KR20190038161A - Copolycarbonate and method for preparing the same - Google Patents

Abstract

The present invention relates to copolycarbonate having excellent weather resistance, and a preparing method thereof. The copolycarbonate of the present invention comprises a repeating unit represented by chemical formula 1, a repeating unit represented by chemical formula 2, and a terminal capping group represented by chemical formula 3.

Description

≪ Desc / Clms Page number 1 > COPOLYCARBONATE AND METHOD FOR PREPARING THE SAME [

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

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

As the application fields of these polycarbonate resins have been expanded in recent years, it is required to develop a novel structure of the copolycarbonate having improved weatherability while maintaining the inherent physical properties of the polycarbonate resin.

Accordingly, attempts have been made to obtain desired properties by copolymerizing aromatic diols having two or more different structures to introduce the monomers having different structures into the main chain of the polycarbonate. However, most of the technologies have a limit in that the transparency is lowered when the production cost is high, the chemical resistance or the impact strength is increased, and the chemical resistance and the impact strength are lowered when the transparency is improved.

Therefore, there is still a need for research and development on a novel structure of copolycarbonate which is excellent in mechanical properties such as tensile strength, impact strength and weatherability.

The present invention is to provide a copolycarbonate having excellent weatherability and a process for producing the same.

The present invention provides a copolycarbonate comprising a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), and a terminal capping group represented by the formula (3).

A method for producing the copolycarbonate, which comprises polymerizing a composition comprising a monomer represented by formula (4), a monomer represented by formula (5), a terminal capping agent comprising an aromatic diol represented by formula (6), and a carbonate precursor .

The copolycarbonate according to a specific embodiment of the invention and its preparation process will be described in more detail below.

According to one embodiment of the present invention, there can be provided a copolycarbonate comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a terminal capping group represented by the following formula (3)

[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3,

R ₁ to R ₈ are each independently a 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 the general formulas (1) to (3) are each independently substituted or unsubstituted C _1-20 alkyl, more preferably 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 decyl.

Preferably, a, b, c, d, e, f, o and p in the general formulas 1 to 3 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 the formulas (1) and (2) may exhibit long-term weatherability due to the structure in which fries rearrangement can occur.

In addition, the repeating unit represented by the above formula (3) can exhibit an excellent weather resistance due to a structure capable of keto-enol tautomerization.

Accordingly, since the copolycarbonate contains the repeating unit, it can exhibit excellent properties such as impact resistance, numerical stability, heat resistance and transparency, which are inherent characteristics of existing polycarbonate, and excellent weather resistance and hardness.

The repeating unit represented by the formula (1) may be, for example, a repeating unit represented by the following formula (1-1).

[Formula 1-1]

The repeating unit represented by the formula (2) may be, for example, a repeating unit represented by the following formula (2-1).

[Formula 2-1]

The terminal capping group represented by the formula (3) may be, for example, a terminal capping group represented by the following formula (3-1).

[Formula 3-1]

The molar ratio of the repeating unit represented by the formula (1) to the repeating unit represented by the 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 terminal capping unit represented by the above-mentioned 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. If the weight average molecular weight of the copolycarbonate is less than 20,000 g / mol, the impact amount may be very low. If the weight average molecular weight exceeds 100,000 g / mol, problems may arise in injection properties.

According to another embodiment of the present invention, there is provided a composition comprising a monomer represented by the following formula (4), a monomer represented by the following formula (5), a terminal capping agent comprising an aromatic diol represented by the following formula (6), and a carbonate precursor The method comprising the steps of: polymerizing the copolycarbonate,

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the above formulas 4 to 6,

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

a, b, c, d, e, f, o and p are independently an integer of 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, 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 decyl.

Preferably, a, b, c, d, e, f, o and p in formulas 4 to 6 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 preparation method according to this embodiment may be carried out by a method comprising the steps of: polymerizing a composition comprising a monomer represented by the formula (4), a monomer represented by the formula (5), a terminal capping agent comprising an aromatic diol represented by the formula (6), and a carbonate precursor , And through this polymerization step, a copolycarbonate including the repeating unit represented by the formula (1), the repeating unit represented by the formula (2), and the terminal capping group represented by the formula (3) can be obtained.

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

The monomer represented by Formula 4 may exhibit long-term weatherability due to the structure in which fries rearrangement can occur.

The monomer represented by the formula (4) may be, for example, a monomer represented by the following formula (4-1).

[Formula 4-1]

The monomer represented by the formula (5) The effect of long-term weathering can be shown by the structure in which fries rearrangement can occur.

The monomer represented by the formula (5) may be, for example, a monomer represented by the following formula (5-1).

[Formula 5-1]

In addition, the aromatic diol represented by Formula 6 is a terminal capping agent used for controlling the molecular weight of the copolycarbonate in polymerization. Since the structure is capable of keto-enol tautomerization, have.

The aromatic diol represented by the formula (6) has a substituted or unsubstituted phenol bonded to both of the carbonyl groups. Specifically, a phenol group in which the carbonyl group and the hydroxy group are ortho-substituted, and a phenol group in which the carbonyl group and the hydroxy group are para- Lt; / RTI > may be included.

The hydroxy group contained in the para-substituted phenol group is relatively far from the carbonyl group and thus acts as a terminal capping agent because of its high reaction selectivity for the polymerization reaction with the monomer represented by Chemical Formulas 4 and 5, while the ortho-substituted phenol The hydroxy group contained in the group is relatively short in distance from the carbonyl group, so that the selectivity to the polymerization reaction is low and the monomer may not be polymerized. Therefore, although the aromatic diol represented by Formula 6 contains two hydroxyl groups, only the hydroxyl groups contained in the para-substituted phenol groups participate in the polymerization reaction and act as end capping agents, so that the copolycarbonate containing the aromatic diol has weatherability This has an excellent effect.

The aromatic diol represented by the formula (6) may be, for example, an aromatic diol represented by the following formula (6-1).

[Formula 6-1]

The end capping agent may further comprise, for example, a mono-alkyl phenol. The mono-alkylphenol may, for example, be selected from the group consisting of p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and Triacontylphenol, and the like.

The end capping agent may be added before the initiation of polymerization, during the initiation of polymerization or after initiation 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 examples thereof include phosgene, triphosgene, (Diphenyl carbonate), diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenylsulfonyl) carbonate, dibutyl ) Carbonate and a bishaloformate.

The composition may include 40 to 60 moles of the monomer represented by the formula (4) and 40 to 60 moles of the monomer represented by the formula (5), based on 100 moles of the monomer represented by the formula (4) have.

The content of the terminal capping agent may be 0.0001 to 0.1 mole based on 100 moles of the monomer represented by the formula (4) and the monomer represented by the formula (5).

The carbonate precursor may be contained in an amount of 100 to 150 moles per 100 moles of the monomer represented by the formula (4) and the monomer represented by the formula (5).

At this time, it is preferable that the polymerization is performed by interfacial polymerization, and polymerization reaction is possible at an atmospheric pressure and a low temperature in the interfacial polymerization, and the molecular weight can be easily controlled.

The polymerization temperature is preferably 0 ° C to 40 ° C, and the reaction time is preferably 10 minutes to 5 hours. The pH during the reaction is preferably maintained at 9 or more or 11 or more.

The solvent usable in the above polymerization is not particularly limited as long as it is a solvent used in the art for polymerization of the copolycarbonate. For example, halogenated hydrocarbons such as methylene chloride and chlorobenzene can be used.

The polymerization is preferably carried out in the presence of an acid binding agent, and as the acid binding agent, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or an amine compound such as pyridine can be used.

In order to accelerate the polymerization reaction, a reaction such as a tertiary amine compound such as triethylamine, tetra-n-butylammonium bromide or tetra-n-butylphosphonium bromide, a quaternary ammonium compound or a quaternary phosphonium compound Additional accelerators may be used.

According to the present invention, it is possible to provide a copolycarbonate excellent in weatherability and a method of producing the same.

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

Examples: Preparation of copolycarbonate

Example 1

A 20 L glass reactor was charged with 1,014.57 g of bisphenol A (BPA), 1,785 g of a 40% aqueous solution of NaOH, 2-hydroxyphenyl (4-hydroxyphenyl) methanone, bis (3-hydroxyphenyl) isophthalate, bis (3-hydroxyphenyl) isophthalate, And 7,500 g of distilled water were charged 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 Respectively. 3,850 g of methylene chloride dissolved in 565.3 g of triphosgene was added dropwise thereto over 1 hour. At this time, the NaOH aqueous solution was maintained at pH 12. After the dropwise addition, 44 g of PTBP dissolved in 400 g of methylene chloride is added dropwise. After the completion of the dropping, the mixture was aged for 15 minutes and 10 g of triethylamine was added thereto. After 10 minutes, the pH was adjusted to 3 with a 1N aqueous hydrochloric acid solution, followed by washing with water three times with distilled water. The methylene chloride phase was separated and precipitated in methanol to obtain a powdery copolycarbonate resin.

Examples 2 and 3

Copolycarbonate was prepared in the same manner as in Example 1, except that the reactants were used in the amounts 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

Into a 20 L glass reactor were charged 978.4 g of bisphenol A (BPA), 3.927 g of bis (4- (2- (4-hydroxyphenyl) propan-2-yl) phenyl) decanedioate, 1,620 g of a 32% aqueous solution of NaOH, After 7,500 g of 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 dissolved in 542.5 g of triphosgene was added dropwise thereto over 1 hour. At this time, the NaOH aqueous solution was maintained at pH 12. After completion of the dropwise addition, the mixture was aged for 15 minutes, and 195.7 g of triethylamine was dissolved in methylene chloride. After 10 minutes, the pH was adjusted to 3 with a 1N hydrochloric acid aqueous solution, followed by washing three times with distilled water. The methylene chloride phase was separated and precipitated in methanol to obtain a powdery copolycarbonate resin.

Comparative Example 2

232 g of bisphenol A (BPA), 385 g of NaOH 32% aqueous solution and 1,784 g of distilled water were placed in a 20 L glass reactor and 14.3 g of p-tert-butylphenol (PTBP) (Weight ratio 95: 5) of 12.54 g of -PDMS (2-allylphenol-substituted-polydimethylsiloxane) and 0.66 g of MBHB-PDMS (2-methyl-1-butene hydroxybenzoic acid-substituted-polydimethylsiloxane) And mixed. 3,850 g of methylene chloride dissolved in 128 g of triphosgene was added dropwise thereto over 1 hour. At this time, the NaOH aqueous solution was maintained at pH 12. After completion of the dropwise addition, the mixture was aged for 15 minutes, and 46 g of triethylamine was dissolved in methylene chloride. After 10 minutes, the pH was adjusted to 3 with a 1N hydrochloric acid aqueous solution, followed by washing three times with distilled water. The methylene chloride phase was separated and 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 polycarbonate injection specimens prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were measured by the following methods, and the results are shown in Table 2 below.

* Weight average molecular weight (g / mol): Measured by PS standard using Agilent 1200 series.

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

* Weatherability: YI (YI) was measured by UV irradiation using a Quick-UV instrument.

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 Impact strength at room temperature (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 the above 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 apparatus, the lower the YI (Yellow Index) value appearing on the surface of the copolycarbonate by UV irradiation, the better the weatherability. Examples 1 to 4 show that after 500 hours of UV irradiation, 1,000 hours , 1,500 hours, and 2,000 hours, the YI value was lower than that of Comparative Examples 1 to 4, and it was confirmed that the weather resistance was remarkably excellent.

Claims (16)

A copolycarbonate comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a terminal capping group represented by the following formula (3)
[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3,
R ₁ to R ₈ are each independently a 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 according to claim 1,
Wherein the repeating unit represented by the formula (1) is a repeating unit represented by the following formula (1-1).
[Formula 1-1]

The method according to claim 1,
Wherein the repeating unit represented by the formula (2) is a repeating unit represented by the following formula (2-1).
[Formula 2-1]

The method according to claim 1,
Wherein the end capping group represented by the formula (3) is a terminal capping group represented by the following formula (3-1).
[Formula 3-1]

In the formula (3-1), an asterisk (*) denotes a bonding point.
The method according to claim 1,
Wherein the molar ratio of the repeating unit represented by the formula (1) to the repeating unit represented by the formula (2) is 1: 0.001 to 1.
The method according to claim 1,
The content of the terminal capping group represented by the above formula (3) is 0.0001 to 0.1 mol% based on the total weight of the copolycarbonate.
The method according to claim 1,
The copolycarbonate has a weight average molecular weight of from 20,000 to 100,000 g / mol.
Polymerizing a composition comprising a monomer represented by the following formula (4), a monomer represented by the following formula (5), a terminal capping agent comprising an aromatic diol represented by the following formula (6), and a carbonate precursor Manufacturing method:
[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the above formulas 4 to 6,
R ₁ to R ₈ , a, b, c, d, e, f, o and p are as defined in claim 1.
9. The method of claim 8,
Wherein the monomer represented by the formula (4) is a monomer represented by the following formula (4-1).
[Formula 4-1]

9. The method of claim 8,
Wherein the monomer represented by the formula (5) is a monomer represented by the following formula (5-1).
[Formula 5-1]

9. The method of claim 8,
Wherein the aromatic diol represented by the formula (6) is an aromatic diol represented by the following formula (6-1).
[Formula 6-1]

9. The method of claim 8,
The end capping agent may be selected from the group consisting of p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and triacontylphenol Lt; RTI ID = 0.0 > 1, < / RTI >
9. The method of claim 8,
The carbonate precursor may be selected from the group consisting of phosgene, triphosgene, diphosgene, bromophosgene, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, (Diphenyl) carbonate, and bishaloformate, wherein the polycarbonate is at least one member selected from the group consisting of polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polycarbonate, polycarbonate,
9. The method of claim 8,
Wherein the composition comprises 40 to 60 moles of the monomer represented by the formula (4) and 40 to 60 moles of the monomer represented by the formula (5) based on 100 moles of the monomer represented by the formula (4) and the monomer represented by the formula (5) A method for producing a copolycarbonate.
15. The method of claim 14,
Wherein the content of the terminal capping agent is 0.0001 to 0.1 mole relative to 100 moles of the monomer represented by the formula (4) and the monomer represented by the formula (5).
15. The method of claim 14,
Wherein the content of the carbonate precursor is 100 to 150 moles relative to 100 moles of the monomer represented by the formula (4) and the monomer represented by the formula (4).