CN108334734A - A kind of high-molecular copolymer degradation modeling and simulation method - Google Patents

A kind of high-molecular copolymer degradation modeling and simulation method Download PDF

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CN108334734A
CN108334734A CN201710785288.1A CN201710785288A CN108334734A CN 108334734 A CN108334734 A CN 108334734A CN 201710785288 A CN201710785288 A CN 201710785288A CN 108334734 A CN108334734 A CN 108334734A
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strand
fracture
shearing
cellular
copolymer
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CN108334734B (en
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张桃红
周绍楠
金戈愉
马瑞
李存芳
张德政
孙义
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University of Science and Technology Beijing USTB
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Abstract

The present invention provides a kind of high-molecular copolymer and degrades modeling and simulation method, can realize the emulation of the shear fracture of microcosmic lower strand to the model diffusion realization degradation process under macroscopical.The method includes：High-molecular copolymer is separated into cellular；Based on discrete obtained cellular, random selection participates in the strand of shearing；Ingredient based on copolymer establishes high-molecular copolymer strand shear fracture model, the model is used to determine the fracture position of the strand for participating in shearing in a probabilistic manner by roulette according to the fracture probability between ester bond unit in pre-set strand；The strand for participating in shearing is broken in the determining fracture position；After determining fracture position fracture, oligomer is diffused the strand for participating in shearing outward.The present invention relates to degradable high polymer material technical fields.

Description

A kind of high-molecular copolymer degradation modeling and simulation method
Technical field
The present invention relates to degradable high polymer material fields, particularly relate to a kind of high-molecular copolymer degradation modeling and simulation Method.
Background technology
In recent years, degradable macromolecule copolymer is widely used in life, such as the organizational project material in terms of medical treatment Material, drug release material, prostheses and implants and controlled drug delivery system etc..High-molecular copolymer belongs to high-molecular compound, high score Sub- compound refers to：The relative molecular weight mainly formed with Covalent bonding together by numerous atoms or atomic group is 10,000 or more Compound.
Difference of the different copolymer of copolymer than that can lead to its mechanical performance, biology performance, degradation property, can be by changing Become the different demands that the mode of its copolymerization ratios meets practical application to material.Whether the application of these different performance demands succeeds Whether controllable it is heavily dependent on degradation process.The degradation process of high-molecular copolymer is complicated, being total between different copolymer object Poly- ratio can generate variation over time during degradation.It can be with to the research of high molecular polymer degradation process It is divided into traditional experimental method and emerging computer modeling method, and the method for computer modeling just compensates for traditional reality The disadvantage of proved recipe method period length.But current computer modeling method is the modeling to the degradation process of macromolecule list polymers mostly Research, even if being related to copolymer, and two co-polymeric shares is treated as a monomer, not to total in degradation process Polymers ingredient modeled, is also not directed to the fault analysis of different copolymer strand.
Invention content
The technical problem to be solved in the present invention is to provide a kind of high-molecular copolymer degradation modeling and simulation methods, to solve High-molecular copolymer degradation model present in the prior art does not grind copolymer ingredient and copolymerization molecule chain break The problem of studying carefully.
In order to solve the above technical problems, the embodiment of the present invention provides a kind of high-molecular copolymer degradation modeling and simulation side Method, including：
High-molecular copolymer is separated into cellular；
Based on discrete obtained cellular, random selection participates in the strand of shearing；
Ingredient based on copolymer establishes high-molecular copolymer strand shear fracture model, and the model is used for according to pre- Fracture probability in the strand being first arranged between ester bond unit determines the participation shearing by roulette in a probabilistic manner The fracture position of strand；
The strand for participating in shearing is broken in the determining fracture position；
After determining fracture position fracture, oligomer is diffused the strand for participating in shearing outward.
Further, described based on discrete obtained cellular, the strand that random selection participates in shearing includes：
Based on discrete obtained cellular, strand and the shear fracture for participating in shearing are randomly choosed by Monte carlo algorithm Reaction time interval.
Further, the fracture probability according between ester bond unit in pre-set strand, by roulette with The mode of probability determines that the fracture position of the strand for participating in shearing includes：
It is random in a probabilistic manner by roulette according to the fracture probability between ester bond unit in pre-set strand Select the fracture position of the strand for participating in shearing.
Further, the fracture probability according between ester bond unit in pre-set strand, by roulette with The mode of probability randomly chooses the fracture position of strand for participating in shearing：
Generate a random number R, whereinqiIndicate the cleavage between ester bond unit It sets,Indicate ester bond unit in qiLocate the probability of fracture, M indicates the position number that can be broken in strand；
Judge whether random number R meetsWherein, q0、For preset value, j ∈ [1, M]；
If satisfied, then the fracture position of the strand for participating in shearing is qj。
Further, the strand for participating in shearing is broken in the determining fracture position, and is recorded newly Chain number includes：
The strand for participating in shearing is in fracture position qjChain fracture is carried out, two new chains are generated, and records two newly The position of each ester bond unit of chain.
Further, the diffusion of oligomer is calculated using macroscopical diffusion equation, the macroscopic view diffusion equation is expressed as：
Wherein, CeFor high-molecular copolymer ester bond concentration, ColFor oligomeric bulk concentration, k1It is anti-for the hydrolysis of no catalytic action condition Answer rate constant, k2It is diffusion coefficient to have catalytic action condition Hydrolysis rate constant, D, grad indicates gradient, div tables Show divergence.
Further, the diffusion coefficient D is expressed as：
D=D0+(1.3ε2-0.3ε3)(D1-D0)
Wherein, D0The diffusion coefficient for being oligomer in polymer, D1The diffusion coefficient for being oligomer in hole, ε is hole Gap rate.
Further, the porosity ε is expressed as：
Wherein, CellsliquidFor moment t when liquid cellular total quantity, CellssumFor the total quantity of copolymer cellular.
Further, in the strand for participating in shearing after determining fracture position fracture, oligomer is outside After being diffused, the method further includes：
The physical attribute of statistic record cellular, the ratio of copolymer composition, and update the state of cellular, wherein the physics Attribute includes：Chain number, molecular weight, quality；
The chain number of statistics is fed back into corresponding cellular, it is anti-to carry out the shear fracture of copolymer molecule chain of next round It answers.
Further, all cellulars are being traversed, the chain number of statistics is fed back to corresponding cellular by statistic chain number, so as into After the shear fracture reaction of the copolymer molecule chain of row next round, the method further includes：
According to the physical attribute of record, high-molecular copolymer is calculated in the variable quantity of degradation process, while being predicted in cellular Influence of the different copolymer ingredient of strand to copolymerization ratios.
The above-mentioned technical proposal of the present invention has the beneficial effect that：
In said program, high-molecular copolymer is separated into cellular；Based on discrete obtained cellular, random selection participates in cutting The strand cut；Ingredient based on copolymer establishes high-molecular copolymer strand shear fracture model, and the model is used for root According to the fracture probability between ester bond unit in pre-set strand, determine that the participation is cut in a probabilistic manner by roulette The fracture position for the strand cut；The strand for participating in shearing is broken in the determining fracture position；The ginseng With the strand of shearing after determining fracture position fracture, oligomer is diffused outward, to realize it is microcosmic under Model diffusion under the shear fracture of strand to macroscopic view realizes the emulation of degradation process.
Description of the drawings
Fig. 1 is the flow diagram of high-molecular copolymer provided in an embodiment of the present invention degradation modeling and simulation method；
Fig. 2 is roulette schematic diagram provided in an embodiment of the present invention；
Fig. 3 is copolymer molecule chain schematic diagram provided in an embodiment of the present invention；
Fig. 4 fracture probability roulette schematic diagrames between ester bond unit provided in an embodiment of the present invention；
Fig. 5 is that the chain of high-molecular copolymer provided in an embodiment of the present invention shears schematic diagram；
Fig. 6 (a) is PLGA (53 provided in an embodiment of the present invention:47) molecular weight is with degradation time change schematic diagram；
Fig. 6 (b) is PLGA (53 provided in an embodiment of the present invention:47) mass loss changes over time schematic diagram；
Fig. 7 (a) is PLGA (75 provided in an embodiment of the present invention:25) molecular weight is with degradation time change schematic diagram；
Fig. 7 (b) is PLGA (75 provided in an embodiment of the present invention:25) mass loss changes over time schematic diagram；
Fig. 8 is the G% contrast schematic diagrams of different fracture probabilities provided in an embodiment of the present invention.
Specific implementation mode
To keep the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with attached drawing and tool Body embodiment is described in detail.
The present invention does not break to copolymer ingredient and copolymerization strand for existing high-molecular copolymer degradation model The problem of being studied is split, a kind of high-molecular copolymer degradation modeling and simulation method is provided.
The modeling and simulation method as shown in Figure 1, high-molecular copolymer provided in an embodiment of the present invention is degraded, including：
High-molecular copolymer is separated into cellular by S101；
S102, based on discrete obtained cellular, random selection participates in the strand of shearing；
S103, the ingredient based on copolymer establish high-molecular copolymer strand shear fracture model, and the model is used for According to the fracture probability between ester bond unit in pre-set strand, the participation is determined in a probabilistic manner by roulette The fracture position of the strand of shearing；
S104, the strand for participating in shearing are broken in the determining fracture position；
S105, after determining fracture position fracture, oligomer is expanded the strand for participating in shearing outward It dissipates.
High-molecular copolymer degradation modeling and simulation method described in the embodiment of the present invention, high-molecular copolymer is separated into Cellular；Based on discrete obtained cellular, random selection participates in the strand of shearing；It is total that ingredient based on copolymer establishes macromolecule Polymers strand shear fracture model, the model are used for general according to the fracture between ester bond unit in pre-set strand Rate determines the fracture position of the strand for participating in shearing by roulette in a probabilistic manner；Point for participating in shearing Subchain is broken in the determining fracture position；The strand for participating in shearing is broken in the determining fracture position Afterwards, oligomer is diffused outward, to realize it is microcosmic under strand shear fracture to the lower model diffusion realization of macroscopic view The emulation of degradation process.
In the present embodiment, roulette schematic diagram is as shown in Figure 2, wherein qxIndicate position,Indicate position qxFracture Probability, x=1,2 ..., M, M indicate the position number that can be broken in strand.
In the specific implementation mode that aforementioned high-molecular copolymer degrades modeling and simulation method, further, the base In discrete obtained cellular, the strand that random selection participates in shearing includes：
Based on discrete obtained cellular, strand and the shear fracture for participating in shearing are randomly choosed by Monte carlo algorithm Reaction time interval.
In the present embodiment, in order to determine the fracture position of the strand for participating in shearing, high-molecular copolymer need to be established Strand shear fracture model.Since the ester bond unit in strand has different hydrophilies, ester bond unit is caused to be connected Ester linkage breaking probability is different, and high-molecular copolymer strand shear fracture model can be established based on the ingredient of copolymer.Assuming that The strand of copolymer is as shown in Figure 3, wherein △, zero indicate two different copolymers respectively.
In the present embodiment, it is assumed that △ indicate polylactic acid (PLA), zero indicate polyglycolic acid (PGA), by taking PLA, PGA as an example into Row explanation, if qiIt indicates the fracture position between ester bond unit, is recorded with storage of array, wherein i=1,2 ..., M；m、s、n (this example simplifies probability to the fracture probability at the different chain combinations of the default setting of expression (between ester bond unit), by ester bond respectively Between fracture probability be only divided into three kinds, i.e. P (PLA-PLA)：P(PLA-PGA)：P (PGA-PGA)=m:s:n).Chain shearing is disconnected When splitting, the position of fracture can in a probabilistic manner be randomly choosed by roulette,.
In the present embodiment, the cleavage of the strand for participating in shearing is randomly choosed in a probabilistic manner by roulette The step of setting may include：
As shown in figure 4, from q1Position starts, and counterclockwise respectively represents q in Fig. 3 chains Chain_c1To qx+y-1Fracture Probability.
Fracture position qjSelect thinking for：
Generate a random number R, whereinThe value of i be i=1,2 ..., M, M indicate strand in can The position number of fracture, M are the integer more than or equal to 1；
Increase constant q0、Wherein, q0=0,Judge whether random number R meets formula (1)：
If random number R meets formula (1), the fracture position of the strand for participating in shearing is qj, wherein j ∈ [1, M]。
In the present embodiment, the strand for participating in shearing is in fracture position qjChain fracture is carried out, two new chains are generated, and Record the position of each ester bond unit of two new chains.
In the specific implementation mode that aforementioned high-molecular copolymer degrades modeling and simulation method, further, utilization is macro The diffusion that diffusion equation calculates oligomer is seen, the macroscopic view diffusion equation is expressed as：
Wherein, CeFor high-molecular copolymer ester bond concentration, ColFor oligomeric bulk concentration, k1It is anti-for the hydrolysis of no catalytic action condition Answer rate constant, k2It is diffusion coefficient to have catalytic action condition Hydrolysis rate constant, D, grad indicates gradient, div tables Show divergence.
In the specific implementation mode that aforementioned high-molecular copolymer degrades modeling and simulation method, further, the expansion Coefficient D is dissipated to be expressed as：
D=D0+(1.3ε2-0.3ε3)(D1-D0)
Wherein, D0The diffusion coefficient for being oligomer in polymer, D1The diffusion coefficient for being oligomer in hole, ε is hole Gap rate.
In the specific implementation mode that aforementioned high-molecular copolymer degrades modeling and simulation method, further, the hole Gap rate ε is expressed as：
Wherein, CellsliquidFor moment t when liquid cellular total quantity, CellssumFor the total quantity of copolymer cellular.
In the specific implementation mode that aforementioned high-molecular copolymer degrades modeling and simulation method, further, described The strand of shearing is participated in after determining fracture position fracture, after oligomer is diffused outward, the method is also Including：
The physical attribute of statistic record cellular, the ratio of copolymer composition, and update the state of cellular, wherein the physics Attribute includes：Chain number, molecular weight, quality；
The chain number of statistics is fed back into corresponding cellular, it is anti-to carry out the shear fracture of copolymer molecule chain of next round It answers.
In the specific implementation mode that aforementioned high-molecular copolymer degrades modeling and simulation method, further, traversing The chain number of statistics feeds back to corresponding cellular by all cellulars, statistic chain number, to carry out the copolymer molecule chain of next round After shear fracture reaction, the method further includes：
According to the physical attribute of record, high-molecular copolymer is calculated in the variable quantity of degradation process, while being predicted in cellular Influence of the different copolymer ingredient of strand to copolymerization ratios.
To sum up, in the present embodiment, high-molecular copolymer is subjected to discretization in a manner of cellular, based on discrete obtained member Born of the same parents randomly choose on different cellulars the microcosmic lower strand for participating in shearing by Monte carlo algorithm, based on copolymer at It is to randomly choose the ginseng in a probabilistic manner by roulette to divide the high-molecular copolymer strand shear fracture model established With the fracture position of the strand of shearing, macroscopical diffusion equation coupling is recycled to calculate the diffusion of oligomer, count and recorded each The physical attributes such as the chain number of cellular, molecular weight, quality calculate high-molecular copolymer and were degrading according to the physical attribute of record The variable quantity of journey；Influence of the different copolymer ingredient of strand in cellular to copolymerization ratios is predicted simultaneously, discloses polymer copolymerization The emulation of model diffusion realization degradation process of the object from the shear fracture of the strand under microcosmic to macroscopic view, is high-molecular copolymer Precision medicinal equipment optimization design provide data foundation.The present invention is suitable for the various of degradable macromolecule device Different application field.The high-molecular copolymer degradation modeling and simulation method that the present embodiment proposes in order to better understand, By taking Poly(D,L-lactide-co-glycolide (PLGA) as an example, to the high-molecular copolymer degradation modeling and simulation of the present embodiment proposition Method is described in detail：
In the present embodiment, with the PLGA (53 of two groups of different copolymer ratios:47)、PLGA(75:25) experimental data carries out high The degradation of molecule copolymer calculates；The parameter of computation model is set as：β=1000, β indicate that high-molecular copolymer is separated into equal portions The size of born of the same parents, the fracture probability between ester bond unit are set as m:s:N=11:12:13, other parameters are shown in Table 1, wherein Mn is indicated Molecular weight.
The parameter of the computation model of 1 different copolymer ratio of table
Case Mn(g mol-1) D0(m2day-1) D1(m2day-1) k1 k2
PLGA(53:47) 1.4×104 4×10-10 1000×D0 12.9×10-3 0.001
PLGA(75:25) 1.3×104 1.2×10-10 1000×D0 10.3×10-3 0.005
It is as follows：
(1) as shown in figure 5, high-molecular copolymer PLGA to be separated into the cellular (member of mesoscopic size size of β × β equal portions Born of the same parents), cellular is initialized, two-dimensional array Cell [] [] is used in combination to store, cellular (a, b) is denoted as：Cell[a][b].In t1 The strand at moment is denoted as：Chain_c (c=0,1,2 ..., H), contain X PLA ester bonds unit and Y PGA ester bond list Member, H indicate that the number of strand in cellular, middle section chain correspond to the position of cellular, are stored by one-dimension array Temp [].
(2) setting cellular state Cell [a] [b] _ state, Cell [a] [b] _ state points are three kinds：
4 neighbor model of von Neumann may be used in neighbours' cellular.
(3) as shown in figure 5, traversing all cellulars, statistic chain number CI(I=0,1,2 ..., L), specifically：Statistics contains There is the chain number (C of different repeat unitsIIndicate that repetitive unit is the chain of I and has CIItem), it is deposited with one-dimension array ChainNumber [] Storage.
(4) as shown in figure 5, determined at random according to Monte carlo algorithm the strand u (selection fracture chain) for participating in shearing and Shear fracture reaction time interval of delta t；Wherein, the Monte carlo algorithm includes：
αv=πvxAxB
Wherein, πvIndicate the reaction constant of v-th of shear fracture reaction, xA、xBIt indicates to participate in v-th of shear fracture reaction Reactant molecule number, αvIndicate the reaction probability of shear fracture reaction, r1、r2Indicate that two unit intervals generated are uniformly divided The random number of cloth；△ t are the time interval of two shear fractures reaction, and u is anti-for u-th of shear fracture of the subsequent time generation The strand u, N for answering or participating in shearing indicate the number of shear fracture reaction.
(5) in t1+ time Δt, according to the fracture position q for the strand that the participation that formula (1) determines is shearedj, carry out chain It is broken (ester linkage breaking), generates two new chains, update current cellular, specifically：Record each ester bond unit of two new chains Position.(6) product of recording step (5) and the cellular seen that is situated between, count the physical attribute of cellular and update cellular state, wherein The physical attribute includes：Chain number, molecular weight, quality.
(7) renewal time t1=t1+Δt1, work as t1<Δt2When (Δ t2：Time step), step (3) is returned to, is otherwise executed Step (8).
(8) diffusion of oligomer is calculated using macroscopical diffusion equation, wherein copolymerization ratios can be by the various ester bond lists that spread The quantity of member generates variation.
(9) result of calculation, the physical attribute of statistic record cellular, the ratio of copolymer composition are exported, and updates the shape of cellular State, wherein the physical attribute includes：Chain number, molecular weight, quality；
(10) renewal time t2=t2+Δt2, the shear fracture of the copolymer molecule chain of return to step (3) progress next round Reaction, until t2More than preset value, stop iteration.
In the present embodiment, PLGA (53:47)、PLGA(75:25) calculated value and experimental data compare respectively as Fig. 6 (a), 6 (b), Fig. 7 (a), 7 (b) are shown, the result verification that 6 (a), 6 (b), Fig. 7 (a), the calculated value of 7 (b) and experimental data compare The correctness of high-molecular copolymer degradation modeling and simulation method described in the present embodiment.
To inquire into influence of the different probability to degradation process, the fracture probability parameter m between another group of ester bond unit is set:s: N=10:5:1, it calculates accounting results of the PGA in copolymerization and is compared with the result of calculation under previous probability scenarios, compared Figure is as shown in Figure 8.By Fig. 8 it can be found that fracture probability can cause copolymerization ratios (G%) with the variation of time between ester bond unit And change.By polymer degradation knowledge, PGA ester bonds unit ratio PLA ester bond unit hydrophilies are stronger, i.e. PGA proportions Should be fewer and fewer, probability is m in Fig. 8:s:N=11:12:13 calculated value be actually consistent, and be broken between ester bond unit general Rate is m:s:N=10:5:1 calculated value does not conform to the actual conditions, illustrate described in the present embodiment high-molecular copolymer degradation modeling with Emulation mode to different copolymer in the degradation of copolymer than calculating be correct.By the high-molecular copolymer described in the present embodiment Degradation modeling and simulation method can obtain influence of the fracture probability between ester bond unit to degradation process.
In the present embodiment, the high-molecular copolymer strand shear fracture model based on foundation studies copolymer molecule chain Influence of the fracture to copolymer degradation.The specific steps are：By the way that high-molecular copolymer equipment is separated into mesoscopic size size Cellular；Determine when certain strand is being carved and be broken by Monte carlo algorithm；Between being set ester bond unit in strand Different fracture probabilities is set, determines that the ester bond unit of which position is broken by its probability size；Count the chain of cellular The state etc. of number, molecular weight, cellular, oligomer couple calculating with macroscopical diffusion equation, new chain number are fed back to cellular, carry out The shear fracture of the copolymer molecule chain of next round is reacted, and the iteration in a manner of this multi-scale coupling calculates the degradation of copolymer Process.
It should be noted that herein, relational terms such as first and second and the like are used merely to a reality Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation In any actual relationship or order or sequence.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art For, without departing from the principles of the present invention, several improvements and modifications can also be made, these improvements and modifications It should be regarded as protection scope of the present invention.

Claims (10)

  1. A kind of modeling and simulation method 1. high-molecular copolymer is degraded, which is characterized in that including：
    High-molecular copolymer is separated into cellular；
    Based on discrete obtained cellular, random selection participates in the strand of shearing；
    Ingredient based on copolymer establishes high-molecular copolymer strand shear fracture model, and the model is used for basis and sets in advance Fracture probability in the strand set between ester bond unit determines the molecule for participating in shearing by roulette in a probabilistic manner Chain break position；
    The strand for participating in shearing is broken in the determining fracture position；
    After determining fracture position fracture, oligomer is diffused the strand for participating in shearing outward.
  2. The modeling and simulation method 2. high-molecular copolymer according to claim 1 is degraded, which is characterized in that it is described based on from Obtained cellular is dissipated, the strand that random selection participates in shearing includes：
    Based on discrete obtained cellular, the strand for participating in shearing is randomly choosed by Monte carlo algorithm and shear fracture is reacted Time interval.
  3. The modeling and simulation method 3. high-molecular copolymer according to claim 1 is degraded, which is characterized in that the basis is pre- Fracture probability in the strand being first arranged between ester bond unit determines the participation shearing by roulette in a probabilistic manner The fracture position of strand includes：
    According to the fracture probability between ester bond unit in pre-set strand, randomly choosed in a probabilistic manner by roulette The fracture position of the strand for participating in shearing.
  4. The modeling and simulation method 4. high-molecular copolymer according to claim 3 is degraded, which is characterized in that the basis is pre- Fracture probability in the strand being first arranged between ester bond unit is randomly choosed the participation by roulette and cut in a probabilistic manner The fracture position for the strand cut includes：
    Generate a random number R, whereinI=1,2 ..., M, qiIndicate the fracture position between ester bond unit,Indicate ester bond unit in qiLocate the probability of fracture, M indicates the position number that can be broken in strand；
    Judge whether random number R meetsWherein, q0、For preset value, j ∈ [1, M]；
    If satisfied, then the fracture position of the strand for participating in shearing is qj。
  5. The modeling and simulation method 5. high-molecular copolymer according to claim 4 is degraded, which is characterized in that the participation is cut The strand cut is broken in the determining fracture position, and is recorded new chain number and included：
    The strand for participating in shearing is in fracture position qjChain fracture is carried out, generates two new chains, and two new chains of record is every The position of a ester bond unit.
  6. The modeling and simulation method 6. high-molecular copolymer according to claim 1 is degraded, which is characterized in that expanded using macroscopic view The diffusion of equation calculation oligomer is dissipated, the macroscopic view diffusion equation is expressed as：
    Wherein, CeFor high-molecular copolymer ester bond concentration, ColFor oligomeric bulk concentration, k1For no catalytic action condition hydrolysis speed Rate constant, k2It is diffusion coefficient to have catalytic action condition Hydrolysis rate constant, D, grad indicates that gradient, div indicate to dissipate Degree.
  7. The modeling and simulation method 7. high-molecular copolymer according to claim 6 is degraded, which is characterized in that the diffusion system Number D is expressed as：
    D=D0+(1.3ε2-0.3ε3)(D1-D0)
    Wherein, D0The diffusion coefficient for being oligomer in polymer, D1The diffusion coefficient for being oligomer in hole, ε is hole Rate.
  8. The modeling and simulation method 8. high-molecular copolymer according to claim 7 is degraded, which is characterized in that the porosity ε is expressed as：
    Wherein, CellsliquidFor moment t when liquid cellular total quantity, CellssumFor the total quantity of copolymer cellular.
  9. The modeling and simulation method 9. high-molecular copolymer according to claim 1 is degraded, which is characterized in that in the participation The strand of shearing is after determining fracture position fracture, and after oligomer is diffused outward, the method further includes：
    The physical attribute of statistic record cellular, the ratio of copolymer composition, and update the state of cellular, wherein the physical attribute Including：Chain number, molecular weight, quality；
    The chain number of statistics is fed back into corresponding cellular, is reacted to carry out the shear fracture of copolymer molecule chain of next round.
  10. The modeling and simulation method 10. high-molecular copolymer according to claim 1 is degraded, which is characterized in that in traversal institute There are the cellular, statistic chain number the chain number of statistics is fed back to corresponding cellular, the copolymer molecule chain to carry out next round is cut After cutting cleavage reaction, the method further includes：
    According to the physical attribute of record, high-molecular copolymer is calculated in the variable quantity of degradation process, while predicting molecule in cellular Influence of the different copolymer ingredient of chain to copolymerization ratios.
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