KR102178646B1 - Copolycarbonate and method for preparing the same - Google Patents

Abstract

The present invention relates to a copolycarbonate having excellent weather resistance and a method for producing the same.

Description

Copolycarbonate and its manufacturing method {COPOLYCARBONATE AND METHOD FOR PREPARING THE SAME}

The present invention relates to a copolycarbonate excellent in weather resistance and a method for producing the same.

Polycarbonate resin is a polymer material that is widely used in fields such as exterior materials of electric and electronic products, automobile parts, construction materials, and optical parts due to its excellent impact strength, numerical stability, heat resistance, and transparency.

As the application field of such polycarbonate resin is expanded in recent years, development of a new structure of copolycarbonate having improved weather resistance while maintaining the inherent physical properties of the polycarbonate resin is required.

Accordingly, studies have been attempted to obtain desired physical properties by copolymerizing two or more types of aromatic diols having different structures to introduce units having different structures into the main chain of polycarbonate. However, most of the technologies have limitations in that the production cost is high, and when the chemical resistance or impact strength increases, the transparency decreases, and when the transparency is improved, the chemical resistance or impact strength decreases.

Accordingly, there is still a need for research and development on a new structure of copolycarbonate having excellent mechanical properties such as tensile strength and impact strength and excellent weather resistance.

The present invention is to provide a copolycarbonate excellent in weather resistance and a method for producing the same.

The present invention provides a copolycarbonate comprising a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, and an end capping group represented by Formula 3.

A method for producing the copolycarbonate comprising polymerizing a composition comprising a monomer represented by Formula 4, a monomer represented by Formula 5, an end capping agent including an aromatic diol represented by Formula 6, and a carbonate precursor Provides.

Hereinafter, a copolycarbonate according to a specific embodiment of the present invention and a method for preparing the same will be described in more detail.

According to one embodiment of the invention, a copolycarbonate including a repeating unit represented by the following Formula 1, a repeating unit represented by the following Formula 2, and an end capping group represented by the following Formula 3 may be provided:

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,

R ₁ to R ₈ are each independently substituted or unsubstituted C _1-60 alkyl,

a, b, c, d, e, f, o and p are each independently an integer of 0 to 4,

An asterisk (*) means a bonding point.

Preferably, R ₁ to R ₈ in Formulas 1 to 3 are each independently a substituted or unsubstituted C _1-20 alkyl, or more preferably, a substituted or unsubstituted C _1-10 alkyl. have.

Specifically, R ₁ to R ₈ may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or dekyl.

Preferably, in Formulas 1 to 3, a, b, c, d, e, f, o and p may be an integer of 0 to 3, or an integer of 0 to 2.

More preferably, a, b, c, d, e, f, o and p may be 0 or 1.

The repeating units represented by Chemical Formulas 1 and 2 may exhibit long-term weather resistance due to a structure in which fries rearrangement can occur.

Further, the repeating unit represented by Formula 3 may exhibit excellent weather resistance due to a structure capable of keto-enol tautomerization.

Therefore, since the copolycarbonate includes the repeating unit, it may exhibit excellent properties such as impact strength, numerical stability, heat resistance, and transparency, which are inherent characteristics of conventional polycarbonate, and excellent weather resistance and hardness.

The repeating unit represented by Formula 1 may be, for example, a repeating unit represented by Formula 1-1 below.

[Formula 1-1]

The repeating unit represented by Formula 2 may be, for example, a repeating unit represented by Formula 2-1 below.

[Formula 2-1]

The end capping group represented by Formula 3 may be, for example, an end capping group represented by Formula 3-1 below.

[Formula 3-1]

Further, the molar ratio of the repeating unit represented by Formula 1 and the repeating unit represented by Formula 2 may be 1:0.001 to 1, 1:0.01 to 0.9, or 0.1 to 0.5.

The content of the end capping group represented by Formula 3 may be 0.0001 to 0.1 mol%, 0.001 to 0.05 mol%, or 0.01 to 0.03 mol%, based on the total weight of the copolycarbonate.

In addition, the copolycarbonate may have a weight average molecular weight of 20,000 to 100,000 g/mol, or 50,000 to 700,000 g/mol. When the weight average molecular weight of the copolycarbonate is less than 20,000 g/mol, there may be a problem that the amount of impact is very reduced. If the weight average molecular weight exceeds 100,000 g/mol, a problem may occur in injection properties.

Meanwhile, according to another embodiment of the present invention, a composition comprising a monomer represented by the following formula 4, a monomer represented by the following formula 5, an end capping agent including an aromatic diol represented by the following formula 6, and a carbonate precursor A method for preparing the copolycarbonate, including:

[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 4 to 6,

R ₁ to R ₈ are each independently substituted or unsubstituted C _1-60 alkyl,

a, b, c, d, e, f, o and p are independently integers from 0 to 4.

Preferably, in Formulas 4 to 6, R ₁ to R ₈ are each independently a substituted or unsubstituted C _1-20 alkyl, or more preferably, a substituted or unsubstituted C _1-10 alkyl. have.

Specifically, R ₁ to R ₈ may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or dekyl.

Preferably, in Formulas 4 to 6, a, b, c, d, e, f, o, and p may be an integer of 0 to 3, or an integer of 0 to 2.

More preferably, a, b, c, d, e, f, o and p may be 0 or 1.

The manufacturing method according to the embodiment comprises a polymerization step of polymerizing a composition comprising a monomer represented by Formula 4, a monomer represented by Formula 5, an end capping agent including an aromatic diol represented by Formula 6, and a carbonate precursor. And, through such a polymerization step, a copolycarbonate including a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, and an end capping group represented by Formula 3 may be obtained.

More specifically, the repeating unit represented by Formula 1 is formed by polymerization of a monomer represented by Formula 4, and the repeating unit represented by Formula 2 is formed by polymerization of a monomer represented by Formula 5, and the formula The end capping group represented by 3 may be formed by polymerizing an aromatic diol represented by Chemical Formula 6 with a monomer represented by Chemical Formula 4 or Chemical Formula 5.

The monomer represented by Formula 4 may exhibit an effect of long-term weather resistance due to a structure in which fries rearrangement can occur.

The monomer represented by Formula 4 may be, for example, a monomer represented by Formula 4-1 below.

[Formula 4-1]

In addition, the monomer represented by Formula 5 Due to the structure in which fries rearrangement can occur, the effect of long-term weatherability can be exhibited.

The monomer represented by Formula 5 may be, for example, a monomer represented by Formula 5-1 below.

[Chemical Formula 5-1]

In addition, the aromatic diol represented by Chemical Formula 6 is an end capping agent used to control the molecular weight of the copolycarbonate during polymerization, and can exhibit excellent weather resistance due to a structure capable of keto-enol tautomerization. have.

The aromatic diol represented by Formula 6 is a substituted or unsubstituted phenol bonded to both sides of a carbonyl group, specifically, a phenol group in which a carbonyl group and a hydroxy group are ortho substituted, and a carbonyl group and a hydroxy group are para substituted Phenolic groups may be included.

The hydroxy group contained in the para-substituted phenol group is relatively far from the carbonyl group, so the reaction selectivity for the polymerization reaction with the monomers represented by Formulas 4 and 5 is high, and acts as an end capping agent, whereas the ortho-substituted phenol Since the hydroxy group contained in the group is relatively close to the carbonyl group, the selectivity for the polymerization reaction is low, and thus the monomer may not be polymerized. Therefore, although the aromatic diol represented by Formula 6 contains two hydroxy groups, only the hydroxy group included in the para-substituted phenol group participates in the polymerization reaction to act as an end capping agent, so that the copolycarbonate containing the aromatic diol is weather resistant. This has an excellent effect.

The aromatic diol represented by Formula 6 may be, for example, an aromatic diol represented by Formula 6-1 below.

[Formula 6-1]

The end capping agent may further include, for example, mono-alkylphenol. The mono-alkylphenol is, for example, p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and It is at least one selected from the group consisting of triacontylphenol.

The end capping agent may be added before the start of polymerization, during the start of polymerization, or after the start of polymerization.

The carbonate precursor serves to link the compound represented by Formula 4, the compound represented by Formula 5, and/or the aromatic diol represented by Formula 6, and specific examples thereof include phosgene, triphosgene, diphosgene, Bromophosgene, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl ) It may be one or more selected from the group consisting of carbonate and bishaloformate.

The composition may include 40 to 60 moles of the monomer represented by Formula 4 and 40 to 60 moles of the monomer represented by Formula 5 with respect to 100 moles of the monomer represented by Formula 4 and the monomer represented by Formula 5. have.

The content of the end capping agent may be 0.0001 to 0.1 moles based on 100 moles of the monomer represented by Chemical Formula 4 and the monomer represented by Chemical Formula 5.

The content of the carbonate precursor may be 100 to 150 moles based on 100 moles of the monomer represented by Chemical Formula 4 and the monomer represented by Chemical Formula 5.

In this case, the polymerization is preferably performed by interfacial polymerization, and the polymerization reaction is possible at normal pressure and low temperature during interfacial polymerization, and molecular weight control is easy.

The polymerization temperature is preferably 0 ℃ to 40 ℃, the reaction time is 10 minutes to 5 hours. In addition, it is preferable to maintain the pH of 9 or more or 11 or more during the reaction.

The solvent that can be used for the polymerization is not particularly limited as long as it is a solvent used for polymerization of copolycarbonate in the art, and for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene may be used.

In addition, the polymerization is preferably carried out in the presence of an acid binder, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine may be used as the acid binder.

In addition, in order to accelerate the polymerization reaction, reactions such as triethylamine, tetra-n-butylammonium bromide, and tertiary amine compounds such as tetra-n-butylphosphonium bromide, quaternary ammonium compounds, quaternary phosphonium compounds, etc. Additional accelerators can be used.

According to the present invention, a copolycarbonate having excellent weather resistance and a method for producing the same can be provided.

The invention will be described in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

Example: Preparation of Copolycarbonate

Example 1

In a 20L glass reactor, bisphenol A (BPA) 1,014.57g, NaOH 40% aqueous solution 1,785g, the following (2-hydroxyphenyl)(4-hydroxyphenyl)methanone ((2-hydroxyphenyl)(4-hydroxyphenyl) methanone) 130g, the following bis (3-hydroxyphenyl) isophthalate (bis (3-hydroxyphenyl) isophthalate) 130g and 7,500g of distilled water were added, and after confirming that BPA was completely dissolved in a nitrogen atmosphere, 4,700 g of methylene chloride and 64 g of bis (3-hydroxyphenyl) terephthalate were added and mixed. I did. Here, 3,850 g of methylene chloride in which 565.3 g of triphosgene was dissolved was added dropwise for 1 hour. At this time, the NaOH aqueous solution was maintained at a pH of 12. After the dropwise addition is complete, 44 g of PTBP dissolved in 400 g of methylene chloride is added dropwise. After completion of the 6g dropwise addition, it was aged for 15 minutes, and 10 g of triethylamine was added. After 10 minutes, the pH was adjusted to 3 with 1N hydrochloric acid aqueous solution, washed three times with distilled water, and the methylene chloride phase was separated and then precipitated in methanol to obtain a powdery copolycarbonate resin.

Examples 2 and 3

It was prepared in the same manner as in Example 1, but a copolycarbonate was obtained by using a reaction material in the amount shown in Table 1 below.

Unit: g Example 1 Example 2 Example 3 Bis(3-hydroxyphenyl) isophthalate 130 130 130 Bis(3-hydroxyphenyl) terephthalate 130 130 130 (2-hydroxyphenyl)(4-hydroxyphenyl)methanone 64 38 18.95 p-tert-butylphenol (PTBP) 44 44 44

Comparative example One

In a 20L glass reactor, bisphenol A (BPA) 978.4 g, BPDA (bis(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl) decanedioate) 3.927 g, NaOH 32% aqueous solution 1,620 g, distilled water After 7,500 g was added and it was confirmed that BPA was completely dissolved in a nitrogen atmosphere, 3,670 g of methylene chloride and 17.9 g of p-tert-butylphenol (PTBP) were added and mixed. 3,850 g of methylene chloride in which 542.5 g of triphosgene was dissolved was added dropwise for 1 hour. At this time, the NaOH aqueous solution was maintained at pH 12. After completion of the dropwise addition, it was aged for 15 minutes, and 195.7 g of triethylamine was dissolved in methylene chloride and added. After 10 minutes, the pH was adjusted to 3 with 1N hydrochloric acid aqueous solution, washed three times with distilled water, and the methylene chloride phase was separated and then precipitated in methanol to obtain a powdery copolycarbonate resin.

Comparative Example 2

After adding 232 g of bisphenol A (BPA), 385 g of NaOH 32% aqueous solution, and 1,784 g of distilled water to a 20L glass reactor, and confirming that BPA is completely dissolved in a nitrogen atmosphere, p-tert-butylphenol (PTBP) 14.3 g -PDMS (2-allylphenol-substituted-polydimethylsiloxane) 12.54g and MBHB-PDMS (2-methyl-1-butenehydroxybenzoic acid-substituted-polydimethylsiloxane) 0.66g mixed solution (weight ratio 95:5) was added And mixed. 3,850 g of methylene chloride in which 128 g of triphosgene was dissolved was added dropwise for 1 hour. At this time, the NaOH aqueous solution was maintained at pH 12. After completion of the dropwise addition, it was aged for 15 minutes, and 46 g of triethylamine was dissolved in methylene chloride and added. After 10 minutes, the pH was adjusted to 3 with 1N hydrochloric acid aqueous solution, washed three times with distilled water, and the methylene chloride phase was separated and then precipitated in methanol to obtain a powdery copolycarbonate resin.

Comparative Example 3

70% by weight of the copolycarbonate of Comparative Example 1 and 30% by weight of the copolycarbonate of Comparative Example 2 were mixed to obtain a copolycarbonate composition.

Comparative Example 4

50% by weight of the copolycarbonate of Comparative Example 1 and 50% by weight of the copolycarbonate of Comparative Example 2 were mixed to obtain a copolycarbonate composition.

Experimental Example: Evaluation of physical properties of copolycarbonate

The properties of the injection specimens of polycarbonate prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were measured by the following method, and the results are shown in Table 2 below.

* Weight average molecular weight (g/mol): Using the Agilent 1200 series, it was measured by calibrating with PS standard.

* Impact strength (J/m): measured at 23°C according to ASTM D256 (1/8 inch, Notched Izod).

* Weather resistance: UV was irradiated using a Quick-UV instrument to measure YI (YI) for each time period.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Molecular Weight
(g/mol) 52,000 52,000 52,000 52,000 52,000 52,000 52,000 Room temperature impact strength (j/m) 844 854 851 875 823 855 846 Q-UV 0hr YI 1.13 1.59 1.34 1.05 3.53 2.23 2.88 Q-UV 500hr YI 8.35 6.51 6.52 17.48 21.48 16.78 19.13 Q-UV 1000hr YI 10.55 8.44 7.98 22.95 30.81 17.81 19.31 Q-UV 1500hr YI 15.76 12.35 15.37 31.24 34.53 18.97 26.75 Q-UV 2000hr YI 20.57 14.97 16.55 38.23 42.19 27.79 34.99

According to Table 2, the copolycarbonates of Examples 1 to 3 and Comparative Examples 1 to 4 have similar physical properties such as impact strength. However, in the weather resistance evaluation using a Quick-UV device, the lower the YI (Yellow Index) value that appears on the surface of the copolycarbonate by UV irradiation, the better the weather resistance. Examples 1 to 4 are after 500 hours of UV irradiation and 1,000 hours. , After 1,500 hours, and after 2,000 hours, the YI value was lower than in Comparative Examples 1 to 4, and it was confirmed that the weather resistance is remarkably excellent.

Claims (16)

Copolycarbonate comprising a repeating unit represented by the following Formula 1, a repeating unit represented by the following Formula 2, and an end capping group represented by the following Formula 3:
[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,
R ₁ to R ₈ are each independently substituted or unsubstituted C _1-60 alkyl,
a, b, c, d, e, f, o and p are each independently an integer of 0 to 4,
An asterisk (*) means a bonding point.
The method of claim 1,
The repeating unit represented by Formula 1 is a repeating unit represented by the following Formula 1-1, copolycarbonate.
[Formula 1-1]

The method of claim 1,
The repeating unit represented by Formula 2 is a repeating unit represented by Formula 2-1 below, a copolycarbonate.
[Formula 2-1]

The method of claim 1,
The end capping group represented by Formula 3 is an end capping group represented by the following Formula 3-1, copolycarbonate.
[Formula 3-1]

In Formula 3-1, an asterisk (*) means a bonding point.
The method of claim 1,
The repeating unit represented by Formula 1 and the repeating unit represented by Formula 2 have a molar ratio of 1:0.001 to 1, copolycarbonate.
The method of claim 1,
The content of the end capping group represented by Formula 3 is 0.0001 to 0.1 mol%, based on the total mol of copolycarbonate, copolycarbonate.
The method of claim 1,
Copolycarbonate is a copolycarbonate having a weight average molecular weight of 20,000 to 100,000 g/mol.
Polymerizing a composition comprising a monomer represented by Formula 4 below, a monomer represented by Formula 5 below, an end capping agent including an aromatic diol represented by Formula 6 below, and a carbonate precursor; of a copolycarbonate containing Manufacturing method:
[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 4 to 6,
Descriptions of R ₁ to R ₈ , a, b, c, d, e, f, o and p are as defined in claim 1.
The method of claim 8,
The monomer represented by Formula 4 is a monomer represented by the following Formula 4-1, a method for producing a copolycarbonate.
[Formula 4-1]

The method of claim 8,
The monomer represented by Formula 5 is a monomer represented by the following Formula 5-1, a method for producing a copolycarbonate.
[Chemical Formula 5-1]

The method of claim 8,
The aromatic diol represented by Formula 6 is an aromatic diol represented by Formula 6-1 below.
[Formula 6-1]

The method of claim 8,
The end capping agent is composed of p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and triacontylphenol. A method for producing a copolycarbonate further comprising at least one selected from the group.
The method of claim 8,
The carbonate precursors are phosgene, triphosgene, diphosgene, bromophosgene, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cre Sil carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate and at least one selected from the group consisting of bishaloformate, a method for producing a copolycarbonate.
The method of claim 8,
The composition comprises 40 to 60 moles of the monomer represented by Formula 4 and 40 to 60 moles of the monomer represented by Formula 5 with respect to 100 moles of the monomer represented by Formula 4 and the monomer represented by Formula 5, Method for producing copolycarbonate.
The method of claim 14,
The content of the end capping agent is 0.0001 to 0.1 moles based on 100 moles of the monomer represented by Chemical Formula 4 and the monomer represented by Chemical Formula 5, wherein the method for producing a copolycarbonate.
The method of claim 14,
The carbonate precursor content is 100 to 150 moles, based on 100 moles of the monomer represented by Formula 4 and the monomer represented by Formula 5, a method for producing a copolycarbonate.