KR101790973B1 - Preparation Method of epoxy functionalized acrylate polymers having low molecular weight and low polydispersity - Google Patents
Preparation Method of epoxy functionalized acrylate polymers having low molecular weight and low polydispersity Download PDFInfo
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- KR101790973B1 KR101790973B1 KR1020160006853A KR20160006853A KR101790973B1 KR 101790973 B1 KR101790973 B1 KR 101790973B1 KR 1020160006853 A KR1020160006853 A KR 1020160006853A KR 20160006853 A KR20160006853 A KR 20160006853A KR 101790973 B1 KR101790973 B1 KR 101790973B1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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Abstract
The present invention is based on the finding that when polymerizing acrylate and / or methacrylate having an epoxy group with styrene and methylmethacrylate, a low molecular weight of 5,000 to 10,000 (Mw) and a low molecular weight of 2 to 3 And to provide a method for producing a polymer having a distribution.
Description
The present invention relates to a process for preparing an epoxy-containing acrylate copolymer in the presence of a polar aprotic solvent, which has a conversion of 90 wt% or more, a molecular weight of 5,000 to 10,000, a molecular weight distribution of 2 to 3, And to provide a method for producing an epoxy-based acrylate oligomer.
In the preparation of epoxy-containing acrylate copolymers, there is a disadvantage in that the polymerization reaction rate is high and the polymerization rate is fast and therefore the reaction rate is difficult to control. Thus, when preparing the epoxy acrylate oligomer, A reactive oligomer having an epoxy reactive group having a distribution diagram can not be produced smoothly.
Conventionally, an oligomer having a low molecular weight epoxy reactive group could not be manufactured uniformly reliably and repetitively. For example, although an initiator can be used in an excessively low molecular weight, a polymer having a molecular weight of several hundreds of thousands to several millions There is no reproducibility when used as a final reactive oligomer, and the physical properties vary from batch to batch, so that there are many limitations to the additives used in the final product.
That is, there is a problem in quality such as difficulty in controlling the molecular weight of the finally produced polymer, and thus the reproducibility of the reaction is poor.
These disadvantages, when used as a reactive oligomer, are that macroscopic molecular properties such as the molecular weight, molecular weight distribution, solution viscosity, etc. of the oligomer polymer used do not affect physical properties such as physical, mechanical and rheological properties of the polymer, Because they are key factors, they are often not commercially viable if they are not manufactured reproducibly.
It is not easy to obtain a polymer having a low molecular weight in the production of a polymer. Particularly, in the polymerization reaction of the epoxy acrylate, the reaction heat control is important for establishing a safe reaction system and controlling the molecular weight of the polymer.
For example, US pat. 5,256,452 (1993) discloses a method of producing a polymer by heat dissipation through a reflux reaction at the boiling point of xylene and the like. However, in actual analysis, the average molecular weight is at least a large amount of polymer and the molecular weight distribution is wide, Is difficult to produce.
Another method is a low-temperature polymerization method, but it takes a long time and has a disadvantage that it is difficult to secure a sufficient conversion ratio.
The present invention is based on the finding that when polymerizing acrylate and / or methacrylate having an epoxy group with styrene and methylmethacrylate, a low molecular weight of 5,000 to 10,000 (Mw) and a low molecular weight of 2 to 3 And to provide a method for producing a polymer having a distribution.
By adopting an effective polymerization system, the present invention can produce an epoxy-reactive polymer having a low molecular weight of Mw of 5,000 to 10,000 and a uniform physical property having a low polydispersity of 2 to 3 despite a conversion ratio of 90% or more, A polymer having an effect that the physical properties of the transition temperature and the epoxy equivalent are not largely lowered, and a variety of products using the polymer.
In the present invention, it is difficult to control the molecular weight to a desired level in the production of a polymer, and it is difficult to control the polymerization reaction heat to solve various problems in the prior art.
The present invention has been made in an attempt to solve the problem of controlling the molecular weight by using an initiator and a chain transfer agent in the polymerization process. The monomer, the reaction solvent, and the chain transfer agent were appropriately selected and dosed at a constant flow rate, The heat of polymerization and the molecular weight can be controlled, thereby completing the present invention.
The present invention relates to a process for preparing a polymerization mixture by mixing a chain transfer agent with a monomer containing an epoxy acrylate and / or epoxy methacrylate monomer, styrene and methyl methacrylate,
Preparing a polar neutral solution containing an initiator;
Polymerizing the polymerization mixture and the polar neutral solution into the reactor while continuously and constantly introducing the mixture;
Wherein the polymerization reaction has a weight average molecular weight of from 5,000 to 10,000 and a molecular weight distribution of from 2 to 3 when having a conversion of 90% or more.
The present invention relates to a process for preparing a polymer having a low molecular weight of Mw of 5,000 to 10,000 and a low polydispersity of 2 to 3, that is, easy control of molecular weight to a desired level, A polymer containing an acidic reactive epoxy group can be provided.
In addition, the present invention can produce a polymer which is easy to control the molecular weight and is excellent in reproducibility, and can be used as a chain extender in polymer processing due to its low molecular weight and low polydispersity properties. For example, The present invention can provide a method for producing a polymer that can be usefully used in polymer processing.
1 shows a polymerization reaction apparatus according to an example of the present invention.
Hereinafter, the present invention will be described in more detail. The terminology used herein is for the purpose of describing specific examples effectively, and is not intended to limit the invention. Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.
The present invention relates to a process for preparing a polymer such as a reactive epoxy acrylate oligomer, which is a conventional exothermic reaction and has a wide molecular weight distribution and a high weight average molecular weight using a large amount of an initiator, A polymer fraction with a high polymerization degree is generated to solve the problem that when the polymer is used as a chain extender in the processing of a polymer, the physical properties of the final product are changed so that the polymer can not be practically used.
That is, the present invention relates to a reactive epoxy resin composition having a low molecular weight and low molecular weight distribution to produce a reproducible oligomer having homogeneous physical properties in each reaction reactor so as to have a low molecular weight distribution by controlling the production of a high- Acrylate polymer oligomer.
The present inventors have long studied a method capable of producing a reactive oligomer used as a chain extender and the like so as to have a uniform low degree of polymerization and a low molecular weight distribution. As a result, it has been found that a specific selection of monomers, reaction solvents, chain transfer agents, , It was found that a low molecular weight, low molecular weight reactive epoxy polymer having a molecular weight of 5,000 to 10,000 and a molecular weight distribution of 2 to 3 can be produced at a temperature of 100 ° C or lower despite a high conversion rate.
The present invention relates to a process for preparing a polymerization mixture by mixing a chain transfer agent with a monomer containing an epoxy acrylate and / or epoxy methacrylate monomer, styrene and methyl methacrylate,
Preparing a polar neutral solution containing an initiator;
Polymerizing the polymerization mixture and the polar neutral solution into the reactor while continuously and constantly introducing the mixture; Containing acrylate polymer. ≪ Desc /
Specifically, the present invention can use glycidyl acrylate as the epoxy acrylate monomer, glycidyl methacrylate monomer as the epoxy methacrylate monomer, and further includes styrene and methyl methacrylate To prepare a main monomer, and then a chain transfer agent is added thereto to prepare a polymerization mixture.
Epoxy polymer oligomers can be produced with a low molecular weight distribution at a conversion rate of 90% or more by introducing a polar neutral solution containing an initiator into the reactor for a predetermined time to polymerize the polymerization mixture.
Therefore, in the present invention, an important method of achieving the object of the present invention by performing a polymerization reaction in a polar neutral solution containing an initiator and polymerizing a monomer polymerization mixture containing a chain transfer agent (CTA) do.
More specifically, although not limiting, the present invention is characterized in that each of the compositions is supplied to another reactor at a constant flow rate for 4 to 8 hours and continuously supplied by a metering pump.
In order to achieve the above object, the polymer of the present invention preferably forms a copolymer structure in which glycidyl acrylate and / or glycidyl methacrylate, styrene, and methyl methacrylate compounds are bonded.
The reaction solvent used in the polymerization reaction of the present invention may be a polar aprotic solvent such as dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) Is not limited as far as the reaction heat can be controlled well, but the polar neutral solvent is not limited. For example, the solvent is preferably used in an amount of about 20 to 50% by weight based on 100 parts by weight of the total monomers.
When the polar neutral solvent is not used as a reaction solvent in the present invention, the distribution of the degree of polymerization is widened and problems occur in reproducibility every polymerization batch.
As the polymerization initiator of the present invention, a combination of azobisisobutyronitrile (AIBN) in an amount of 5 to 8 wt% based on the monomer and alkyl mercaptan (NDM) in a chain transfer agent in a range of 1 to 4 wt% But the present invention is not limited thereto. However, the molecular weight distribution tends to be widened when the above combination is deviated.
Unlike the polymerization method of the present invention, in a batch reactor, when a monomer and an initiator are charged in a batch, a product having a large degree of polymerization can not be obtained due to a large number of products having a large degree of polymerization, and the molecular weight of the obtained polymer varies greatly The molecular weight distribution could not be obtained consistently.
In the present invention, although the reaction time is not limited to a great extent, it is possible to produce a reactive oligomeric polymer having a degree of polymerization and a degree of polymerization distribution, which can reach a satisfactory conversion rate in a polymerization time of about 4 to 8 hours, But is not limited thereto.
In the present invention, the method of introducing the polymerization mixture of the monomer and the chain transfer agent and the reactor of the polar neutral solution containing the initiator is required to be continuously carried out while maintaining a constant speed, and when the charging speed is changed or the speed is changed during polymerization, The polymer for the purpose of the invention can not be obtained.
The polymerization temperature of the present invention is not particularly limited in the range of achieving the object of the present invention, but it is not a big problem to achieve the object of the present invention by performing the polymerization at a constant or multi-stage, for example, at 70 to 100 ° C. That is, the present invention is advantageous in that a polymer having a low molecular weight and a low molecular weight distribution can be obtained through the production method of the present invention even if a rapid reaction is performed at a high temperature.
According to the polymerization method of the present invention, it is difficult to control the reactivity in a polymerization system comprising conventional glycidyl methacrylate and / or glycidyl acrylate monomers to obtain an oligomeric polymer having a desired molecular weight and a desired molecular weight distribution When the polymerization method of the present invention is used, it is easy to control the molecular weight, and as a result, the reaction reproducibility is excellent.
Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention. In the present invention, "%" means weight% unless otherwise specified.
[Example 1]
First, 25 g of DMF (dimethylformamide) was added to a 1 L round-bottom flask reactor, and 143 g of a solution containing 6 wt% of AIBN (azobisisobutyronitrile) relative to the monomer in DMF was injected through a syringe pump at a rate of 0.75 ml / min and 390 g of a mixed monomer of glycidyl methacrylate, styrene and methyl methacrylate (GMA: SM: MMA = 50: 35: 15) was supplied at a flow rate of 1.7 ml / min through a metering pump . The mixed monomer contained 2.8w% of NDM (n-dodecylmercaptan) relative to the monomer. The polymerization reaction time was maintained at 80 ° C for 7 hours and at 100 ° C for 1 hour and purged with nitrogen during the reaction. After the reaction was completed, the solution was precipitated in water to obtain a polymer, followed by filtration and drying. The yield was 95% by weight and the molecular weight (Mw) was 7,500 and the poly dispersity was 2.26 by GPC analysis. The molecular weight and polydispersity of the above experiment were changed within 3%.
[Reaction Scheme 1]
[Example 2]
In a 2 L glass flask reactor, 50 g of DMF solvent was first charged, and 183 g of 18% AIBN solution dissolved in DMF was supplied at a flow rate of 1.3 ml / min through a metering pump. At the same time, mixed monomer (GMA 280 g, SM 175 g, MMA 50 g) and 15 g of NDM were fed at a flow rate of 2.4 ml / min. The mixed monomer contained 2.8w% of NDM (n-dodecylmercaptan) relative to the monomer. The polymerization reaction time was maintained at 80 ° C for 7 hours and at 100 ° C for 1 hour and purged with nitrogen during the reaction. After the reaction was completed, the solution was precipitated in water to obtain a polymer, followed by filtration and drying. The yield was 91% and the molecular weight (Mw) was 8,089 and the polydispersity was 2.35 through GPC analysis. As a result of three experiments, the molecular weight and the polydispersity were changed within 5%.
[Example 3]
Initiator 590 g of AIBN was dissolved in 3900 g of DMF and fed to a 20 L jacketed reactor at a flow rate of 21 ml / min by means of a metering pump. 985 g of DMF were placed in the reactor in advance so that the feed liquids were stirred smoothly. 9,764 g and 292 g of the mixed monomer (GMA: SM: MMA = 55: 35: 10) and NDM were supplied at a flow rate of 48 ml / min by the metering pump. The polymerization reaction time was maintained at 80 ° C for 7 hours and at 100 ° C for 1 hour and purged with nitrogen during the reaction. After the reaction was completed, the solution was precipitated in water to obtain a polymer, followed by filtration and drying. The yield was 94% and the molecular weight (Mw) was 7,500 and the polydispersity was 2.12 by GPC analysis. The molecular weight and polydispersity of the above experiment were changed within 3%.
[Comparative Example 1]
The procedure of Example 1 was repeated except that the solvent and the initiator were added and the reaction mixture was added at a total flow rate of 1.7 ml / min. The molecular weight (Mw) was 15,623 and the polydispersity was 6.02 through GPC analysis.
[Comparative Example 2]
In the same manner as in Comparative Example 1 except that toluene was used as a solvent, and the initiator and the reaction mixture were added in a batch. Through GPC analysis, the molecular weight (Mw) was 6,862 and the polydispersity was 3.4. In this case, it is difficult to collect precipitates in water, making recovery in products difficult.
[Comparative Example 3]
Example 1 was repeated except that tert-butyl hydroperoxide (TBP) was used as an initiator in Example 1 and toluene was used as a solvent. As a result, the molecular weight (Mw) was 16,330 and the polydispersity was 5.90 by GPC analysis. As a result of repeating the experiment three times in succession, the maximum molecular weight showed 21% and the dispersion showed 30%.
[Comparative Example 4]
30 g of GMA, 20 g of SM, 33 g of MMA, 17 g of BMA (butyl methacrylate), 6.5 g of TBP as initiator and 40 g of xylene were put into a 500 ml round-bottomed flask without using a metering pump and stirred at room temperature. It was purged with nitrogen without using CTA and polymerized at 138 ° C for 3 hours. After the reaction was completed, the solution was precipitated in water to obtain a polymer, followed by filtration and drying. The molecular weight (Mw) was 69,788 and the polydispersity was 18.18 by GPC analysis.
[Comparative Example 5]
30 g of GMA, 20 g of SM, 33 g of MMA, 17 g of BMA, 6.5 g of TBP as an initiator and 80 g of xylene were put into a 500 ml round-bottomed flask without using a metering pump and stirred at room temperature. CTA was not used and xylene solvent was used twice for Comparative Example 4. Purged with nitrogen and polymerized at 138 ° C for 3 hours. After the reaction was completed, the solution was precipitated in water to obtain a polymer, followed by filtration and drying. The molecular weight (Mw) was 101,961 and the polydispersity was 17.18 by GPC analysis.
While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. Therefore, the above description does not limit the scope of the present invention defined by the limitations of the following claims.
Claims (6)
Preparing a polar neutral solution containing an initiator;
Polymerizing the polymerization mixture and the polar neutral solution into the reactor for 4 to 8 hours, respectively, continuously and continuously;
And having a weight average molecular weight of 5,000 to 10,000 and a molecular weight distribution of 2 to 3 when the polymerization reaction has a conversion of 90% or more.
Wherein the chain transfer agent comprises 1 to 4 parts by weight based on 100 parts by weight of the monomer and 5 to 8 parts by weight of the initiator.
Wherein the initiator is azobisisobutyronitrile and the chain transfer agent is n-dodecyl mercaptan.
Wherein the polar neutral solution contains a reaction solvent and the reaction solvent is 20 to 50 parts by weight based on 100 parts by weight of the monomer.
Wherein the reaction solvent is at least one selected from the group consisting of dimethylacetamide, dimethylformamide and N-methylpyrrolidone as a polar, neutral solvent.
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| JP2009102663A (en) | 1998-03-12 | 2009-05-14 | Lucite Internatl Uk Ltd | Polymer composition |
| WO2015020099A1 (en) * | 2013-08-09 | 2015-02-12 | 東亞合成株式会社 | Active-energy-ray-curable adhesive composition for plastic film or sheet |
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| JP2009102663A (en) | 1998-03-12 | 2009-05-14 | Lucite Internatl Uk Ltd | Polymer composition |
| WO2015020099A1 (en) * | 2013-08-09 | 2015-02-12 | 東亞合成株式会社 | Active-energy-ray-curable adhesive composition for plastic film or sheet |
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