KR20170055155A - Polymerizable composition - Google Patents

Abstract

The present invention relates to a polymerizable composition and, more specifically, to a polymerizable composition capable of forming an oxidized polymer having excellent solvent resistance. The polymerizable composition comprises: a mixture of an aromatic compound including a compound represented by chemical formula 1 and a compound represented by chemical formula 2; and an oxidizer.

Description

Polymerizable composition [0002]

The present application is directed to a polymerizable composition.

PPO (poly (phenylene oxide)) is one of representative engineering plastics and is applied to various fields including automobile materials, electronic devices, and electric appliances. Such PPO has advantages such as high glass transition temperature, impact resistance and low dielectric constant, but generally has a disadvantage in that it is poor in solvent dissolution property, that is, solvent resistance to a solvent containing a benzene ring, The scope of use is limited.

Patent Document 1: Korean Patent Laid-Open Publication No. 1998-0073758

The present application is directed to a polymerizable composition. The present application provides a polymerizable composition capable of forming a polymer of PPO (poly (phenylene oxide)) series with greatly improved solvent resistance.

The present application is directed to a polymerizable composition. The present inventors have found that when a certain amount of a monomer having at least two or more hydroxyl groups is copolymerized with a monomer forming a PPO series polymer and the monomer is superimposed on the monomer, a polymer having remarkably improved solvent resistance can be obtained Respectively. Although the reason why the solvent resistance is improved is not clear, the monomer having at least two or more hydroxyl groups superimposed on the copolymerized monomer, that is, the monomer forming the PPO series polymer, It is predicted that the copolymer is copolymerized with the monomer forming the PPO series polymer and forms a branch structure due to the presence of the additional hydroxyl group, thereby improving the solvent resistance.

Accordingly, the polymerizable composition of the present application may comprise a mixture of an aromatic compound comprising a compound of the following formula (1) and a compound of the following formula (2). The compound of formula (2) may be contained in an amount of 0.02 to 1 part by weight based on 100 parts by weight of the compound of formula (1). In the present application, the term " weight portion " may mean the ratio of the weight between the components unless otherwise specified.

[Chemical Formula 1]

In formula (1), R ₁ to R ₆ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkynyl group or a hydroxy group, and one of R ₁ to R ₆ is a hydroxyl group.

(2)

In formula (2), R ₇ to R ₁₂ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkynyl group or a hydroxy group, and at least two of R ₇ to R ₁₂ are hydroxyl groups.

The term alkyl group or alkoxy group in the present application includes, unless otherwise specified, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms Or an alkoxy group, and these alkyl groups or alkoxy groups may be substituted or unsubstituted.

Unless otherwise specified, the term alkenyl or alkynyl group in this application means a straight chain, branched or cyclic alkyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms or 2 to 4 carbon atoms, An alkenyl group or an alkynyl group, and the alkenyl group or alkynyl group may be substituted or unsubstituted.

The compound of the formula (1) may be a main component of the polymerizable composition. Accordingly, the compound of Formula 1 may contain at least about 80%, at least about 85%, at least about 90%, or at least about 95% of the compound of Formula 1 based on weight.

The specific kind of the compound of the formula (1) is not particularly limited. For example, the compound may be a compound wherein R ₁ is a hydroxy group and R ₂ and R ₆ are an alkyl group, for example, an alkyl group having 1 to 4 carbon atoms or a methyl group in the formula (1). In this case, R ₃ to R ₅ in the general formula (1) may be a hydrogen atom, an alkenyl group, an alkoxy group, an alkynyl group or the like.

The compound of formula (2) is a comonomer that is copolymerized with the compound of formula (1). As described above, it is expected that the compound acts to improve the solvent resistance by imparting a branching structure to the polymer in the polymerization process.

The compound of formula (2) may be used without limitation as long as it can perform the above-mentioned actions. For example, as the compound of formula (2), compounds wherein two of R ₇ to R ₉ in formula (2) are hydroxyl groups and the remaining substituents are hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups or alkoxy groups or hydrogen atoms can be used , In another example, R ₇ and R ₈ in the general formula (2) are a hydroxyl group, and R ₉ to R ₁₂ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group or a hydrogen atom.

The compound of formula (2) may be contained in an amount of 0.02 to 1 part by weight, 0.04 to 1 part by weight, 0.06 to 1 part by weight, 0.06 to 0.5 part by weight or 0.06 to 0.1 part by weight based on 100 parts by weight of the compound of formula (1). If the proportion of the compound of the general formula (2) is too small, the effect of improving the solvent resistance is deteriorated due to formation of an excessive branch structure or reduction of the reaction efficiency, etc., .

The polymerizable composition may further comprise an oxidizing agent. As the oxidizing agent, those used for forming the oxidized polymer can be used without limitation. The mechanism by which a polymer is formed by polymerization through oxidation by an oxidizing agent is a known reaction that can occur in nature.

As such an oxidizing agent, for example, an enzyme or a copper salt such as peroxidase, oxidase, oxygenase or laccase may be used. The copper salt may be at least one selected from the group consisting of Cu (I) Cl, Cu (II) Cl ₂ , Cu (NO ₃ ) ₂ and CuSO ₄ .

The ratio of the oxidizing agent in the polymerizable composition is not particularly limited as long as it is capable of inducing polymerization of the compounds of the formulas (1) and (2). For example, the oxidizing agent may be used in an amount of 1 to 30 parts by weight, 5 to 30 parts by weight, 10 to 30 parts by weight, or 15 to 30 parts by weight, based on 100 parts by weight of the compound of Formula 1, but is not limited thereto.

The polymerizable composition may further contain, in addition to the above-mentioned components, additional components known to contribute to the polymerization reaction by, for example, an oxidizing agent.

The present application is also directed to oxidized polymers. The term oxidized polymer in the present application may mean a polymer formed by polymerization by an oxidation reaction with an oxidizing agent.

The oxidized polymer of the present application may be one formed by polymerization of the above-mentioned polymerizable composition.

Thus, for example, the oxidized polymer may include a polymerized unit derived from the compound of formula (1) and a polymerized unit derived from the compound of formula (2).

In the polymer, the polymerization unit of the formula (1) may be a main polymerization unit of the polymer. Thus, the polymerization unit of the compound of the formula (1) may be at least 80%, at least 85%, at least 90% Or about 95% or more.

The polymerized unit derived from the compound of formula (2) in the oxidized polymer is used in an amount of about 0.02 to 1 part by weight, 0.04 to 1 part by weight, 0.06 to 1 part by weight, 0.06 to 0.5 part by weight Or 0.06 to 0.1 part by weight. Under these ratios, it is expected that an appropriate level of branching structure capable of securing solvent resistance in the polymer is formed.

The specific structures of the compounds of the formulas (1) and (2) are as described above.

As described above, the oxidized polymer may include a branched structure, and therefore excellent solvent resistance can be ensured.

The oxidized polymer may have a weight average molecular weight within the range of 4,000 to 60,000, but the molecular weight may be changed according to the purpose.

Such a polymer can be mixed with various other polymers with good miscibility as well as securing solvent resistance. For example, the oxidized polymer may be blended with polystyrene with good miscibility, for example, up to about 80% by weight with common polystyrene.

Accordingly, the present application relates to a polymer composition comprising the oxidized polymer and polystyrene.

The specific kind or mixing ratio of polystyrene in the polymer composition is not particularly limited, and known polystyrene can be used, and the ratio can also be changed according to the purpose.

The present application also relates to a method for producing the above-mentioned oxidized polymer. The above production method can be carried out, for example, by using the above-mentioned polymerizable composition.

For example, the production method may include a step of inducing polymerization of the compound of Formula 1 and the compound of Formula 2 by the oxidizing agent in the polymerizable composition described above.

The specific manner of carrying out the polymerization in the above is not particularly limited, and can be carried out, for example, using a known method applied to the production of PPO.

The present application provides a polymerizable composition. In the present application, a polymerizable composition capable of forming an oxidized polymer having excellent solvent resistance can be provided.

Fig. 1 is a photograph showing the solvent resistance of the polymers produced in Examples and Comparative Examples.

Hereinafter, the pressure-sensitive adhesive composition will be described in more detail with reference to Examples and Comparative Examples, but the scope of the pressure-sensitive adhesive composition is not limited to the following examples.

Example 1.

A monomer mixture was prepared by mixing 2,6-dimethyl phenol (2,6-dimethyl phenol) and catechol (2) as the compound of formula (1). In the mixture, catechol was used in an amount of about 0.08 parts by weight based on 100 parts by weight of 2,6-DMP. Polymerization was carried out by using a known method of preparing a phenol polymer by using CuCl as an oxidizing agent in the above mixture to prepare a polymer.

Comparative Example 1

Polymerization was carried out in the same manner as in Example 1 except that 2,6-DMP alone was polymerized as a monomer to produce a general PPO resin.

Comparative Example 2

Polymerization was carried out in the same manner as in Example 1 except that about 17 parts by weight of resorcinol was used instead of catechol, relative to 100 parts by weight of 2,6-DMP.

Test example.

The polymers prepared in Example 1 and Comparative Examples 1 and 2 were dried to obtain powders, and dissolved in THF (tetrahydrofuran) as a solvent at a concentration of about 1 mg / mL. The dissolution was carried out at a rate of about 60 rpm for 24 hours by introducing the polymer powder. Fig. 1 is a photograph showing the results of the dissolution, with the right side being the case of Example 1, the center being the case of Comparative Example 1, and the leftmost being the case of Comparative Example 2. It can be seen from the drawing that in the case of Example 1, the polymer including the branched structure is not dissolved and precipitated in THF. In the case of Example 1, when the weight recovery rate was examined after filtering through the filter, it was confirmed that the original weight was restored to about 90%. On the other hand, in the case of Comparative Example 1, almost no particles were filtered by the filter because it was almost dissolved in THF. Also in the case of Comparative Example 2, the solvent resistance to THF was not ensured.

Claims (12)

A polymerizable composition comprising a mixture of an aromatic compound and an oxidizing agent comprising a compound of the following formula (1) and 0.02 to 1 part by weight of a compound of the following formula (2) based on 100 parts by weight of the compound of the formula
[Chemical Formula 1]

Wherein R ₁ to R ₆ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkynyl group or a hydroxy group, and one of R ₁ to R ₆ is a hydroxyl group;
(2)

In formula (2), R ₇ to R ₁₂ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkynyl group or a hydroxy group, and at least two of R ₇ to R ₁₂ are hydroxyl groups. The method of claim 1, wherein R ₁ is a hydroxy group in Formula 1, R ₂ and R ₆ is an alkyl group, R ₃ to R ₅ is a hydrogen atom in the polymerization composition. The polymerizable composition according to claim 1, wherein two of R ₇ to R ₉ in the general formula (2) are a hydroxyl group and the remaining substituents are a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group. 2. The polymerizable composition according to claim 1, wherein R < ₇ > and R < ₈ > in the general formula (2) are a hydroxyl group and R ₉ to R ₁₂ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group. The polymerizable composition according to claim 1, wherein the oxidizing agent is a peroxidase, an oxidase, an oxygenase, a lactase or a copper salt. The method of claim 4 wherein the copper salt is _{CuCl, CuCl 2, Cu (NO} 3) 2 and CuSO ₄ is at least one selected from the group consisting of a polymerizable composition. The coating composition according to claim 1, wherein the oxidizing agent is contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the compound of the formula (1). An oxidizing polymer comprising polymerized units derived from a compound of the following formula 1 and 0.02 to 1 part by weight of polymerized units derived from a compound of the following formula 2 based on 100 parts by weight of the compound of the formula 1:
[Chemical Formula 1]

Wherein R ₁ to R ₆ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkynyl group or a hydroxy group, and one of R ₁ to R ₆ is a hydroxyl group;
(2)

In formula (2), R ₇ to R ₁₂ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkynyl group or a hydroxy group, and at least two of R ₇ to R ₁₂ are hydroxyl groups. 9. The oxidized polymer according to claim 8, having a branched structure. Wherein the weight average molecular weight is in the range of 4,000 to 60,000. A polymer composition comprising the oxidized polymer of claim 8 and polystyrene. A process for producing an oxidized polymer comprising the step of inducing polymerization of a compound of formula (1) and a compound of formula (2) by an oxidizing agent in the polymerizable composition of claim 1.

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