KR20200033539A - Method for manufacturing polymer - Google Patents

Abstract

The present specification provides a method for manufacturing a polymer and a polymer manufactured by using the same. The manufacturing method of a polymer comprises: a preparation step of a composition by dissolving two or more monomers in a first solvent; a first polymerization step of inducing a reaction of the composition at 70 to 120°C; and a second polymerization step of inducing a reaction at 70 to 150°C by adding a second solvent after the first polymerization step.

Description

Polymer manufacturing method {METHOD FOR MANUFACTURING POLYMER}

The present specification relates to a polymer manufacturing method and a polymer produced using the same.

Among the polymerization methods for producing the polymer, the still polymerization method is generally used because of its high yield. However, the still (stille) polymerization method, depending on the batch (batch), the molecular weight and the degree of dispersion (Polydispersity index, PDI) is variously polymerized, there is a problem that the uniformity of the molecular weight and molecular weight distribution of the polymer is lowered.

On the other hand, the microwave reaction used to produce a polymer having a high molecular weight also has a problem of lowering the uniformity of the polymer structure by causing side reactions such as homo coupling rather than cross coupling.

Therefore, research on a manufacturing method for producing a constant polymer having a high molecular weight and a low dispersibility is required.

Lee, Sang Myeon, et al. "Stepwise heating in Stille polycondensation toward no batch-to-batch variations in polymer solar cell performance." Nature communications 9 (2018).

The present specification provides a polymer manufacturing method and a polymer prepared using the same.

An exemplary embodiment of the present specification is a step of preparing a composition by dissolving two or more monomers in a first solvent;

A first polymerization step of reacting the composition at 70 ° C to 120 ° C; And

After the first polymerization step to provide a method for producing a polymer comprising a second polymerization step of reacting at 70 ℃ to 150 ℃ by adding a second solvent.

One embodiment of the present specification provides a polymer prepared using the above manufacturing method.

The method for preparing a polymer according to an exemplary embodiment of the present specification is capable of preparing a polymer having a high molecular weight and a low dispersion degree.

In addition, the method for preparing a polymer according to an exemplary embodiment of the present specification enables production of a polymer having improved solubility and electrical properties.

1 is a schematic diagram of a manufacturing method according to an exemplary embodiment of the present specification.
2 is a GPC measurement result of the polymer prepared according to one embodiment of the present specification.

Hereinafter, this specification will be described in detail.

In this specification, when it is said that a part "includes" a certain component, this means that other components may be further included instead of excluding other components unless otherwise specified.

In the present specification, "monomer" means a starting material for synthesizing a polymer by polymerization. That is, the monomer means a material that is a unit constituting the polymer.

A method for preparing a polymer according to an exemplary embodiment of the present specification includes dissolving two or more monomers in a first solvent to prepare a composition;

A first polymerization step of reacting the composition at 70 ° C to 120 ° C; And

And a second polymerization step of reacting at 70 ° C to 150 ° C by adding a second solvent after the first polymerization step.

In one embodiment of the present specification, the first polymerization step and the second polymerization step are performed in-situ. At this time, in-situ means that the second polymerization proceeds immediately in the heated state after the first polymerization reaction.

In one embodiment of the present specification, after the step of preparing the first composition, further comprising adding a catalyst.

In one embodiment of the present specification, the catalyst may be used without limitation as long as it is a catalyst used for stille reaction in the art. For example, the catalyst may be a palladium-based catalyst. Specifically, the catalyst may be tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ).

In one embodiment of the present specification, the first solvent is one solvent or a mixture of two or more solvents.

In one embodiment of the present specification, the first solvent is one solvent or a mixture of two solvents.

In one embodiment of the present specification, the first solvent is toluene, dimethylformamide, or a mixture thereof.

In one embodiment of the present specification, the first solvent is a mixture of toluene and dimethylformamide.

In one embodiment of the present specification, the first solvent is a mixture of toluene and dimethylformamide in a volume ratio of 10: 1 to 1: 1.

In one embodiment of the present specification, the first polymerization step is performed under an inert gas atmosphere. At this time, the inert gas atmosphere means that the inside air of a place (for example, a flask) in which a polymerization reaction occurs by introducing two or more monomers and a first solvent is made of only an inert gas. For example, the inert gas is nitrogen or argon,

In one embodiment of the present specification, the first polymerization step includes refluxing.

In one embodiment of the present specification, the second solvent is one solvent or a mixture of two or more solvents.

In one embodiment of the present specification, the second solvent is one solvent or a mixture of two solvents.

In one embodiment of the present specification, the first solvent and the second solvent are different from each other.

In one embodiment of the present specification, the second solvent is chlorobenzene, dichlorobenzene, or a mixture thereof.

In one embodiment of the present specification, the second solvent is chlorobenzene.

In one embodiment of the present specification, the second polymerization step includes refluxing.

In one embodiment of the present specification, after the refluxing step, one or more of precipitation, filtration, and Soxhlet extraction steps are performed.

In one embodiment of the present specification, the first polymerization step is performed for 6 hours to 72 hours. Specifically, the first polymerization step is performed for 15 hours to 60 hours. More specifically, the first polymerization step proceeds from 30 hours to 60 hours.

In one embodiment of the present specification, in the first polymerization step, the molecular weight increases rapidly at the beginning of the reaction (for example, within about 6 hours), and then the rate of increase in molecular weight proceeds slowly.

In one embodiment of the present specification, the second polymerization step may proceed after confirming that the molecular weight of the intermediate polymer produced in the first polymerization step does not increase any more. For example, when the molecular weight is no longer increased when the molecular weight is re-measured after 6 hours from the time when the molecular weight is measured in the first polymerization step, the second polymerization step is performed by introducing a second solvent.

In one embodiment of the present specification, the polymer after the second polymerization step has an increased molecular weight and a reduced dispersion degree than the intermediate polymer after the first polymerization step. This is because the coupling between the oligomer or the intermediate polymer prepared in the first polymerization step was further performed by proceeding with the polymerization in two steps.

In one embodiment of the present specification, the molecular weight after the second polymerization step is increased by 1.2 to 4 times than the molecular weight after the first polymerization step.

In one embodiment of the present specification, the second polymerization step is performed for 1 hour to 12 hours.

In one embodiment of the present specification, the number of the monomers is not limited, for example, 5 or less.

In one embodiment of the present specification, the monomer is a heterocyclic compound. The heterocyclic compound includes, for example, diketopyrrolopyrrole-based, benzodithiophene-based, thiophene-based, benzothiadiazole-based, and the like, but is not limited thereto.

In one embodiment of the present specification, the "~ system" means a structure including a compound exemplified before the system. For example, benzodithiophene-based monomers include substituted or unsubstituted benzodithiophene.

In one embodiment of the present specification, the monomer includes a conjugated monomer.

In the present specification, "conjugated (conjugated) monomer" means that two or more multiple bonds exist in the structure of a compound with one single bond interposed therebetween and represent interactions. At this time, the conjugated monomer means both the first conjugated monomer and the second conjugated monomer.

In one embodiment of the present specification, the conjugated monomer includes a combination of 1 or 2 or more of a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted divalent heterocyclic group. do.

In one embodiment of the present specification, the conjugated monomer is one or a combination of two or more of the following structures.

In the above structure,

a, a ', b and b' are each an integer from 1 to 5,

When a, a ', b and b' are each 2 or more, the substituents in parentheses are the same as or different from each other,

X10 to X21 and X23 to X40 are the same as or different from each other, and each independently S, O, Se, Te, NR _d , CR _d R _e , SiR _d R _e , PR _d or GeR _d R _e ,

X22 and X23 are the same as or different from each other, and each independently C, Si or Ge,

R110 to R132, R _d and R _e are the same as or different from each other, and each independently hydrogen; Halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In the present specification, “combination” means connecting several structures or connecting different types of structures.

는 다른 치환기, 단량체 또는 결합부에 결합되는 부위를 의미한다.In this specification,

Means a site bonded to another substituent, monomer or linkage.

The term "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and when two or more are substituted , 2 or more substituents may be the same or different from each other.

In this specification, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Carbonyl group; Ester groups; Hydroxy group; Alkyl groups; Cycloalkyl group; Alkoxy groups; Alkenyl group; Silyl group; Amine group; Aryl group; And one or two or more substituents selected from the group consisting of heterocyclic groups, or substituted with two or more substituents among the above-described substituents, or having no substituents. For example, "a substituent having two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 30. Specific examples are methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like. It is not.

In the present specification, the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it has 10 to 30 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

In the present specification, the heterocyclic group includes one or more non-carbon atoms, heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but preferably 2 to 30 carbon atoms, and the heterocyclic group may be monocyclic or polycyclic. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrol group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Jolyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidyl group, pyridopyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, pe Nanthrolyl group (phenanthroline), thiazolyl group, isooxazolyl group, oxadiazolyl group, thiadiazolyl group, phenothiazinyl group, and dibenzofuranyl group, but are not limited thereto.

In this specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the oxygen or carbon of the ester group may be substituted with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. It may be, but is not limited to this.

In the present specification, the alkenyl group may be straight chain or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, styrenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

In the present specification, the amine group is -NH ₂ ; Alkylamine groups; N-aryl alkylamine group; Arylamine group; N-aryl heteroarylamine group; It may be selected from the group consisting of N-alkylheteroarylamine groups and heteroarylamine groups, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group are methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 9-methyl-anthracenylamine group , Diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, and the like, but is not limited thereto.

In the present specification, the description of the alkenyl group described above may be applied, except that the alkenylene group is a divalent group.

In the present specification, the description of the aryl group described above may be applied, except that the arylene group is a divalent group.

In the present specification, the description of the aforementioned heterocyclic group may be applied except that the divalent heterocyclic group is a divalent group.

One embodiment of the present specification provides a polymer prepared by the above manufacturing method.

In one embodiment of the present specification, the polymer produced by the above production method has an advantage of high molecular weight and low dispersion.

In one embodiment of the present specification, the molecular weight of the polymer is measured by a gel permeation chromatography (GPC) method.

In one embodiment of the present specification, the dispersion degree of the polymer is measured by a gel permeation chromatography (GPC) method.

The method for preparing the polymer will be specifically described in the Examples below. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited by them.

Example 1.

In a nitrogen (N ₂ ) atmosphere, the flask was charged with monomer A (1.019 g, 1 mmol), monomer B (0.466 g, 1 mmol), 10 mL of toluene and 5 mL of dimethylformamide for 30 minutes. Thereafter, tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (0.023g, 0.02mmol) was added and stirred at 100 ° C for 48 hours. Then, 10 mL of chlorobenzene was added and stirred at 100 ° C. for 2 hours. The product was then poured into a mixed solution (180 mL methanol + 20 mL HCl (2M concentration)) to filter the precipitate. The product was subjected to Soxhlet extraction in the order of methanol, acetone, hexane, dichloromethane and chlorobenzene. The extract extracted with chlorobenzene was put in methanol to form a precipitate. The resulting precipitate was collected and purified, and dried under vacuum to obtain Polymer 1.

The number average molecular weight (Mn) of the produced polymer 1 was 87,000 g / mol, and the dispersion degree was 1.5.

Figure 1 (a) is the result of GPC measurement of the polymer 1 prepared

Comparative Example 1.

In a nitrogen (N ₂ ) atmosphere, the flask was charged with monomer A (1.019 g, 1 mmol), monomer B (0.466 g, 1 mmol), 10 mL of toluene and 5 mL of dimethylformamide for 30 minutes. Thereafter, tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (0.023 g, 0.02 mol%) was added thereto and stirred at 100 ° C. for 48 hours. The product was then poured into a mixed solution (180 mL methanol + 20 mL HCl (2M concentration)) to filter the precipitate. The product was subjected to Soxhlet extraction in the order of methanol, acetone, hexane, dichloromethane and chlorobenzene. The extract extracted with chlorobenzene was put in methanol to form a precipitate. The resulting precipitate was collected and purified, and dried under vacuum to obtain Polymer 1.

The number average molecular weight (Mn) of the produced polymer 1 was 25,000 g / mol, and the dispersion degree was 3.28.

1 (b) is a GPC measurement result of polymer 1 prepared in Comparative Example 1.

Comparing Figures 1 (a) and (b), the PDI of the polymer of Example 1 prepared according to one embodiment of the present specification exhibits a lower PDI compared to the polymer prepared in Comparative Example 1 that has undergone only the first polymerization step. You can confirm that.

Example 2.

In a nitrogen (N ₂ ) atmosphere, the flask was charged with monomer C (0.452 g, 0.5 mmol), monomer D (0.236 g, 0.5 mmol), 10 mL of toluene and 5 mL of dimethylformamide for 30 minutes. Thereafter, tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (11.6mg, 0.01mmol) was added and stirred at 100 ° C for 48 hours. Then, 5 mL of chlorobenzene was added and stirred at 100 ° C. for 2 hours. The product was then poured into a mixed solution (180 mL methanol + 20 mL HCl (2M concentration)) to filter the precipitate. The product was subjected to Soxhlet extraction in the order of methanol, acetone, hexane, dichloromethane and chlorobenzene. The extract extracted with chlorobenzene was put in methanol to form a precipitate. The resulting precipitate was collected and purified, and dried under vacuum to obtain Polymer 2.

The number average molecular weight (Mn) of the produced polymer 2 was 54,000 g / mol, and the dispersion degree was 1.74.

Comparative Example 2.

In a nitrogen (N ₂ ) atmosphere, the flask was charged with monomer C (0.452 g, 0.5 mmol), monomer D (0.236 g, 0.5 mmol), 10 mL of toluene and 5 mL of dimethylformamide for 30 minutes. Thereafter, tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (11.6mg, 0.01mmol) was added and stirred at 100 ° C for 48 hours. The product was then poured into a mixed solution (180 mL methanol + 20 mL HCl (2M concentration)) to filter the precipitate. The product was subjected to Soxhlet extraction in the order of methanol, acetone, hexane, dichloromethane and chlorobenzene. The extract extracted with chlorobenzene was put in methanol to form a precipitate. The resulting precipitate was collected and purified, and dried under vacuum to obtain Polymer 2.

The prepared polymer 2 had a number average molecular weight (Mn) of 31,000 g / mol and a dispersion degree of 2.12.

Claims (7)

Preparing a composition by dissolving two or more monomers in a first solvent;
A first polymerization step of reacting the composition at 70 ° C to 120 ° C; And
A method of preparing a polymer comprising a second polymerization step of reacting at 70 ° C to 150 ° C by adding a second solvent after the first polymerization step. The method according to claim 1,
The first solvent is a method for producing a polymer that is different from the second solvent. The method according to claim 1,
The first solvent is toluene, dimethylformamide, or a mixture of these polymer production method. The method according to claim 1,
The second solvent is chlorobenzene, dichlorobenzene or a polymer production method that is a mixture thereof. The method according to claim 1,
The first polymerization step is a polymer production method that is performed for 6 hours to 72 hours. The method according to claim 1,
The second polymerization step is a method for producing a polymer that is performed for 1 hour to 12 hours. A polymer produced by the method of claim 1.

Images