CN104268405A - Monte carlo molecular simulation research method for kinetic process of polymerization reaction - Google Patents
Monte carlo molecular simulation research method for kinetic process of polymerization reaction Download PDFInfo
- Publication number
- CN104268405A CN104268405A CN201410502870.9A CN201410502870A CN104268405A CN 104268405 A CN104268405 A CN 104268405A CN 201410502870 A CN201410502870 A CN 201410502870A CN 104268405 A CN104268405 A CN 104268405A
- Authority
- CN
- China
- Prior art keywords
- reaction
- motion
- polymerization reaction
- polyreaction
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a monte carlo molecular simulation research method for the kinetic process of polymerization reaction. The method comprises the step that the polymerization reaction simulation process is divided into two parts, namely, a systemic movement part and a polymerization reaction part; when in the polymerization reaction part, the occurrence probability of triggering, chain growth, chain transfer, chain termination and other elementary reactions are controlled through different reaction probability; when in the systemic movement part, a local-global concentration potential difference which shows the difference of the local concentration and the global concentration of components is introduced to determine the concentration distribution state of each unit component in the system, in order to realize the balanced distributing state of the component unit in the polymerization reaction process; the monte carlo energy criterion for controlling unit particle movement involves a chemical key part and a non-key part. The method is simple and efficient; the problem of non-uniform distribution of the component unit in the simulation system caused by the consumption of an initiator and a monomer under the polymerization reaction can be avoided, and the kinetic process of the experiment system can be really reflected by being compared with the traditional molecular simulation method.
Description
Technical field
The present invention relates to a kind of illiteracy holder Caro molecular simulation research method of kinetics of polymerization reaction process.
Background technology
The study of computer simulation kinetics of polymerization reaction process is utilized to have important theory and practice meaning to analyzing polymers composition, raising polyreaction efficiency and design Chemical Manufacture route.Study kinetics of polymerization reaction process by experiment, impact by factors such as operating conditions, detection technique and sampling interval is difficult to realize monitoring continuously and accurately resolve, computer modeling technique can the full detail of instantaneous monitoring reaction system, is the effective ways of research kinetics of polymerization reaction process.
The study of computer simulation of kinetics of polymerization reaction process is applied in practice by people.To have based on the method for covering holder Caro molecular simulation research kinetics of polymerization reaction process: (Chinese science B collects chemistry 2005 for the modeling effories such as Ding Jiandong chain polymerization and polycondensation reaction, 35 (1): 27-32), Jan Genzer uses the illiteracy holder Caro method modeling effort of bondfluctuation model living polymerization process (Macromolecules 2006,39,7157-7169).This type of model, based on illiteracy holder Caro molecule simulation method, has taken into full account the concentration fluctuation that the volume excluding effect of moving cell in polymerization reaction system and molecular motion are formed, can the full detail of statistics and convergence reaction system and dynamic process.
But by the restriction of current computing power, molecule simulation method can only consider the model system of coarse, and the number of particles of simulated system is generally 10
3~ 10
5.When replica polymerization reacts, in system, the consumption of regional area initiating agent and monomer will cause simulated system constituent unit local concentration too low.And owing to covering the randomness of holder Caro molecular motion, constituent unit also may be caused at localized clusters, form the phenomenon of constituent unit local excessive concentration.In actual polymerization reaction system, due to mechanical raking and concentration of component diffusional effect, the component local concentration of system and overall concentration are consistent or close.Therefore, in simulated system, realizing system component local concentration keep close or consistent with overall concentration, is the important channel of improving modeling effort accuracy.
The present invention proposes with local-overall concentration potential difference equation
the difference of representation system component local concentration and overall concentration, and the illiteracy holder Caro derivation of energy formula revising molecular motion
the excessive situation of local concentration and overall concentration difference in polyreaction simulated system is overcome with this, make the computer simulation state of kinetics of polymerization reaction and true experimental system more close, improve modeling effort to the explanation of real system experimental phenomena and predictive ability.
Summary of the invention
The object of the invention is, propose a kind of new polyreaction and cover holder Monte Carlo Simulation of Ions Inside algorithm, make simulated system each component distribution in polymerization process keep homogeneously dispersed state, make emulation mode and experimental fact more close, thus improve simulated system to the emulator of testing time of day.
The modeling algorithm that the present invention proposes covers holder Caro molecule simulation method based on tradition, introduce the local-overall concentration potential difference criterion of adjustment and control system constituent unit distribution, improve tradition and cover the energy criterion of holding in the palm in Caro molecular simulation, system component is moved there is concentration diffusional effect.The advantage of the method is: analog programming is simple, the basis of conventional molecular simulation is revised and increases energy and concentration criterion; Proposed by the invention improving one's methods is applicable to cover holder Caro grid pattern and Off-lattice model, and can use for reference for the analogy method such as molecular dynamics and Dissipative Particle Dynamics.
Concrete operation step of the present invention is as follows:
(1) according to polymerization process, theorize research model, determines all possible elementary reaction of polymerization reaction system, polymerisation process and reaction conditions.Set the population of the size of simulated system, initiating agent and monomer, regulate and control the reaction probability of each elementary reaction, the parameters such as the feed way of initiating agent and monomer, feed rate are set.
(2) experimentally data and simulation exploration result arrange interaction force numerical value, the illiteracy holder Caro criterion threshold value in system between different component unit, and counting system constituent unit mean concentration gradient gesture, establishes non-one-tenth key energy equation
in the numerical value of each parameter.
(3) with the parameter initialization simulated system determined in (2), following steps replica polymerization course of reaction is performed successively:
A () judges system component unit overall situation disperse state: according to quantity and the system size of constituent unit, in counting system, the overall situation of each constituent unit is evenly distributed situation; Constituent unit local area distribution situation under calculating simulation system current state.According to above-mentioned result of calculation, determine constituent unit local-overall concentration potential difference
judge system component overall situation disperse state accordingly.
(b) motion and reaction and judgement: judge whether to react, as local-overall concentration potential difference according to system component unit overall situation disperse state
meet system requirement, then can react; Otherwise can only move, until local-overall concentration potential difference meets the demands.
C () motion is attempted: pass through randomizer; Stochastic choice moving cell (on initiating agent, monomer particle or strand certain link units) and direction of motion; judge direction of motion and apart from the upper system particle whether having space or coarse; if there is space, calculate the energy difference of the system before and after motion
then illiteracy holder Caro motion determination is carried out; If be the system particle of coarse, the polyreaction of carrying out as described in (d) judges.
(d) polyreaction judge: if select two kinds of particles have reaction may, as one be free radical another be monomer, then there is corresponding polyreaction (e); If the particle (end of the chain of cessation reaction occurs for uncracked initiating agent, the link units in strand) that two kinds of particles are reactionless activity then can not carry out polyreaction.
(e) polyreaction: two kinds of constituent unit that can react, becoming bond length from interior, carry out judging whether to react with reaction probability.As reaction probability allows, two kinds of particles are connected chaining, and polymerization activity transfers to chain end or disappearance (cessation reactions of two kinds of chain free radicals); As reaction probability does not allow, then do not carry out polyreaction.
(4) analog result statistical method: the information utilizing array of pointers record moving cell (on initiating agent, monomer particle or strand certain link units) and strand, after the polyreaction of certain number of times, the number of residual monomer in statistics system, calculates monomer conversion; The number of statistical subchain, the link units number of every bar strand, calculate molecular weight and molecualr weight distribution.
Accompanying drawing explanation
Describe exemplary embodiment of the present invention in more detail by referring to accompanying drawing, above and other aspect of the present invention and advantage will become and more be readily clear of, in the accompanying drawings:
The process flow diagram of the illiteracy holder Caro molecular simulation research method of a kind of kinetics of polymerization reaction process of Fig. 1 the present invention;
In Fig. 2 embodiment 1, monomer conversion is with the Changing Pattern of polymerization reaction time;
In Fig. 3 embodiment 1, polymer molecular weight is with the Changing Pattern of polymerization reaction time;
In Fig. 4 embodiment 1, polymer molecular weight distribution is with the Changing Pattern of polymerization reaction time.
Embodiment
Hereinafter, more fully the present invention is described with reference to the accompanying drawings, embodiment shown in the drawings.But the present invention can implement in many different forms, and should not be interpreted as being confined to embodiment set forth herein.On the contrary, provide these embodiments to make the disclosure will be thoroughly with completely, and scope of the present invention is conveyed to those skilled in the art fully.
Hereinafter, with reference to the accompanying drawings exemplary embodiment of the present invention is described in more detail.
Embodiment 1: the illiteracy holder Monte Carlo Simulation of Ions Inside research of radically homo reaction kinetics process.Polymerization reaction system monomer concentration is 0.08 (v/v), and initiating agent is 0.064 with monomeric charge ratio, and reaction process process is disposable feeding intake, and does not consider any radical transfer reaction occurred in polymerization process.Physical simulation step is as follows:
(1) polyreaction model is set up, setting system parameter
Be 50 at volume
3space in, the monomer of evenly distributed respective concentration and initiating agent particle.Setting initiating agent causes probability P i and is set to 10
-6, polyreaction probability P a=10
-3, polymerization cessation reaction probability P t=0.1, wherein coupling termination and disproportionation termination equiprobability occur.In illiteracy holder Caro energy in non-one-tenth bond energy equation
arrange κ=1.0kT, ζ=0.08kT, wherein kT is system environment heating bath temperature.
(2) replica polymerization reaction kinetics process
As shown in Figure 1, after simulated system initialization, because be evenly distributed, so system directly enters motion/reaction and judgement.
(a) motion and reaction and judgement: pass through randomizer, Stochastic choice moving cell (on initiating agent, monomer particle or strand certain link units) and direction of motion, judge direction of motion and apart from the upper system particle whether having space or coarse, if there is space, then the motion carried out as described in (b) is attempted; If be the system particle of coarse, the polyreaction of carrying out as described in (c) judges.
B () motion is attempted: according to motion and reaction and judgement result, calculates the energy difference of the system before and after motion
carry out illiteracy holder Caro energy with a random number to judge.If random number is greater than cover holder Caro energy threshold, system is not moved; If random number is less than cover holder Caro energy threshold, system moves, the moving cell of selection and space switch.
(c) polyreaction judge: if select two kinds of particles have reaction may, as one be free radical another be monomer, then there is corresponding polyreaction (d); If the particle (end of the chain of cessation reaction occurs for uncracked initiating agent, the link units in strand) that two kinds of particles are reactionless activity then can not carry out polyreaction.
(d) polyreaction: two kinds of constituent unit that can react, becoming bond length from interior, carry out judging whether to react with reaction probability.As reaction probability allows, two kinds of particles are connected chaining, and polymerization activity transfers to chain end or disappearance (cessation reactions of two kinds of chain free radicals); As reaction probability does not allow, then do not carry out polyreaction.
Polymerization reaction system carries out 10
2secondary polyreaction (comprising motion and reaction) is carried out system component unit overall situation disperse state and is judged, as described in (e) after attempting.
E () system component unit overall situation disperse state judges: the local concentration of constituent unit and overall mean concentration potential difference in counting system
if higher than threshold value (0.4kT), carry out motion and attempt, until component unit CONCENTRATION DISTRIBUTION reaches uniform distribution requirement, namely concentration potential difference is less than 0.4kT.
In simulation process, often carry out 10
8secondary motion and reaction attempt after statistics system information: according to the change information of the moving cell recorded in array of pointers (on initiating agent, monomer particle or strand certain link units) and strand, the number of residual monomer in statistics system, calculate monomer conversion, as shown in Figure 2; The number of statistical subchain, the link units number of every bar strand, calculate molecular weight and molecualr weight distribution as shown in figures 3 and 4.
Claims (3)
1. an illiteracy holder Caro molecular simulation research method for kinetics of polymerization reaction process, is characterized in that:
Described method comprises the steps:
(1) set all elementary reactions of polymerization reaction system to be simulated and technological process, experimentally data and experience arrange initiating agent, the monomer concentration of simulated system, the type of various elementary reaction and reaction rate;
(2) to set up research model according to polymeric reaction condition, determine the population of the size of simulated system, initiating agent and monomer, regulate and control the reaction probability of each elementary reaction, the physical simulation parameters such as the feed way of initiating agent and monomer, feed rate are set; Arrange the interaction force numerical value in system between different component unit, cover holder Caro criterion threshold value, counting system constituent unit overall situation mean concentration gesture, establishes non-binding effect energy equation
in the numerical value of each parameter;
(3) simulation steps of polyreaction is:
The system parameter arranged in (a) basis (2), to each parameter assignment of simulated system, in the simulated system determining size, the initiating agent of evenly distributed coarse and monomer particle;
B () system component unit overall situation disperse state judges: local concentration gesture and overall mean concentration potential difference in counting system
if local-overall concentration potential difference is higher than certain threshold value, carries out motion and attempt, until local-overall concentration potential difference meets the requirement of system component uniform distribution, namely system overall situation disperse state meets simulated system requirement, just can carry out polyreaction;
(c) motion and reaction and judgement: pass through randomizer, Stochastic choice moving cell (on initiating agent, monomer particle or strand certain link units) and direction of motion, judge direction of motion and apart from the upper system particle whether having space or coarse, if there is space, then carries out motion and attempt; If be the system particle of coarse, the polyreaction of carrying out as described in (e) judges;
D () motion is attempted: according to motion and reaction and judgement result, and the maximum system energy calculated before and after motion is poor
carry out illiteracy holder Caro energy with a random number to judge; If random number is greater than cover holder Caro energy threshold, system is not moved; If random number is less than cover holder Caro energy threshold, system moves, the moving cell of selection and space switch;
(e) polyreaction judge: if select two kinds of particles have reaction may, as one be free radical another be monomer, then there is corresponding polyreaction (f); If the particle (end of the chain of cessation reaction occurs for uncracked initiating agent, the link units in strand) that two kinds of particles are reactionless activity then can not carry out polyreaction;
(f) polyreaction: two kinds of constituent unit that can react, becoming bond length from interior, carry out judging whether to react with reaction probability; As reaction probability allows, two kinds of particles are connected chaining, and polymerization activity transfers to chain end or disappearance (cessation reactions of two kinds of chain free radicals); As reaction probability does not allow, then do not carry out polyreaction;
(4) analog result statistical method: the information utilizing array of pointers record moving cell (on initiating agent, monomer particle or strand certain link units) and strand, after the polyreaction of certain number of times, the number of residual monomer in statistics system, calculates monomer conversion; The number of statistical subchain, the link units number of every bar strand, calculate molecular weight and molecualr weight distribution.
2. according to the method described in claim 1, it is characterized in that: in step (3), (b) introduces local-overall concentration potential difference
with the adjustment and control system motion of system component unit overall situation disperse state and reaction.
3. according to the method described in claim 1, it is characterized in that: in step (3), in (d) system motion process, interaction energy combines to become bond energy and non-bond energy two parts
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410502870.9A CN104268405B (en) | 2014-09-26 | 2014-09-26 | A kind of illiteracy support Caro molecular simulation research method of kinetics of polymerization reaction process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410502870.9A CN104268405B (en) | 2014-09-26 | 2014-09-26 | A kind of illiteracy support Caro molecular simulation research method of kinetics of polymerization reaction process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104268405A true CN104268405A (en) | 2015-01-07 |
| CN104268405B CN104268405B (en) | 2017-12-08 |
Family
ID=52159926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410502870.9A Expired - Fee Related CN104268405B (en) | 2014-09-26 | 2014-09-26 | A kind of illiteracy support Caro molecular simulation research method of kinetics of polymerization reaction process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104268405B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107798213A (en) * | 2017-10-24 | 2018-03-13 | 辽宁工程技术大学 | A kind of Fast simulation computational methods of palladium metal catalytic performance change |
| CN108984852A (en) * | 2018-06-22 | 2018-12-11 | 温州大学 | Monte-Carlo Simulation Method of the macromolecular chain in adsorption property under external force |
| CN109686409A (en) * | 2019-02-01 | 2019-04-26 | 华南理工大学 | A kind of research of Dissipative Particle Dynamics comprising can break chemical bonds carrier micelle drug release process analogy method |
| CN110517735A (en) * | 2019-09-11 | 2019-11-29 | 江西省科学院能源研究所 | A kind of Dissipative Particle Dynamics method for simulating gel mould interface polymerization reaction process |
| CN110767273A (en) * | 2019-10-30 | 2020-02-07 | 华南理工大学 | Simulation method for self-assembly behavior of rigid block copolymer solution |
| CN111483976A (en) * | 2020-04-26 | 2020-08-04 | 南通大学 | Preparation method of novel patterned nanostructure based on special-shaped double-cylinder array |
| CN111498798A (en) * | 2020-04-26 | 2020-08-07 | 南通大学 | Preparation method of ordered microstructure based on array-limited self-assembly |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050042663A1 (en) * | 2003-08-19 | 2005-02-24 | Blinov Michael L. | Rule-based modeling of biochemical networks |
| CN102298668A (en) * | 2011-05-30 | 2011-12-28 | 复旦大学 | Monte Carlo simulation method of batch charging process condition in copolymerization |
-
2014
- 2014-09-26 CN CN201410502870.9A patent/CN104268405B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050042663A1 (en) * | 2003-08-19 | 2005-02-24 | Blinov Michael L. | Rule-based modeling of biochemical networks |
| CN102298668A (en) * | 2011-05-30 | 2011-12-28 | 复旦大学 | Monte Carlo simulation method of batch charging process condition in copolymerization |
Non-Patent Citations (2)
| Title |
|---|
| JAN GENZER: "In Silico Polymerization: Computer Simulation of Controlled Radical Polymerization in Bulk and on Flat Surfaces", 《MACROMOLECULES 2006》 * |
| 陈鹏等: "Monte Carlo模拟研究聚合诱导高分子自组装", 《安徽大学学报(自然科学版)》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107798213A (en) * | 2017-10-24 | 2018-03-13 | 辽宁工程技术大学 | A kind of Fast simulation computational methods of palladium metal catalytic performance change |
| CN107798213B (en) * | 2017-10-24 | 2020-07-28 | 辽宁工程技术大学 | Rapid simulation calculation method for palladium metal catalytic performance change |
| CN108984852A (en) * | 2018-06-22 | 2018-12-11 | 温州大学 | Monte-Carlo Simulation Method of the macromolecular chain in adsorption property under external force |
| CN108984852B (en) * | 2018-06-22 | 2022-12-13 | 温州大学 | Monte Carlo simulation method for adsorption property of polymer chain on surface under external force action |
| CN109686409A (en) * | 2019-02-01 | 2019-04-26 | 华南理工大学 | A kind of research of Dissipative Particle Dynamics comprising can break chemical bonds carrier micelle drug release process analogy method |
| CN109686409B (en) * | 2019-02-01 | 2020-08-18 | 华南理工大学 | Simulation method of drug release process of drug-loaded micelle containing cleavable chemical bond |
| CN110517735A (en) * | 2019-09-11 | 2019-11-29 | 江西省科学院能源研究所 | A kind of Dissipative Particle Dynamics method for simulating gel mould interface polymerization reaction process |
| CN110767273A (en) * | 2019-10-30 | 2020-02-07 | 华南理工大学 | Simulation method for self-assembly behavior of rigid block copolymer solution |
| CN110767273B (en) * | 2019-10-30 | 2023-03-31 | 华南理工大学 | Simulation method for self-assembly behavior of rigid block copolymer solution |
| CN111483976A (en) * | 2020-04-26 | 2020-08-04 | 南通大学 | Preparation method of novel patterned nanostructure based on special-shaped double-cylinder array |
| CN111498798A (en) * | 2020-04-26 | 2020-08-07 | 南通大学 | Preparation method of ordered microstructure based on array-limited self-assembly |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104268405B (en) | 2017-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104268405A (en) | Monte carlo molecular simulation research method for kinetic process of polymerization reaction | |
| Xue et al. | Inverse prediction and optimization of flow control conditions for confined spaces using a CFD-based genetic algorithm | |
| ARAI et al. | Simulation model for the rate of bulk polymerization over the complete course of reaction | |
| Monteiro | Modeling the molecular weight distribution of block copolymer formation in a reversible addition–fragmentation chain transfer mediated living radical polymerization | |
| Retkute et al. | Dynamics of DNA replication in yeast | |
| Yoon et al. | Recent advances in polymer reaction engineering: modeling and control of polymer properties | |
| Li et al. | Model‐based production of polymer chains having precisely designed end‐to‐end gradient copolymer composition and chain topology distributions in controlled radical polymerization, A review | |
| CN102184454A (en) | Granulator formula generation method based on neural network system | |
| Zubov et al. | Bringing the on‐line control and optimization of semibatch emulsion copolymerization to the pilot plant | |
| CN102289559B (en) | Method for predicting copolymer sequence distribution in free radical copolymerization system by Monte Carlo simulation | |
| Gao et al. | Acceleration of kinetic monte carlo simulations of free radical copolymerization: A hybrid approach with scaling | |
| Nasresfahani et al. | An automated recipe generator for semi-batch solution radical copolymerization via comprehensive stochastic modeling and derivative-free algorithms | |
| Sarmoria et al. | Prediction of molecular weight distributions in polymers using probability generating functions | |
| CN102063544B (en) | Multicore parallel solving method for computation of polymer molecular weight distribution | |
| Tongtummachat et al. | Understanding the formation of linear olefin block copolymers with dynamic Monte Carlo simulation | |
| CN104268120A (en) | Monte carlo simulation parallel computing method for kinetic process of polymerization reaction | |
| Dong et al. | Modelling of multiphase flow in ironmaking blast furnace | |
| Chaimberg et al. | Kinetic modeling of free-radical polymerization: a conservational polymerization and molecular weight distribution model | |
| Staggs | Population balance models for the thermal degradation of PMMA | |
| Chaloupka et al. | Real-time hybrid Monte Carlo method for modelling of 4 monomer semi-batch emulsion copolymerization | |
| CN107726533B (en) | Air conditioner load power oscillation suppression control method | |
| Zhang et al. | Multi-Objective Optimization for Gas Distribution in Continuous Annealing Process | |
| Serajian et al. | The impacts of feed fraction on copolymer microstructure in ATRcP: a kinetic Monte Carlo simulation | |
| Zhao et al. | GA-BP Neural Network Based Meta-Model Method for Computational Fluid Dynamic Approximation | |
| Asteasuain | Deterministic approaches for simulation of nitroxide-mediated radical polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171208 Termination date: 20190926 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |