phase.So, the concentration of the hydrogen that the concentration of the hydrogen of measuring thus and expection are reached, the comparer that adopts known custom to use compares, and on the basis of comparative result, automatically control the feed valve of hydrogenation in reactor, the hydrogen that constantly adds shortcoming thus in reactor makes that the concentration of hydrogen maintains constant level basically in the gas phase.Just can control the polyacrylic molecular weight of product.
Yet when carrying out polymerization with the reactor that reflux exchanger is housed, gas phase and liquid phase always are not in equilibrium state.In addition, as mentioned above, As time goes on, the change in concentration of hydrogen depends on the load of reflux exchanger to a great extent in the gas phase.As a result, if only can not control the polyacrylic molecular weight of product by resembling above-mentioned the sort of simple autocontrol method.
Implement the used typical polymerization catalyzer of the present invention, the catalyst system that can form by known transition-metal catalyst of people and organometallic compound.If necessary or want, also can be used in combination a kind of improving agent of or several taxiss.Though following typical polymerization catalyzer is not particularly limited, can comprise the titanous chloride that obtains with reductive agent such as aluminium, organoaluminum or organic-magnesium reduction titanium tetrachloride as the example of polymerizing catalyst, titanous chloride carries out the active titanous chloride that activation treatment obtains with oxygen-containing organic compound, titanium tetrachloride etc. to it after grinding; Load has titanous chloride or the formed catalyzer of titanium tetrachloride or the like on the carrier such as magnesium chloride.As typical organometallic compound can be organoaluminum such as trialkylaluminium, dialkyl aluminum halide, aluminum alkyls sesquihalide and alkyllithium dihalide, also can be organic-magnesium such as dialkyl magnesium.
Example of the present invention will be narrated below, and with reference to accompanying drawing.
Fig. 1 is applicable to an example implementing the inventive method equipment, be decorated with the reactor (1) that agitator is housed among the figure, a horizontal tube and shell heat exchanger is used as reflux exchanger (2), the chuck (3) of reactor (1), the feed-pipe (5) of adding slurry in reactor (1).If reactor (1) is as single still polymerization or as many first stills of still series connection polymeric, feed-pipe (5) is used for adding catalyst slurry.If reactor (1) is second or the still of back in the series reaction still, feed-pipe (5) is used for introducing reaction slurry from previous reactor.Also have on the figure from reactor (1) outwards discharge slurry vomit pipe (6), add a stopple coupon (9) and a gas blower (18) that the filling tube (7) of propylene and catalyzer, gas phase from reactor (1) are got the gas sample, there not being the gas under the condensation to send back in the reactor (1) in reflux exchanger (2), this non-condensable gas is made up of hydrogen substantially.Also drawing the flow velocity of measurement reflux exchanger (2) ingress gas and the transmitter (4-1) of temperature on the figure, another transmitter (4-2) is used for detecting flow velocity and the temperature that the phlegma of reactor (1) is got back in condensation later in reflux exchanger (2), flow rate regulating valve (4-3) is used for regulating the hydrogen that enters reactor (1), another transmitter (4-4) is used for measuring the flow velocity and the temperature of cooling (or heating) water that leaves chuck (3), a transmitter (4-5) is used for measuring the flow velocity and the temperature of cooling (or heating) water that enters chuck (3) in addition, water inlet pipe (10-1) is used for introducing water coolant to reflux exchanger (2), and rising pipe (10-2) is used for discharging water coolant.
Following program calculate in the reactor (1) polymerization in the unit time as an example monomer or monomer mixture amount.The data signal a that from transmitter (4-1), (4-2), (4-4), (4-5), exports respectively, b, c, d, be imported in the data processor (8), there, the heat dissipation capacity that can calculate according to the overall structure and the operational condition of paradigmatic system, and by data signal a, b, c, d calculate the heat that reactor (1) is removed in the unit time, proofread and correct with this, can calculate the heat that in the same unit time, is produced in the reactor (1) in the data signal output.Because polymerization monomer or the quantity of monomer mixture and the relation between the reaction heat can be by participating in forming of polymeric monomer or monomer mixture, know with known method in the prior art, in data processor (8), the heat of above-mentioned generation further be scaled in the reactor (1) polymerization in the unit time monomer or the quantity of monomer mixture.
Simultaneously, Fig. 2 represents is relation between the volume of polypropylene molecule amount that expection is formed required hydrogen during with the manufacturing polypropylene, that is to say, can be represented by the formula:
lnη＝lnX+A
In the formula, η is that polyacrylic tetraline solution is at 135 ℃ of intrinsic viscosities that record;
X is the volume of the hydrogen that consumed of Board Lot polypropylene;
A is a constant.
Thereby, earlier above-mentioned expression formula is deposited in the data processor (8) as an equation, then, the polypropylene molecule amount of input expection in data processor (8) so just can be determined the volume of the required hydrogen of unit propylene add-on.
In data processor (8), with aforesaid method calculate polymerization in the unit time earlier monomer or the quantity of monomer mixture, the volume with the required hydrogen of unit polypropylene add-on multiplies each other again, has so just obtained the volume of required hydrogen in the reactor (1).When the inventive method is used for the reaction system of many still series connection successive polymerizations, the molecular weight of polymerisate increases progressively successively by still, from managing the slurry of (5) sending into and from the slurry that pipe (6) is discharged, all being dissolved with hydrogen respectively, thereby along with the slurry of front can be brought hydrogen into, and along with a kind of slurry in back can be taken hydrogen out of.So, must in data processor (8), import the data of the volume of relevant hydrogen, and revise based on these data.That is to say, to on data processor (8), carry out following computing, with the volume of the required hydrogen of Board Lot polypropylene that obtains in front with polymerization the product of amount of monomer, add the volume gained of following the hydrogen that slurry takes out of from reactor (1) and, therefrom deduct the volume of following slurry to enter hydrogen in the reactor (1).The result of this computing is as a signal e of output in the data processor (8).Therefore, may control the volume that enters hydrogen in the reactor (1), the concentration that just can keep hydrogen in the interior gas phase of reactor (1) on constant level, thereby make the polypropylene of molecular weight homogeneous.According to the variation of signal e numerical value, regulate the aperture of hydrogen flow rate variable valve (4-3) and just can accomplish this point.
For the measurements and calculations polymerization reaction heat, in above-mentioned example, from the basis of data signal a, the b of transmitter (4-1) and (4-2) output, calculate the heat that reflux exchanger (2) is removed.Entering the mouth (10-1) and exporting temperature and the flow velocity that (10-2) measures the heat-eliminating medium of reflux exchanger (2) respectively, replace the data signal that obtains so above-mentioned signal a, b to be input in the data processor (8) then, thereby also can calculate the heat that reflux exchanger (2) is discharged.
On the other hand, when carrying out polymerization technique with aforesaid reaction vessel (1) the single still polymerization technique of enforcement or with many stills series connection, each reactor all with reactor (1) same-type, a large amount of propylene in each reactor, all have been full of, it is not only liquid medium, when the reaction beginning, it still is a reaction raw materials.Thereby, even according to the present invention, that is to say the volume of obtaining based on the amount of the polymerization reaction heat of measurements and calculations corresponding to the required hydrogen of polymeric propylene quantity, add hydrogen by this volume again, also can not obtain the polymkeric substance of expection molecular weight.Consider when reaction is contained in the volume of the volume of the liquid propene dissolved hydrogen in each reactor and liquid medium top gas phase when initial, therefore be necessary once to add the hydrogen of liquid propene respective volume when beginning, so carry out polyreaction with polyreaction.Then, measure the polyacrylic molecular weight of product and compare with desired value.Result based on the comparison adds a spot of hydrogen or propylene in reactor.Above-mentioned fine setting operation repeats to the polyacrylic molecular weight of product always and reaches till the desired value.After this, reaction can allow to proceed according to the present invention, just can make the polypropylene of constant molecular weight with this method.
So long as being housed, the reactor of reflux exchanger just can be used to implement the present invention.The heat energy power of moving to reflux exchanger does not have particular determination.In stable state, that is to say that when implementing the present invention remove reactor that heat comes controlled temperature by reflux exchanger and be used for when of the present invention, it is effective especially.
From the viewpoint of industry, the present invention is extremely valuable, because, according to method of the present invention, in the presence of molecular weight regulator hydrogen, carry out bulk propylene polymerization with the reactor that reflux exchanger is housed, not only can be efficiently, and can obtain to fine control the polypropylene of constant molecular weight.
Embodiment:
Structure as shown in Figure 1, inner capacities is that as medium, in the presence of the catalyzer of being made up of titanous chloride and diethyl aluminum chloride, liquid propene carries out continuous bulk polymerization in 70 ℃ with liquid propene in 40 cubic metres the reactor.
When initiated polymerization, in reactor, add the hydrogen of 3000 kilograms of propylene and 35 standard cubic meter earlier.Feed hot water to chuck then medium is heated to 70 ℃.When adding catalyzer and propylene with constant speed again (titanous chloride: 1.0 kilograms/hour, diethyl aluminum chloride: 16 kilograms/hour; 10,000 kilograms/hour of propylene), polyreaction is initiated.In reaction process, from reactor, slurry is taken a sample and the polyacrylic molecular weight of measurement product.Molecular weight that records thus and preset value are compared.On the basis of superincumbent comparative result, in reactor, add a spot of hydrogen, repeat so several times fine setting operation, just can make the polyacrylic molecular weight of product adjust to preset value substantially.Approximately cost just can reach preset value in 30 minutes.
Then, carry out the continuous bulk polymerization of propylene according to method of the present invention.Here it is, and with constant feed rate, promptly the speed with 6000 kilograms/hour, 0.8 kilogram/hour and 8 kilograms/hour adds reactor to propylene, titanous chloride and diethyl aluminum chloride respectively.Simultaneously, slurry with about 6000 kilograms/time speed emit from reactor, like this, in reactor, can keep slurry to be in constant level.In this polymerization process, data signal a, b, c, d are transfused to the data processor from transmitter (4-1), (4-2), (4-4), (4-5), the correction of the heat dissipation capacity that data processor presets earlier, carry out again data be for conversion in the unit time polymerization monomeric quantity.Then, the polypropylene intrinsic viscosity 1.73 that in tetraline solution, records at 135 ℃, as the corresponding numerical value input data processor of the polyacrylic expection molecular weight of final product.According to above-mentioned formula intrinsic viscosity is scaled the volume of the hydrogen that the polypropylene of per unit quantity expection molecular weight need consume again.Then, calculate the polymerization determined in the volume of hydrogen and front the product of amount of monomer.Consider the volume of following the hydrogen that slurry takes out of from reactor again, do further correction.Thus, the volume of used up hydrogen in reactor, e exports from data processor as data signal.When the variation according to data signal e, when control added the volume of hydrogen in the reactor, the successive reaction had just been carried out.
Fig. 3 has represented the dependence of polyacrylic intrinsic viscosity time to time change in the concentration (% volume) of hydrogen in the gas phase sample that the pipe (9) from Fig. 1 takes out and pipe (6) is emitted from Fig. 1 the slurry.Can find out easily that from Fig. 3 the concentration of the hydrogen in the gas phase is changing, and intrinsic viscosity is constant, that is to say that molecular weight is the Be Controlled constant.
In addition, under stable state, just when method of the present invention is implemented, the total heat of removing by chuck and reflux exchanger on average be 86,000 ten thousand cards/hour, wherein average about 65% remove by reflux exchanger.
Claims (2)
1, a kind of method that is used to prepare alfon or multipolymer, this method is to use propylene separately, or use propylene and other can with the mixture of the alpha-olefin of copolymerization of propylene as monomer or monomer mixture, in the presence of molecular weight regulator hydrogen, under constant temperature, in reflux exchanger being housed and carrying out mass polymerization with propylene or monomer mixture self in as the reactor of liquid medium, condensation is to remove at least a portion heat of polymerization in reflux exchanger for the medium steam, and present method comprises:
According in the same unit time from the reactor people thermal value that to be the heat of removing calculate with the heat sum of distributing naturally, thereby calculate in the unit time polymerization monomer or the quantity of monomer mixture;
According to pre-determined following relational expression between the volume (X) of the intrinsic viscosity η of alfon that in 135 ℃ of tetraline solution, records or multipolymer and the alfon of Board Lot or the hydrogen that multipolymer consumes respectively:
1nη=1nX+A
A is a constant in the formula,
Determine that Board Lot has the alfon of expection molecular weight or the volume that multipolymer needs hydrogen;
The volume of the hydrogen of determining according to the front with calculate polymerization the monomer or the quantity of monomer mixture long-pending, add the volume of following the hydrogen that slurry discharges from reactor, deduct the volume of following slurry to enter into reactor hydrogen again, just obtain the volume of used up hydrogen, control the volume that adds hydrogen in the reactor according to the variation of this volume.
2, method according to claim 1 wherein uses propylene as only monomer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP262582/1985 | 1985-11-25 | ||
| JP60262582A JPS62124107A (en) | 1985-11-25 | 1985-11-25 | Control of molecular weight |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN86107933A true CN86107933A (en) | 1987-06-03 |
Family
ID=17377810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198686107933A Pending CN86107933A (en) | 1985-11-25 | 1986-11-25 | The manufacture method of alfon or multipolymer |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS62124107A (en) |
| KR (1) | KR890004064B1 (en) |
| CN (1) | CN86107933A (en) |
| AU (1) | AU573461B2 (en) |
| BE (1) | BE905813A (en) |
| DE (1) | DE3639728A1 (en) |
| FI (1) | FI864776A (en) |
| FR (1) | FR2590579B1 (en) |
| GB (1) | GB2183245B (en) |
| IN (1) | IN166637B (en) |
| IT (1) | IT1199672B (en) |
| NL (1) | NL8602979A (en) |
| PT (1) | PT83807B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069652C (en) * | 1991-04-11 | 2001-08-15 | 国家医药管理局上海医药设计院 | Propene polymerizing method and equipment |
| CN102050892B (en) * | 2009-10-27 | 2013-03-27 | 中国石油化工股份有限公司 | Method for controlling production of broad-distribution polyolefin |
| CN106749820A (en) * | 2016-11-25 | 2017-05-31 | 联泓新材料有限公司 | A kind of production method of atactic copolymerized polypropene |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09216913A (en) * | 1995-12-04 | 1997-08-19 | Mitsubishi Chem Corp | Process for producing polyolefin |
| US5739220A (en) * | 1997-02-06 | 1998-04-14 | Fina Technology, Inc. | Method of olefin polymerization utilizing hydrogen pulsing, products made therefrom, and method of hydrogenation |
| JP2009161590A (en) * | 2007-12-28 | 2009-07-23 | Prime Polymer Co Ltd | Method for producing propylene-based polymer and propylene-based polymer |
| CN114432981A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Method and system for adjusting temperature in polymerization kettle and application thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1040669A (en) * | 1963-08-07 | 1966-09-01 | Rexall Drug & Chemical Company | Improvements in and relating to the production of polyolefins |
| US3356667A (en) * | 1963-10-22 | 1967-12-05 | Phillips Petroleum Co | Process control |
| NL6904266A (en) * | 1969-03-20 | 1970-09-22 | ||
| DE3015089A1 (en) * | 1980-04-19 | 1981-10-22 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING HOMOPOLYMERISATEN OR COPOLYMERISATEN PROPYLENS |
| GB2069369B (en) * | 1981-02-06 | 1984-04-18 | Sumitomo Chemical Co | Method and apparatus for removal of heat from an olefin polymerization reactor |
| DE3123115A1 (en) * | 1981-06-11 | 1982-12-30 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING HOMOPOLYMERISATEN OR COPOLYMERISATEN PROPYLENS |
| EP0069806B1 (en) * | 1981-07-13 | 1985-05-15 | Dow Chemical (Nederland) B.V. | Process for producing polyethylene having constant physical and chemical properties |
| JPS60217210A (en) * | 1984-04-11 | 1985-10-30 | Mitsui Toatsu Chem Inc | Method of polymerization of propylene |
| JPS6181409A (en) * | 1984-09-28 | 1986-04-25 | Mitsui Toatsu Chem Inc | Method of controlling molecular weight |
-
1985
- 1985-11-25 JP JP60262582A patent/JPS62124107A/en active Pending
-
1986
- 1986-11-10 IN IN814/CAL/86A patent/IN166637B/en unknown
- 1986-11-12 AU AU65057/86A patent/AU573461B2/en not_active Ceased
- 1986-11-13 GB GB8627113A patent/GB2183245B/en not_active Expired
- 1986-11-21 DE DE19863639728 patent/DE3639728A1/en active Granted
- 1986-11-24 NL NL8602979A patent/NL8602979A/en not_active Application Discontinuation
- 1986-11-24 FI FI864776A patent/FI864776A/en not_active Application Discontinuation
- 1986-11-24 IT IT22436/86A patent/IT1199672B/en active
- 1986-11-24 FR FR868616324A patent/FR2590579B1/en not_active Expired - Fee Related
- 1986-11-25 CN CN198686107933A patent/CN86107933A/en active Pending
- 1986-11-25 KR KR1019860009951A patent/KR890004064B1/en not_active IP Right Cessation
- 1986-11-25 PT PT83807A patent/PT83807B/en not_active IP Right Cessation
- 1986-11-25 BE BE0/217455A patent/BE905813A/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069652C (en) * | 1991-04-11 | 2001-08-15 | 国家医药管理局上海医药设计院 | Propene polymerizing method and equipment |
| CN102050892B (en) * | 2009-10-27 | 2013-03-27 | 中国石油化工股份有限公司 | Method for controlling production of broad-distribution polyolefin |
| CN106749820A (en) * | 2016-11-25 | 2017-05-31 | 联泓新材料有限公司 | A kind of production method of atactic copolymerized polypropene |
Also Published As
| Publication number | Publication date |
|---|---|
| IN166637B (en) | 1990-06-30 |
| NL8602979A (en) | 1987-06-16 |
| BE905813A (en) | 1987-03-16 |
| FI864776A (en) | 1987-05-26 |
| IT8622436A1 (en) | 1988-05-24 |
| PT83807A (en) | 1986-12-01 |
| PT83807B (en) | 1988-08-17 |
| FR2590579B1 (en) | 1991-01-11 |
| AU573461B2 (en) | 1988-06-09 |
| FI864776A0 (en) | 1986-11-24 |
| DE3639728A1 (en) | 1987-05-27 |
| IT8622436A0 (en) | 1986-11-24 |
| IT1199672B (en) | 1988-12-30 |
| GB2183245B (en) | 1989-11-22 |
| FR2590579A1 (en) | 1987-05-29 |
| GB2183245A (en) | 1987-06-03 |
| GB8627113D0 (en) | 1986-12-10 |
| AU6505786A (en) | 1987-06-11 |
| DE3639728C2 (en) | 1989-08-24 |
| KR870005019A (en) | 1987-06-04 |
| JPS62124107A (en) | 1987-06-05 |
| KR890004064B1 (en) | 1989-10-18 |
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