CN104268434B - A kind of prediction technique of polyolefin microstructure - Google Patents
A kind of prediction technique of polyolefin microstructure Download PDFInfo
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Abstract
The invention discloses a kind of prediction techniques of polyolefin microstructure, for ethylene polymerisation process, using short-chain branch distribution with molecular weight distribution simultaneously as the micro-quality index of polyethylene.Average molecular weight, average co-monomer content and molecular weight distribution, the short-chain branch that this method calculates separately polyolefin using Moment Methods with instantaneous location mode are distributed.The method of the present invention is suitable for a variety of polyolefin production processes, and interval, semicontinuous or continuous mode of operation can be used.Compared with traditional analog technology, this method is beneficial in that the prediction that the distribution of polymer short-chain branch may be implemented, and can be applied to control, optimization and the design of new product, the exploitation of polymerization process.
Description
Technical field
The invention belongs to the modelings of polymerization process and analogue technique field, are related to a kind of prediction side of polyolefin microstructure
Method, more particularly to a kind of prediction technique of polyethylene short-chain branch distribution.
Background technology
Often using melt index and density as the quality index of product in polyolefin industry production, but both of which right and wrong
The property of Chang Hongguan only reflects the average content of the average molecular weight and co-monomer of polymer.With same melt index and close
The product of degree, micro molecule structure may but greatly differ from each other, and mechanical performance and processing performance also differ huge.Reason is to gather
There is alkene complicated chain structure such as molecular weight distribution, short-chain branch to be distributed, and the fine knot such as the distribution of copolymerization composition, sequence distribution
Structure.Just it is that these microstructures play conclusive effect to the end-use properties and processing performance of polyolefin.With highly dense
It spends for polyvinyl piping materials, its processing performance and resistance to slow crack growth performance depend on molecular weight distribution and short-chain branch point
Cloth.Therefore, it develops, produce the especially high-end trade mark of polyolefin new material, PP Pipe Compound, need to carry out its chain structure stringent control
System.However, the molecular weight distribution isodesmic structure of polyolefin can not on-line checking, this give polymeric articles quality real-time control band
Challenge is carried out.Stringent mathematical description carries out industrial polymerisation device using advanced process model building and analogue technique, to molecule
Amount distribution isodesmic structure makes Accurate Prediction, is the important means for realizing polyolefin microstructure hard measurement.
Chinese patent CN 201310659270, CN 201310658747, CN201310658947,
CN201310659245, CN201310659327, CN201310658680, CN201410128990 are counted for melt index
It calculates.United States Patent (USP) US 5687090 discloses a kind of calculating polymer average properties such as average molecular weight, average co-monomer content
Method.It makes a prediction to the average molecular weight of polymer, melt index, density etc., it can be to the trade mark in industrial production really
Fixed and product macroscopic quality control brings certain help, but can not fully understand the chain structure information of polyolefin, to
It is unable to control final products performance.United States Patent (USP) US 6093211 describe can predict polymer molecular structure such as molecular weight and
Its modeling method for being distributed, copolymerization composition and its being distributed, and establish associated analog device.But this method is confined to can not be to short branch
Chain distribution is made a prediction.
Above-mentioned document is pre- only for carry out such as the average molecular weight, polydispersity index, molecular weight distribution of polyolefin with patent
It surveys, without reference to the calculating of short-chain branch distribution.In fact, short-chain branch distribution is high density polyethylene (HDPE), linear low density polyethylene
Particularly important a kind of chain structure, to the length applied to for example high-grade fuel gas polyethylene tube material of high performance structures Material Field
Phase performance has decisive impact.By carrying out mathematical modeling to industrial continuous polymerization unit, the short branch of polyethylene is realized
The Accurate Prediction of chain distribution can be that Dynamic matrix control, optimization and the exploitation of high-performance new grades product of olefin polymerization process carry
For new technology, to improve the economic benefit of factory.
The present invention is directed to ethylene polymerisation process, proposes process model building and mould that prediction target is distributed as with polyethylene short-chain branch
Quasi- method provides new tool for the control and cutting out for end-use properties of polyolefin industry product quality.
Invention content
The object of the present invention is to be directed to ethylene polymerisation process, existing analogue technique and routine business software only needle are overcome
Melt index, density, molecular weight distribution are predicted, cannot reflect the important chain structure of one kind --- the short-chain branch point of polyethylene
The deficiency of cloth provides a kind of prediction technique of polyethylene short-chain branch distribution.
Technical scheme is as follows：
A kind of prediction technique of polyolefin microstructure, includes the following steps：
Step 1：The mathematical model of olefin polymerization process is established, including：
1) form, operating method and condition of polymer reactor are determined；
Commercial olefin polymerization device includes tank reactor, fluidized-bed reactor, annular-pipe reactor, horizontal type agitated bed reaction
Device, vertical mixing bed reactor etc.；Mode of operation has the equal a variety of phases of slurry phase, ontology phase, gas phase, supercritical fluid.
Different types of reactor can regard continuous stirred tank reactor (CSTR) (Fig. 2) or piston flow reactor (PFR) as, or with
Both upper combination.Determine the conditions such as the volume, operation temperature, operating pressure of reactor and reactor into and out of logistics information.
The specific object of the present invention is double-reactor tandem process, is described using two CSTR tandem compounds；
2) polymerization reaction mechanism and kinetics equation are determined；
Olefinic polyreaction mechanism includes mainly：The activation of catalyst activity position, chain initiation, chain growth, chain tra nsfer, activity
The conversion of position and the inactivation of active sites.The activation of catalyst activity position include co-catalyst, hydrogen, monomer activation with
And self-activation etc.；Chain causes the chaininitiation of predominantly monomer；Chain growth includes self-propagation and intersection chain growth；Chain tra nsfer packet
Include to hydrogen chain tra nsfer, to monomer chain tra nsfer, to co-catalyst chain tra nsfer, to solvent chain tra nsfer and from transfer etc.；Active sites
Conversion includes that hydrogen, co-catalyst, solvent, monomer, the transformation of poisonous substance and inverting etc., active sites inactivations include hydrogen
Gas, monomer, solvent, co-catalyst, the deactivation of poisonous substance and oneself inactivation etc..According to the above mechanism or its simplify mechanism,
Write out primitive kinetics equation.The specific polymerization reaction mechanism that the present invention uses is as shown in table 1, considers that catalyst is in multiple activity
The case where position.The meaning of each symbol is illustrated in symbol description in table.
1 olefinic polyreaction mechanism of table
3) consumption of each reactant or the moment equation of generating rate and chain structure are determined；
According to the polymerization reaction mechanism and Moment Methods of table 1, can get each small molecule reaction object through mathematical derivation, (monomer is total to
Monomer, hydrogen, co-catalyst) wear rate and with catalyst, the relevant moment equation of polymer, as shown in table 2.
2 each reactant consumption of table or generating rate and moment equation
Wherein each rank square is defined as follows：
The i rank squares with monomer 1 for the living chain of end generated in j active sites：
The i rank squares with monomer 2 for the living chain of end generated in j active sites：
The i rank squares of the dead polymers generated in j active sites：
4) thermal transport cofficients method and parameter are determined；
Adoption status equation describes the physical property of polymerization system component and balances each other.State equation parameter is by data in literature and reality
It tests Data correction and determines to be suitable for described industrial polymerisation system；
5) reactor model is established, the mass balance of process is carried out；
Using reactor as object, mass balance is made to reactor, it is as follows to the specific balance equation of any reactant：
Step 2：The mathematical model that solution procedure 1 is established, the average molecular weight and average co-monomer for calculating polymer contain
Amount；
The number-average molecular weight of each active sites generation polymer of catalyst and the calculation formula of weight average molecular weight are：
WhereinIt is the average molecular weight that j active sites generate repeating unit of copolymer, is calculated using following formula：
WhereinIt is the molar average content that j active sites generate monomer i in copolymer, mw,iIt is the molecular weight of monomer i,
NmIt is the type of monomer.It can be acquired according to following equation：
Step 3：The average molecular weight of polymer obtained by step 2 and average co-monomer content, using instantaneous distribution
Method calculates short-chain branch distribution and molecular weight distribution；
The description of Flory most Probable distrebutions can be used in the molecular weight distribution that polymer is generated in j active sites：
For more sited catalysts, total molecular weight distribution is that polymer molecular weight distribution is generated on each catalyst
Superposition：
The average short-chain branch content of polymer can be calculated by average co-monomer content using following formula in each active sites：
Wherein subscript 2 and ncThe carbon atom number of co-monomer and co-monomer is represented, then short-chain branch distribution can be calculated by following formula：
The polyolefin includes high density polyethylene (HDPE) and linear low density polyethylene, and the microstructure is short-chain branch distribution
With molecular weight distribution.
The olefin polymerization process is the ethylene polymerisation process using coordination polymerization catalysts.
The mathematical model calculating of step 1 includes average molecular weight, average co-monomer content, transient molecular amount distribution, instantaneously
Short-chain branch distribution, accumulates the information that short-chain branch is distributed in interior polymer molecular structure at accumulation molecular weight distribution.
The mathematical model of step 1 calculates and tracks random time, the polymer molecular structure information of arbitrary reactor.
The mathematical model of step 1, it includes using to write program or software to establish with the method solved.
The implementation of the ethylene polymerisation process is slurry phase, solution phase or gas phase.
The paradigmatic system of the ethylene polymerisation process includes at least a reactor and its flow sheet equipment.
The operating method of the reactor used in the ethylene polymerisation process is continous way, semi continuous or intermittent.
The ethylene polymerisation process is using 1- butylene, 1- hexenes or 1- octenes or other forms being total to for polyethylene short-chain branch
Polycondensation monomer.
The reactor model of step 5 is the combination of CSTR, PFR or both of the above.
The reactor model of step 5 is the stable state or dynamic model of single or multiple reactor serial or parallel connections.
The prediction technique of the present invention is suitable for：(1) high density polyethylene (HDPE), linear low density polyethylene；(2) polycomplexation is used
Close the ethylene polymerisation process of catalyst；(3) use co-monomer for the ethylene copolymer of the alpha-olefins such as 1- butylene, 1- hexenes, 1- octenes
Conjunction process；(4) implementation of polymerization process can be slurry phase, solution phase, gas phase；(5) form of reactor can be connected
Interval, semicontinuous or company can be used in the combination of continuous stirred tank reactor (CSTR), piston flow reactor (PFR) or both of the above
Continuous mode of operation.
Compared with existing analogue technique, advantageous effect is the present invention：
1) present invention realizes under the premise of given catalyst and polymerization process condition, and the molecule of polyethylene is calculated
Amount distribution is distributed with short-chain branch.
2) present invention could apply to the control of product quality of industrial continuous polymerization process, optimization and polymeric articles knots
The design of structure shortens the time of exploitation new grades polymer, to increase economic efficiency.
3) principle of the invention is simply clear, is easy to understand and implements, and is easy to computer programming or is simulated using software, is adapted to
It is wide.
The present invention will be described in detail With reference to embodiment.The scope of the present invention is not with specific embodiment party
Formula is limited, but is limited by the scope of the claims.
Description of the drawings
Fig. 1 is the modeling method schematic diagram of the present invention；
Fig. 2 is two kettles series connection continuous stirred tank reactor model (CSTR) schematic diagram；
Fig. 3 is the short-chain branch distribution and molecule that two kettle series polymerizations technique co-monomer of ethylene is added in a second reactor
Measure the prediction result schematic diagram of distribution；
Fig. 4 is the short-chain branch distribution and divide that two kettle series polymerizations technique co-monomer of ethylene is added in first reactor
The analog result schematic diagram of son amount distribution；
Fig. 5 is the short-chain branch distribution simulation result schematic diagram of polyethylene in single polymer reactor.
Specific implementation mode
Example given below rather than is limited the invention in order to illustrate the present invention.
Embodiment 1
Fig. 1 is the modeling method schematic diagram of the present invention；Fig. 2 is that two kettles series connection continuous stirred tank reactor model (CSTR) shows
It is intended to.
The object of the present embodiment is the high density polyethylene (HDPE) that the double kettle series polymerizations reactors of ethylene produce bimodal distribution
(HDPE), catalyst is Ziegler-Natta titaniums system magnesium chloride load catalyst, steady state operation.The operating pressure of first kettle,
Operation temperature be respectively 64bar, 95 DEG C, no co-monomer, high hydrogen concentration, carry out Slurry-Phase Ethylene homopolymerization reaction.Second
Operating pressure, the operation temperature of kettle be respectively 20bar, 85 DEG C, have co-monomer 1- butylene, a low hydrogen gas concentration, carry out ethylene -1- fourths
Alkene copolymerization.According to the equation of table 2 and formula (1)~(12), calculated first using commercialized Polymer Plus
Software establishes the steady-state model of process, seeks the yield of each reactor and the average molecular weight of product and average co-monomer contains
Amount；Then, molecular weight distribution is calculated using the method being instantaneously distributed to be distributed with short-chain branch.The results are shown in Figure 3.
Fig. 3 the result shows that, the distribution of the polyethylene short-chain branch of prediction and molecular weight distribution and use GPC-FIIR (gel infiltrations
Chromatography and infrared combination) test result coincide it is preferable, it was demonstrated that the method can be produced with Accurate Prediction industrial ethylene polymerization process
The short-chain branch of product is distributed and molecular weight distribution.
Embodiment 2
The object of the present embodiment is the high density polyethylene (HDPE) that the double kettle series polymerizations reactors of ethylene produce bimodal distribution
(HDPE), catalyst is Ziegler-Natta titaniums system magnesium chloride load catalyst, steady state operation.The operating pressure of first kettle,
Operation temperature be respectively 64bar, 95 DEG C, have co-monomer 1- butylene, a high hydrogen concentration, carry out Slurry-Phase Ethylene -1- butenes
Close reaction.Operating pressure, the operation temperature of second kettle be respectively 20bar, 85 DEG C, no co-monomer, low hydrogen gas concentration, carry out second
Polyamino alkenyl closes reaction.According to the equation of table 2 and formula (1)~(12), first calculated using commercialized Polymer Plus soft
Part establishes the steady-state model of process, calculates the yield of each reactor and the average molecular weight of product and average co-monomer contains
Amount；Then, molecular weight distribution is calculated using the method being instantaneously distributed to be distributed with short-chain branch.The results are shown in Figure 4.
The analog result of Fig. 4 shows poly- under the conditions of the prediction technique can calculate two kettle tandem process different operations
Ethylene short-chain branch is distributed and molecular weight distribution.
Embodiment 3
The object of the present embodiment is the high density polyethylene (HDPE) (HDPE) of the single polymer reactor production of ethylene, and catalyst is
Ziegler-Natta titaniums system magnesium chloride load catalyst, steady state operation.Operating pressure, operation temperature be respectively 19bar, 80 DEG C,
There are co-monomer, low hydrogen gas concentration, carries out ethylene -1- butylene gas phase polymerizations.According to the equation of table 2 and formula (1)~
(12), the steady-state model that process is first established using commercialized Polymer Plus software for calculation, calculates the production of each reactor
The average molecular weight and average co-monomer content of amount and product；Then, molecular weight distribution is calculated using the method being instantaneously distributed
It is distributed with short-chain branch.The results are shown in Figure 5.
The analog result of Fig. 5 shows that the prediction technique can calculate polyethylene short-chain branch point prepared by single reactor
Cloth and molecular weight distribution.
Abbreviation explanation：
A co-catalysts, AlEt3
CD(j) catalyst of j active sites inactivation
Dn(j) the dead polymers of a length of n of j active sites chain
J active sites generate the molar average content of monomer i in copolymer
kdi(j) j active sites end is the decay rate constants of the living chain of monomer i, 1/s
ki1(j) initiation rate constant of j active sites monomer 1, L/ (mol s)
ki2(j) initiation rate constant of j active sites monomer 2, L/ (mol s)
kpij(j) j active sites end is the propagationrate constant of monomer j accesses on the living chain of monomer i, L/ (mol
s)
ktHi(j) j active sites end is the living chain of monomer i to the rate constant of hydrogen chain tra nsfer, L0.5/(mol0.5s)
ktij(j) j active sites end is the living chain of monomer i to monomer j chain tra nsfer rate constants, L/ (mol s)
M (j) j active sites generate the mass fraction that polymer accounts for
mw molecular weight of monomer
mw,iThe molecular weight of monomer i
J active sites generate the average molecular weight of repetitive unit in polymer
The molecular weight of MW polymer, (1,2,3 ... ∞)
J active sites generate the number-average molecular weight of polymer
J active sites generate the weight average molecular weight of polymer
ncThe number of carbon atom in co-monomer
N activity bits numbers
NmNumber of monomers
P0(j) the empty active sites of j active sites
Pn,i(j) j active sites end is the living chain of a length of n of monomer i chains
qin,iSubstance i feed rates, m3/s
qout,iSubstance i discharging flows, m3/s
RiThe generating rate of substance i
SP(j) j active sites lateral reactivity position
J active sites generate short-chain branch average content in polymer
V reaction volumes, m3
wlogMW(j) j active sites generate the molecular weight distribution of polymer
WlogMWMore sited catalysts prepare the total molecular weight distribution of polymer
YiSubstance i
[A]Cocatalyst concentration, mol/L
[H2]Density of hydrogen, mol/L
[Mi]The concentration of monomer i, mol/L.
Claims (6)
1. a kind of prediction technique of polyolefin microstructure, which is characterized in that the prediction technique includes the following steps：
Step 1：The mathematical model of olefin polymerization process is established, including：
1) form, operating method and condition of polymer reactor are determined；
2) polymerization reaction mechanism and kinetics equation are determined；
3) consumption of each reactant or the moment equation of generating rate and chain structure are determined；
4) thermal transport cofficients method and parameter are determined；
5) reactor model is established, mass balance is carried out；
Step 2：The mathematical model that solution procedure 1 is established calculates the average molecular weight of polymer and average co-monomer content；
Step 3：Short-chain branch distribution and molecular weight point are calculated according to the method that the mechanism model of step 1 and probability statistics are combined
Cloth；
The polyolefin includes high density polyethylene (HDPE) and linear low density polyethylene, and the olefin polymerization process is using polycomplexation
The ethylene polymerisation process of catalyst is closed, the microstructure is short-chain branch distribution and molecular weight distribution；
It includes the average molecular weight of the generated polymer in each activated centre of catalyst that the mathematical model of the step 1, which calculates, is averaged
In co-monomer content, transient molecular amount are distributed, the distribution of instantaneous short-chain branch, accumulate molecular weight distribution, accumulation short-chain branch is distributed in
Polymer chain architecture parameter.
2. prediction technique according to claim 1, which is characterized in that the implementation of the ethylene polymerisation process is slurry
Phase, solution phase or gas phase.
3. prediction technique according to claim 1, which is characterized in that the reactor used in the ethylene polymerisation process
Operating method is continous way, semi continuous or intermittent.
4. prediction technique according to claim 1, which is characterized in that the ethylene polymerisation process using 1- butylene, 1- oneself
Alkene or 1- octenes form the comonomer of polyethylene short-chain branch.
5. prediction technique according to claim 1, which is characterized in that the reactor model of step 5 is that continuous stirred tank is anti-
Answer the combination of device, piston flow reactor or aforementioned the two.
6. prediction technique according to claim 1, which is characterized in that the reactor model of step 5 is single or multiple anti-
Answer the stable state or dynamic model of device serial or parallel connection.
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| 二元交互参数化PC-SAFT在超临界乙烯配位聚合体系相平衡计算中的应用;陈可冉 等;《化工学报》;20140110;第65卷(第6期);第1979-1986页 * |
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