CN101747453B - Ageing process and equipment for multi-element catalyst of solution polymerization system - Google Patents
Ageing process and equipment for multi-element catalyst of solution polymerization system Download PDFInfo
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- CN101747453B CN101747453B CN2008102277738A CN200810227773A CN101747453B CN 101747453 B CN101747453 B CN 101747453B CN 2008102277738 A CN2008102277738 A CN 2008102277738A CN 200810227773 A CN200810227773 A CN 200810227773A CN 101747453 B CN101747453 B CN 101747453B
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- 230000032683 aging Effects 0.000 title claims abstract description 206
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000010528 free radical solution polymerization reaction Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 28
- 230000008569 process Effects 0.000 title claims description 17
- 239000002904 solvent Substances 0.000 claims abstract description 67
- 239000000178 monomer Substances 0.000 claims abstract description 44
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 230000003068 static effect Effects 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 38
- 230000037048 polymerization activity Effects 0.000 claims description 15
- 238000010790 dilution Methods 0.000 claims description 11
- 239000012895 dilution Substances 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 230000008676 import Effects 0.000 claims description 7
- 238000009434 installation Methods 0.000 claims description 6
- 238000003113 dilution method Methods 0.000 claims description 5
- 238000007086 side reaction Methods 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 238000005086 pumping Methods 0.000 description 14
- 230000037452 priming Effects 0.000 description 11
- 230000029087 digestion Effects 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000029936 alkylation Effects 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 4
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 4
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a multi-catalyst aging process and equipment for a solution polymerization system; synchronously feeding catalyst solutions with different concentrations in a catalyst tank into an aging tank according to a proportion within 10-30 seconds in a polymerization system, aging for 0-60 minutes, adding solvent oil into the aging tank within 10 minutes after an ideal active center is generated, wherein the volume ratio of the solvent oil to the total amount of the catalyst is 5: 1-20: 1, mixing a monomer and the solvent oil through a static mixer, adding the mixture into the aging tank for prepolymerization reaction, wherein the volume ratio of the solvent oil to the monomer is 1: 1-5: 1, the amount of the monomer is based on the initiation of the prepolymerization reaction, the liquid level of the aging tank is controlled at 1/2-2/3, and after the reaction is finished, feeding the mixture into a polymerization first kettle; the requirements of various aging concentrations and time of the catalyst are met, so that the aging can be controlled, the active center is stable, the probability of occurrence of phenomena such as back mixing, polymerization, blockage and the like in a pipeline is reduced, and the phenomenon of implosion carried out at the bottom of the first kettle is inhibited.
Description
Technical field
The present invention relates to a kind of aging process of multiple-catalytic agent in solution polymerization system and equipment.
Background technology
In solution polymerization system, the composition of catalyzer usually comprises Primary Catalysts and promotor, generally is diversification, and each catalyzer produces effective active centre (ageing) earlier by reacting to each other, participate in follow-up polyreaction again, there are homogeneous phase and heterogeneous branch in the active centre.Traditional many still series connection solution polymerization process are to send into each component of catalyzer in the pipeline of certain-length by metering respectively with pump, carry on catalyzer limit ageing therein limit, until entering first still bottom, or after converging, solvent oil and monomer enter again bottom the first still, stirring reaction, enter two stills bottom again from first still top, so low in and high out is finished polymerization to the top discharging of last still.Under this processing condition, if digestion time is short or ageing concentration is low, can not get abundant reaction between each component of catalyzer, just enter toward the active centre that contact does not produce sufficient amount and participate in polyreaction in the polymeric kettle; If digestion time is long or ageing concentration is big, the active centre of generation can not in time be sent in the polymeric kettle, and continues to take place unnecessary side reaction.The sort of situation takes place all can make the catalyzer service efficiency to descend, polymerization activity can not get ensureing that the polymerisate performance reduces, especially for the multiple catalyzing system that produces heterogeneous active centre, under the situation that digestion time is grown or ageing concentration is big, to constantly grow up in the part active centre, form bigger solid particulate, precipitate and be adsorbed on the tube wall, cause active centre quantity to reduce, particle diameter differs greatly, and the uncontrollable situation of proterties of a specified duration will directly be blocked process pipeline.
In addition, in above-mentioned technology, in order to satisfy necessary digestion time and two requirements of ageing concentration, the pumpage of catalyzer is generally not high, and concentration is higher relatively, and transfer rate is then relatively slow, easy like this its back-mixing, unequal problem of ageing in pipeline that cause.Simultaneously, in pipeline, catalyzer and the monomer place of meeting easily cause the still pre-polymerization.In first still bottom, because monomer is relative with catalyst concn higher, if stir insufficient, the generation of side reactions such as the local implode of easy generation, the polymkeric substance that is produced will stop up the import of bottoms material, can't make the subsequent process smooth running, causes unnecessary parking.For the intermittent type solution polymerization process,, avoided in the pipeline basically and the improper polyreaction at the bottom of the still, but the aged quality of catalyzer affect the quality of follow-up polyreaction too because of taking feeding manner more flexibly.
In practice, be not that all solution polymerization process all can run into above-mentioned all problems, but with regard to some specific polyreaction, one of key point of the whole polyreaction really of the aged quality of catalyzer.
Summary of the invention
The purpose of this invention is to provide a kind of aging process of multiple-catalytic agent in solution polymerization system and equipment; under the program that presets, earlier each component of catalyzer is injected aging tank respectively; again by treatment processs such as ageing, dilution, prepolymerizations; make the catalyzer ageing process carrying out in order and under the controllable state, guarantee the stability of active centre quantity and character.In addition, catalyzer ageing process provided by the invention can make the active centre at low concentration, be sent to first still under the higher pumpage condition reposefully and participate in polyreaction, avoided in the process pipeline and the abnormal response bottom the first still, improved the activity of polyreaction and the stability and the quality product of technological operation.
Indication multicomponent catalyst of the present invention comprises catalyzer such as binary, ternary, quaternary, is the implementation method of example explanation the object of the invention below with the three-way catalyst:
The catalyzer volume pump a of catalyzer maturing equipment of the present invention, catalyzer volume pump b, catalyzer volume pump c are for annotating plug formula volume pump, entrance end is connected with catalyst tank a, catalyst tank b, catalyst tank c respectively, and exit end is connected with catalyzer tank enter hole a, catalyzer tank enter hole b, the catalyzer tank enter hole c of aging tank a, aging tank b by valve c, valve d, valve e, valve i, valve j, valve k respectively; Ageing catalyzer volume pump is a diaphragm metering pump, and entrance end goes out a jar hole by valve f, valve l with the ageing catalyzer of aging tank a, aging tank b and is connected, and exit end is connected with first still of polyreaction or intermittence type polymerization reactor; The monomer volume pump is for annotating plug formula volume pump, and an end is connected with the monomer jar, and the other end is by valve b, valve h, and mixing tank a, mixing tank b are connected with aging tank a, 1/3-1/4 place import of aging tank b top; The solvent oil volume pump is for annotating plug formula volume pump, and an end is connected with the solvent oil tank, and the other end is by valve a, valve g, and mixing tank a, mixing tank b are connected with aging tank a, 1/3-1/4 place import of aging tank b top; Valve a, valve b, valve c, valve d, valve e, valve f, valve g, valve h, valve i, valve j, valve k, valve l is the controlled non-return valve of integral type, stirring rake is an anchor formula stirring rake, aging tank a, aging tank b bottom is respectively sharp spill a, point spill b, stirring rake a in jar, stirring rake b bottom is respectively sharp cone distal a, sharp cone distal b, make the sharp cone distal a of stirring rake bottom, sharp cone distal b tries one's best near the sharp spill a of aging tank bottom, point spill b, guarantee to make stirring rake a simultaneously, do not scrape wall during stirring rake b twirl, the ageing catalyzer goes out a jar hole and is located at aging tank a, aging tank b bottom centre, catalyzer tank enter hole a, catalyzer tank enter hole b, catalyzer tank enter hole c arranges near also going out jar hole around the ageing catalyzer; The installation of valve c, valve d, valve valve e, valve i, valve j, valve k, valve f, valve l is respectively near aging tank a, aging tank b bottom, and the installation of valve a, valve g, valve b, valve h is respectively by aging tank a, 1/3-1/4 place, aging tank b top.
Solution polymerization system multicomponent catalyst ageing schedule of operation of the present invention mainly is divided into following two kinds:
1, ageing → dilution → prepolymerization ageing schedule of operation;
In the polymerization system of anhydrous and oxygen-free, start stirring rake a, elder generation is with catalyst tank a under the program that presets, catalyst tank b, the catalyst solution of different concns injects aging tank a respectively in the catalyst tank c, ageing 0-60 minutes, after waiting to produce the ideal activity center, open valve a immediately, starting the solvent oil volume pump added certain amount of solvent oil in the solvent oil tank among the aging tank a in 10 minutes, catalyzer that ageing is finished and the dilution of the active centre of generation were also stirred 5-30 minutes, institute's solubilizing agent oil is about 5:1-20:1 with catalyzer total amount volume ratio, stop the solvent oil volume pump, open valve b, start to add monomer volume pump and solvent oil volume pump mix a certain amount of solvent oil in a certain amount of monomer in the monomer jar and the solvent oil tank through static mixer a after and carry out the prepolymerization reaction among the aging tank a, solvent oil and the monomer volume ratio of this moment are 1:1-5:1, amount of monomer should be as the criterion can cause prepolymerization reaction, is difficult for too much or very few, and the liquid level of aging tank a is controlled at 1/2-2/3.Stop monomer volume pump and solvent oil volume pump, close valve b and valve a, after 0-30 minutes, the prepolymerization reaction finishes, and squeezes into the polymerization activity center in the first still of polymerization and participates in follow-up polyreaction by ageing catalyst transport volume pump; When treating that catalyzer among the aging tank a also has 1-2 hours consumption, begin to carry out the processing such as ageing, dilution and prepolymerization of catalyzer among the aging tank b, when treating that catalyzer among the aging tank a uses up, close valve f, open valve l simultaneously, switch to aging tank b, so circulation, guaranteeing provides the polymerization activity center steadily, continuously to first still.
2, ageing → prepolymerization → dilution ageing schedule of operation;
In the polymerization system of anhydrous and oxygen-free; start stirring rake a; elder generation is with catalyst tank a under the program that presets; catalyst tank b; the catalyst solution of different concns injects aging tank a respectively in the catalyst tank c; ageing 0-60 minutes; after waiting to produce the ideal activity center; open valve a and valve b; start to add monomer volume pump and solvent oil volume pump mix a certain amount of solvent oil in a certain amount of monomer in the monomer jar and the solvent oil tank through static mixer a after and carry out the prepolymerization reaction among the aging tank a; solvent oil and monomer volume ratio are 1:1-5:1; overall control can be combined in complete pre-polymerization; stop monomer volume pump and solvent oil volume pump; close valve b and valve a, after 0-30 minutes, the prepolymerization reaction finishes; though prepolymerization this moment product has played the certain protection effect to the active centre; reduced the possibility that side reaction takes place, but for heterogeneous active centre, grown the time; the prepolymerization product also can be assembled sedimentation, so also need further dilution process.Open valve a, starting the solvent oil volume pump added the certain amount of solvent oil in the solvent oil tank among the aging tank a in 10 minutes, the prepolymerization product is diluted and fully stirring, institute's solubilizing agent oil is about 5:1-20:1 with catalyzer total amount volume ratio, the liquid level of aging tank a is controlled at 1/2-2/3, stop the solvent oil volume pump, close valve a, continued stir about 5-30 minutes.Squeeze into the polymerization activity center in the first still of polymerization and participate in follow-up polyreaction by ageing catalyst transport volume pump, when treating that catalyzer among the aging tank a also has 1-2 hours consumption, begin to carry out ageing, prepolymerization and the dilution process of catalyzer among the aging tank b, when treating that catalyzer among the aging tank a uses up, close valve f, open valve l simultaneously, switch to aging tank b, so circulation, guaranteeing provides the polymerization activity center steadily, continuously to first still.
Above-mentioned two kinds of ageing programs suppose that all the active centre is to produce after each catalyst component meets simultaneously, the catalyzer ageing that has usually is divided into some steps, with above-mentioned three-way catalyst is example, two kinds of catalyzer wherein are reaction earlier, and its product is again with the third catalyst reaction and produce the effective active center.At this moment, catalyzer volume pump a, catalyzer volume pump b, catalyzer volume pump c can not open and the corresponding catalyzer of pumping advances aging tank a, aging tank b carries out ageing synchronously by method recited above, carry out ageing but step by step corresponding catalyzer is sent among aging tank a, the aging tank b according to the program that presets.According to practical situation, can carry out prepolymerization and dilution simultaneously after the ageing, also can only dilute and do not carry out prepolymerization, concrete ageing program is seen embodiment.
This method major advantage shows that it not only can satisfy the requirement of various ageing concentration of catalyzer and digestion time, avoided simultaneously the generation of the bad side reaction of gathering sedimentation of causing or the like again because digestion time, ageing concentration do not match, ageing is carried out fully, to obtain all satisfied active centre of quantity and character in controllable program with in the time.The solvent oil thinning is disperseed the active centre uniformly, has reduced concentration, has avoided it to proceed the generation of other untoward reaction; And the generation of prepolymerization reaction, the prepolymerization product that each active centre is generated surrounds and protects, and has played the effect at stabilizing active center.In addition, after dilution and prepolymerization reaction, catalyst concn among aging tank a, the b reduces greatly, so just can under higher metering and low concentration, carry out pumping, not only reduced the error in the metering in the catalyzer pumping process, and reduced the residence time of catalyzer in pipeline, and reduced the probability that phenomenons such as back-mixing, polymerization, obstruction take place in the pipeline, inhibition has also been played in the implode that first still bottom takes place.
Catalyzer digestion time and catalyst property among the present invention, concentration are relevant, can be by lab scale test conclusive evidence, and digestion time generally is controlled in 2-30 minutes to well, and is oversize, lack and all be difficult for finding accurately desirable ageing point very much.
Before each component ageing of solution polymerization system multicomponent catalyst of the present invention is homogeneous phase solution, and polymerization single polymerization monomer is liquid or liquefied gas.
Description of drawings
Fig. 1 is an aging process of multiple-catalytic agent in solution polymerization system equipment flowsheet synoptic diagram of the present invention.
Fig. 2 is aging tank a of the present invention, aging tank b inner bottom part structure schematic top plan view.
Fig. 3 is aging tank a of the present invention, aging tank b outer bottom structure planing surface synoptic diagram.
Wherein, 1-monomer volume pump, 2-catalyzer volume pump a, 3-catalyst tank a, 4-mixing tank a, 5-catalyzer volume pump b, 6-catalyst tank b, the recessed a of 7-aging tank vertex (vertices), 8-catalyzer volume pump c, 9-catalyst tank c, 10-solvent oil volume pump, 11-mixing tank b, 12-valve a, 13-valve b, 14-aging tank a, 15-stirring rake a, 16-valve c, 17-valve d, 18-valve e, 19-stirring rake pointed cone a, 20-valve f, 21-ageing catalyzer volume pump, 22-valve g, 23-valve h, 24-aging tank b, 25-stirring rake b, 26-valve i, 27-valve j, 28-valve k, 29-stirring rake pointed cone b, 30-valve l, the recessed b of 31-aging tank vertex (vertices), 32-catalyzer tank enter hole a, 33-catalyzer tank enter hole b, 34-catalyzer tank enter hole c, 35-ageing catalyzer goes out a jar hole, A-monomer jar, B-solvent oil tank, first still of C-polyreaction or intermittence type polymerization reactor a, b.
Embodiment
The catalyzer volume pump a2 of catalyzer maturing equipment of the present invention, catalyzer volume pump b5, catalyzer volume pump c8 are for annotating plug formula volume pump, entrance end is connected with catalyst tank a3, catalyst tank b6, catalyst tank c9 respectively, and exit end is connected with catalyzer tank enter hole a32, catalyzer tank enter hole b33, the catalyzer tank enter hole c34 of aging tank a15, aging tank b24 by valve c16, valve d17, valve e18, valve i26, valve j27, valve k28 respectively; Ageing catalyzer volume pump 21 is a diaphragm metering pump, and entrance end goes out jar hole 35 by valve f20, valve 130 with the ageing catalyzer of aging tank a, aging tank b and is connected, and exit end is connected with first still of polyreaction or intermittence type polymerization reactor C; Monomer volume pump 1 is for annotating plug formula volume pump, and an end is connected with monomer jar A, and the other end is by valve b13, valve h23, and mixing tank a11, mixing tank b4 are connected with aging tank a, 1/3-1/4 place import of aging tank b top; Solvent oil volume pump 10 is for annotating plug formula volume pump, and an end is connected with solvent oil tank B, and the other end is by valve a12, valve g22, and mixing tank a, mixing tank b are connected with aging tank a, 1/3-1/4 place import of aging tank b top; Valve a, valve b, valve c, valve d, valve e, valve f, valve g, valve h, valve i, valve j, valve k, valve l is the controlled non-return valve of integral type, stirring rake is an anchor formula stirring rake, aging tank a14, aging tank b24 bottom is respectively sharp spill a7, point spill b31, stirring rake b15 in jar, stirring rake b25 bottom is respectively sharp cone distal a19, sharp cone distal b29, make the sharp cone distal a of stirring rake bottom, sharp cone distal b tries one's best near the sharp spill a of aging tank bottom, point spill b, guarantee to make stirring rake a simultaneously, do not scrape wall during stirring rake b twirl, the ageing catalyzer goes out jar hole 35 and is located at aging tank a, aging tank b bottom centre, catalyzer tank enter hole a32, catalyzer tank enter hole b33, catalyzer tank enter hole c34 arranges near also going out jar hole 35 around the ageing catalyzer; The installation of valve c, valve d, valve e, valve i, valve j, valve k, valve f, valve l is near aging tank a, aging tank b bottom, and the installation of valve a, valve g, valve b, valve h is by aging tank a, 1/3-1/4 place, aging tank b top.
The volume of aging tank a, b is 10 liters, diameter: height=1:2-1:4, and catalyst tank a, b, c volume are 1 liter, diameter: height=1:2-1:3.
Heterogeneous ageing process of solution polymerization system multicomponent catalyst and equipment embodiment are that example is illustrated with the polyreaction of the synthetic cis-1,4-polybutadiene rubber of rare earth catalyst, and technology is 20 liters, four still continuous polymerization techniques, sees embodiment 1,2.This catalyst system is made up of neodecanoic acid neodymium, diisobutylaluminium hydride and a chloro-di-isobutyl aluminum three-way catalyst.In this catalyst system, the active centre comprises heterogeneous and the homogeneous phase two states, and this ageing process with each component of catalyzer is relevant.Facts have proved, the polymerization activity in the heterogeneous active centre that " alkylation after the first chlorination " aging method obtains is the highest, take second place and " carrying out alkylation and chlorination simultaneously " aging method obtains the polymerization activity in homogeneous phase and heterogeneous two kinds of active centre, the polymerization activity in the homogeneous phase active centre that " first alkylation post chlorization " aging method obtains is minimum.Wherein, " alkylation after the first chlorination " aging method is meant that the neodecanoic acid neodymium catalyst elder generation and the chlorination reaction of a chloro-di-isobutyl aluminum catalyzer generate NdCl
3↓ afterwards, the alkylated reaction with the diisobutylaluminium hydride catalyzer generates heterogeneous active centre, i.e. Cl again
2-Nd-R ↓ process.
Polyreaction with poly-1 between solution polymerization system multicomponent catalyst homogeneous phase ageing process and equipment embodiment are synthesized with Fe-series catalyst is that example is illustrated, and technology is the polymerization technique that the two stills of 20 liter intermittent types switch, and sees embodiment 3.This catalyst system is made up of isocaprylic acid iron, diethyl phosphite, triisobutyl aluminium and triethyl aluminum four-way catalyst.In this catalyst system, the active centre is equal phase, the formation in active centre is that the aging method according to " generate earlier title complex carry out alkylation again " obtains, be that isocaprylic acid iron catalyst and diethyl phosphite catalyst reaction generate after the title complex Fe-P, carry out alkylated reaction simultaneously with triisobutyl Al catalysts and triethylaluminium catalyst again and generate homogeneous phase active centre P-(Fe) R
1R
2Process.
Embodiment 1
In the polymerization system of anhydrous and oxygen-free, start stirring rake a15, open valve c16, e18, ejector priming a2, c8, in 30 seconds with 120ml neodecanoic acid neodymium (1.0 * 10 in catalyst tank a3, the c9
-4Mol/ml) catalyzer and 160ml one chloro-di-isobutyl aluminum catalyzer (7 * 10
-4Mol/ml) solution is sent among the aging tank a14 synchronously, and termination of pumping a2, c8 afterwards close valve c16, e18, and valve d17 is opened in ageing 5 minutes, ejector priming b5, in 60 seconds with 500ml diisobutylaluminium hydride (6 * 10 in the catalyst tank b6
-4Mol/ml) catalyzer is sent among the aging tank a14, and termination of pumping b5 closes valve d17, ageing 5 minutes.Open valve a12, ejector priming 10 added 6220ml hexane solvent oil among the solvent oil tank B among the aging tank a14 in 10 minutes, and the catalyzer that termination of pumping 10, ageing finish and the active centre of generation are diluted and stirred 20 minutes.Open valve b13, ejector priming 1 and pump 10 carry out prepolymerization reaction among the adding aging tank a14 with 500ml hexane solvent oil among 500ml 1,3-butadiene monomer among the monomer jar A and the solvent oil tank B after static mixer 11 mixes, and termination of pumping 1 and pump 10 close valve b13 and valve a12.After 0-30 minutes, the prepolymerization reaction finishes, send in first still C with the 1000ml/h amount catalyzer handled well among the aging tank a14 and participate in follow-up polyreaction by pump 21,65 ℃ of first still kick off temperatures, 2,3,4 still jacket temperatures are 75 ℃, and each still pressure is about 0.4MPa, keeps 1 simultaneously, 3-divinylic monomer inlet amount 2.2kg/h, hexane solvent oil inlet amount 8.2kg/h.When treating that catalyzer among the aging tank a14 also has 1-2 hours consumption, begin to carry out the processing such as ageing, dilution and prepolymerization of catalyzer among the aging tank b24, when treating that catalyzer among the aging tank a14 uses up, close valve f20, open valve 130 simultaneously, switch to aging tank b24, switched once in average 8 hours, so circulation, guaranteeing provides the polymerization activity center steadily, continuously to first still C.
Under the condition of above-mentioned technology and equipment, continuous production 10 days is prepared mooney viscosity 47.3, cis-content 97.1%, number-average molecular weight 260,000, the cis-1,4-polybutadiene rubber 300kg ton of molecular weight distribution width 2.9.
Embodiment 2
In the polymerization system of anhydrous and oxygen-free, start stirring rake a15, open valve c16, e18, ejector priming a2, c8, in 30 seconds with 120ml neodecanoic acid neodymium (1.0 * 10 in catalyst tank a3, the c9
-4Mol/ml) catalyzer and 160ml one chloro-di-isobutyl aluminum catalyzer (7 * 10
-4Mol/ml) solution is sent among the aging tank a14 synchronously, and termination of pumping a2, c8 afterwards close valve c16, e18, and valve d17 is opened in ageing 5 minutes, ejector priming b5, in 60 seconds with 500ml diisobutylaluminium hydride (6 * 10 in the catalyst tank b6
-4Mol/ml) catalyzer is sent among the aging tank a14, and termination of pumping b5 closes valve d17, ageing 5 minutes.Open valve b13 and valve a12, ejector priming 1 and pump 10 are with 110ml 1 among the monomer jar A, the 110ml hexane solvent oil carries out the prepolymerization reaction among the adding aging tank a14 among 3-divinylic monomer and the solvent oil tank B after static mixer 11 mixes, termination of pumping 1 and pump 10, close valve b13 and valve a12, after 0-30 minutes, the prepolymerization reaction finishes.Open valve a12, ejector priming 10 added 7000ml hexane solvent oil among the solvent oil tank B among the aging tank a14 in 10 minutes, and valve a12 is closed in termination of pumping 10, diluted and stirred 20 minutes.Send in first still C with the 1000ml/h amount catalyzer handled well among the aging tank a14 and participate in follow-up polyreaction by pump 21,65 ℃ of first still kick off temperatures, 2,3,4 still jacket temperatures are 75 ℃, each still pressure is about 0.4MPa, keep 1 simultaneously, 3-divinylic monomer inlet amount 2.2kg/h, hexane solvent oil inlet amount 8.2kg/h.When treating that catalyzer among the aging tank a14 also has 1-2 hours consumption, begin to carry out the processing such as ageing, dilution and prepolymerization of catalyzer among the aging tank b24, when treating that catalyzer among the aging tank a14 uses up, close valve f20, open valve 130 simultaneously, switch to aging tank b24, switched once in average 8 hours, so circulation, guaranteeing provides the polymerization activity center steadily, continuously to first still C.
Under the condition of above-mentioned improvement technology and equipment, continuous production 10 days is prepared mooney viscosity 47.1, cis-content 97.3%, number-average molecular weight 250,000, the cis-1,4-polybutadiene rubber 300kg of molecular weight distribution width 2.8.
Embodiment 3
In the polymerization system of anhydrous and oxygen-free, start stirring rake a15, open valve c16, e18, ejector priming a2, c8, in 20 seconds with the different eo-acid iron (2 * 10 of 200ml in catalyst tank a3, the c9
-5Mol/ml) catalyzer and 250ml diethyl phosphite catalyzer (5 * 10
-5Mol/ml) solution is sent among the aging tank a14 synchronously, and termination of pumping a2, c8 afterwards close valve c16, e18, and valve d17 is opened in ageing 2 minutes, ejector priming b5, in 15 seconds with the prior equal-volume blended of 140ml triisobutyl Al catalysts (4 * 10 in the catalyst tank b6
-4Mol/ml) and triethylaluminium catalyst (6 * 10
-4Mol/ml) add among the aging tank a14, termination of pumping b5 closes valve d17, ageing 10 minutes.Open valve a12, ejector priming 10 added 7410ml hexane solvent oil among the solvent oil tank B among the aging tank a14 in 10 minutes, and valve a12 is closed in termination of pumping 10, diluted and stirred 20 minutes.By pump 21 catalyzer of handling well among the aging tank a14 is sent among intermittence type polymerization still aC or the intermittence type polymerization still bC and to be participated in polyreaction, wherein every still add-on is 1000ml, and 1, the every still add-on of 3-divinylic monomer is 1.8kg, the hexane solvent oil add-on is 8.6kg, 80 ℃ of polymeric kettle kick off temperatures, pressure is less than 0.5MPa.When treating that catalyzer among the aging tank a14 also has 1-2 hours consumption, begin to carry out ageing, the dilution process of catalyzer among the aging tank b24, when treating that catalyzer among the aging tank a14 uses up, close valve f20, open valve 130 simultaneously, switch to aging tank b24, so circulation, assurance stably provides the polymerization activity center to intermittence type polymerization still aC or intermittence type polymerization still bC, and on average the catalytic amount in each aging tank can provide batch still four secondary response consumptions, and each polymerization cycle is 2 hours.
Under the condition of above-mentioned improvement technology and equipment, continuous production 3 days is prepared 126.8 ℃ of fusing points, 1,2-content 83.3%, unison 75%, between number-average molecular weight 230,000 with poly-1 product 100kg.
Claims (3)
1. solution polymerization system multicomponent catalyst maturing equipment, it is characterized in that: the catalyzer volume pump a of catalyzer maturing equipment, catalyzer volume pump b, catalyzer volume pump c are for annotating plug formula volume pump, entrance end is connected with catalyst tank a, catalyst tank b, catalyst tank c respectively, and exit end is connected with catalyzer tank enter hole a, catalyzer tank enter hole b, the catalyzer tank enter hole c of aging tank a, aging tank b by valve c, valve d, valve e, valve i, valve j, valve k respectively; Ageing catalyzer volume pump is a diaphragm metering pump, and entrance end goes out a jar hole by valve f, valve l with the ageing catalyzer of aging tank a, aging tank b and is connected, and exit end is connected with first still of polyreaction or intermittence type polymerization reactor; The monomer volume pump is for annotating plug formula volume pump, and an end is connected with the monomer jar, and the other end is by valve b, valve h, and mixing tank a, mixing tank b are connected with aging tank a, the 1/3-1/4 place import of aging tank b top; The solvent oil volume pump is for annotating plug formula volume pump, and an end is connected with the solvent oil tank, and the other end is by valve a, valve g, and mixing tank a, mixing tank b are connected with aging tank a, the 1/3-1/4 place import of aging tank b top; Valve a, valve b, valve c, valve d, valve e, valve f, valve g, valve h, valve i, valve j, valve k, valve l is the controlled non-return valve of integral type, stirring rake is an anchor formula stirring rake, aging tank a, aging tank b bottom is respectively sharp spill a, point spill b, stirring rake b in jar, stirring rake b bottom is respectively sharp cone distal a, sharp cone distal b, make the sharp cone distal a of stirring rake bottom, sharp cone distal b tries one's best near the sharp spill a of aging tank bottom, point spill b, guarantee to make stirring rake a simultaneously, do not scrape wall during stirring rake b twirl, the ageing catalyzer goes out a jar hole and is located at aging tank a, aging tank b bottom centre, catalyzer tank enter hole a, catalyzer tank enter hole b, catalyzer tank enter hole c arranges near also going out jar hole around the ageing catalyzer; The installation of valve c, valve d, valve e, valve i, valve j, valve k, valve f, valve l is respectively near aging tank a, aging tank b bottom, and the installation of valve a, valve g, valve b, valve h is respectively by aging tank a, 1/3-1/4 place, aging tank b top.
2. the ageing process of a kind of solution polymerization system multicomponent catalyst maturing equipment according to claim 1, it is characterized in that: in the polymerization system of anhydrous and oxygen-free, start stirring rake a, elder generation is with catalyst tank a under the program that presets, catalyst tank b, the catalyst solution of different concns injects aging tank a respectively in the catalyst tank c, ageing 0-60 minute, after waiting to produce the ideal activity center, open valve a immediately, starting the solvent oil volume pump added certain amount of solvent oil in the solvent oil tank among the aging tank a in 10 minutes, catalyzer that ageing is finished and the dilution of the active centre of generation were also stirred 5-30 minute, institute's solubilizing agent oil is 5 with catalyzer total amount volume ratio: 1-20: 1, stop the solvent oil volume pump, open valve b, start to add monomer volume pump and solvent oil volume pump mix a certain amount of solvent oil in a certain amount of monomer in the monomer jar and the solvent oil tank through static mixer a after and carry out the prepolymerization reaction among the aging tank a, solvent oil and the monomer volume ratio of this moment are 1: 1-5: 1, amount of monomer should be as the criterion can cause the prepolymerization reaction, unsuitable too much or very few, the liquid level of aging tank a is controlled at 1/2-2/3; Stop monomer volume pump and solvent oil volume pump, close valve b and valve a, after 0-30 minute, the prepolymerization reaction finishes, and squeezes into the polymerization activity center in the first still of polymerization and participates in follow-up polyreaction by ageing catalyst transport volume pump; When treating that catalyzer among the aging tank a also has 1-2 hour consumption, the ageing, dilution and the prepolymerization that begin to carry out catalyzer among the aging tank b are handled, when treating that catalyzer among the aging tank a uses up, close valve f, open valve 1 simultaneously, switch to aging tank b, so circulation, guaranteeing provides the polymerization activity center steadily, continuously to first still.
3. the ageing process of a kind of solution polymerization system multicomponent catalyst maturing equipment according to claim 1, it is characterized in that: in the polymerization system of anhydrous and oxygen-free, start stirring rake a, elder generation is with catalyst tank a under the program that presets, catalyst tank b, the catalyst solution of different concns injects aging tank a respectively in the catalyst tank c, ageing 0-60 minute, after waiting to produce the ideal activity center, open valve a and valve b, start to add monomer volume pump and solvent oil volume pump mix a certain amount of solvent oil in a certain amount of monomer in the monomer jar and the solvent oil tank through static mixer a after and carry out the prepolymerization reaction among the aging tank a, solvent oil and monomer volume ratio are 1: 1-5: 1, overall control can be combined in complete pre-polymerization, stop monomer volume pump and solvent oil volume pump, close valve b and valve a, after 0-30 minute, the prepolymerization reaction finishes, though prepolymerization this moment product has played the certain protection effect to the active centre, reduced the possibility that side reaction takes place, but for heterogeneous active centre, time has been grown, the prepolymerization product also can be assembled sedimentation, so also need further dilution process; Open valve a, starting the solvent oil volume pump added the certain amount of solvent oil in the solvent oil tank among the aging tank a in 10 minutes, the prepolymerization product is diluted and fully stirring, institute's solubilizing agent oil is 5 with catalyzer total amount volume ratio: 1-20: 1, the liquid level of aging tank a is controlled at 1/2-2/3, stop the solvent oil volume pump, close valve a, continue to stir 5-30 minute; Squeeze into the polymerization activity center in the first still of polymerization and participate in follow-up polyreaction by ageing catalyst transport volume pump, when treating that catalyzer among the aging tank a also has 1-2 hour consumption, begin to carry out ageing, prepolymerization and the dilution process of catalyzer among the aging tank b, when treating that catalyzer among the aging tank a uses up, close valve f, open valve l simultaneously, switch to aging tank b, so circulation, guaranteeing provides the polymerization activity center steadily, continuously to first still.
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