WO2017039189A1

WO2017039189A1 - Copolycarbonate and preparation method therefor

Info

Publication number: WO2017039189A1
Application number: PCT/KR2016/009043
Authority: WO
Inventors: 이기재; 손영욱; 홍무호; 반형민; 박정준
Original assignee: 주식회사 엘지화학
Priority date: 2015-09-01
Filing date: 2016-08-17
Publication date: 2017-03-09

Abstract

Provided are: a copolycarbonate, which comprises a repeating unit represented by chemical formula 1 and a repeating unit represented by chemical formula 2, and has a weight average molecular weight of 1,000 to 100,000 g/mol; and a preparation method therefor. The copolycarbonate has an excellent mechanical property and weather resistance.

Description

【Specification】

[Name of invention]

Copolycarbonate and its manufacturing method

Cross Citation with Related Application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0123707 dated September 1, 2015 and Korean Patent Application No. 10-2016-0019091 dated February 18, 2016. All content disclosed in the literature is included as part of this specification.

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

[Technique to become background of invention]

Polycarbonate resin is a polymer material that is used in various fields such as exterior materials, automotive parts, building materials, optical parts, etc. of electrical and electronic products due to its excellent lamella strength, numerical stability, heat resistance and transparency.

As the polycarbonate resin is recently expanded in application fields, it is required to develop a novel copolycarbonate having improved heat resistance and weather resistance while maintaining the inherent properties of the polycarbonate resin.

Accordingly, studies have been attempted to obtain desired physical properties by copolymerizing two or more kinds of aromatic diols having different structures to introduce units having different structures into the main chain of polycarbonate. However, most of the technologies have high production costs, and if the chemical resistance or impact strength is increased, the transparency is lowered. If the transparency is improved, the chemical resistance or the laminar strength is lowered. Therefore, there is still a need for research and development on a novel copolycarbonate having excellent mechanical properties such as hardness and excellent weatherability.

[Content of invention]

Problem to be solved The present invention is to provide a copolycarbonate having excellent mechanical properties and excellent weather resistance, and a method for producing the same.

[Measures of problem]

The present invention provides a copolycarbonate comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2) and having a weight average molecular weight of 1,000 to 100, 000 g / mol.

In addition, the present invention provides a method for producing the copolycarbonate, comprising the step of polymerizing a composition comprising a compound represented by the following formula (3), an aromatic diol compound and a carbonate precursor.

In addition, the present invention provides a molded article made of the copolycarbonate. Hereinafter, a copolycarbonate according to a specific embodiment of the present invention, a manufacturing method thereof, and a molded article will be described in more detail. According to an embodiment of the present invention, a copolycarbonate is provided, comprising a repeating unit represented by the following Chemical Formula 1 and a repeating unit represented by the following Chemical Formula 2, and having a weight average molecular weight of 1,000 to 10,000 g / mol. Can be:

In Chemical Formula 1,

Ri to ¾ are each independently hydrogen or d- ₁₀ alkyl,

Y is CHO alkylene,

Z is a bond, -0C0- or -C00-,

And ₁₅ cycloalkylene, 0, S, SO, S0 _2, or CO, - Xi to ¾ are each independently unsubstituted or substituted by a phenyl alkylene, Beach substituted with unsubstituted or alkyl substituted C ₃ to

[Formula 2]

In Chemical Formula 2,

R ₉ to ₂ are each independently hydrogen, d- ₁₀ alkyl, d-ω alkoxy, or halogen,

¾ is unsubstituted or substituted by phenyl or C- ₁₀ alkylene, unsubstituted or substituted with alkyl or a C ₃ -. ₁₅ cycloalkylene, 0, S, SO, S0 _{2 (or} CO in particular, the nose Since polycarbonates contain functional groups linked to Alkyl chains around thio functional groups, polycarbonates can exhibit additional fluidity and weather resistance properties while being excellent in layer resistance, transparency, and heat resistance. have.

At this time, it is preferable that said Y is d- ₅ alkylene.

In addition, it is preferable that ¾ to ¾ are each independently hydrogen or d- ₄ alkyl.

And ¾ to R ₁₂ are each independently hydrogen, methyl, chloro, or bromo. Also preferably, ¾ to ¾ are each independently unsubstituted or substituted with phenyl, straight or branched Cwo alkylene, more preferably methylene, ethane 1,1-diyl, propane-2,2- Diyl, butane-2,2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene. Also preferably, ¾ to ¾ are cyclonucleic acid -1,1-diyl, 0, S, SO, S0 ₂ , or CO.

In addition, 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, preferably 1: 0.001 to 1: 0.3.

The repeating unit represented by the formula (1) is characterized by excellent fluidity and weather resistance, the repeating unit represented by the formula (2) is characterized by excellent transparency and impact resistance, which are prepared when including them in the molar ratio Copolycarbonate is preferred because it can exhibit better mechanical properties, fluidity and weather resistance.

In addition, the copolycarbonate may have a weight average molecular weight of 1,000 to 100,000 g / mol, preferably 10,000 to 100,000 g / mol, more preferably 10,000 to 40,000 g / mol.

In addition, the copolycarbonate may have a yellowness change amount (dYI) of 20 or less, preferably 1 to 15, and more preferably 3 to 13, based on ASTM G155. On the other hand, according to another embodiment of the invention, comprising the step of polymerizing a composition comprising a compound represented by the formula (3), an aromatic diol compound and a carbonate precursor; comprising, a method for producing the copolycarbonate may be provided :

[Formula 3]

In Chemical Formula 3,

Ri to ¾ are each independently hydrogen or Cwo alkyl,

Y is Cwo alkylene,

Z is a bond, -0C0- or -coo-,

Xi to ¾ is unsubstituted or substituted with d- ₁₀ alkylene, unsubstituted or Cwo alkyl, substituted phenyl C ₃ - ₁₅ cycloalkylene, 0, S, SO, S0 _2, or CO.

In addition, the aromatic diol compound is a compound represented by the formula (4), and is represented by the formula (2).

[Formula 4]

In Chemical Formula 4, X ₃ and R ₉ to R ₁₂ are as defined in Chemical Formula 2.

Specific examples of the aromatic diol compound include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1, 1-bis (4-hydroxyphenyl) ethane, 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A) , 2,2-bis (4-hydroxyphenyl) butane, 1, 1-bis (4-hydroxyphenyl) cyclonucleic acid (bisphenol Z), 2, 2-bis (4-hydroxy— 3, 5-di Bromophenyl) propane, 2, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 2, 2-bis (4-hydroxy-3-bromophenyl) propane, 2, 2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis ^' (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3, 5-dimethylphenyl) propane And 1,1-bis (4-hydroxyphenyl) -1-phenylethane From may comprise at least one compound selected.

In addition, the .carbonate precursor serves to connect the compound represented by the formula (3) and the compound represented by the formula (4), specific examples thereof phosgene, triphosgene, diphosgene, bromophosgene, dimethyl carbonate, diethyl Carbonate, dibutyl carbonate, dicyclonuclear carbonate diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthylcarbonate, bis (diphenyl) carbonate or bishaloformate Can be.

In the polymerization, the compound represented by Formula 3 is 0.1 wt% or more, 1 wt% or more, or 3 wt% or more, 20 wt% or less, 10 wt% or less, based on 100 wt% of the composition, or Up to 7% by weight can be used. In addition, the aromatic di compound, 40% by weight or more, 50% by weight or more, or 55% by weight or more, or more than 80% by weight, 70% by weight or less, or 65% by weight or less with respect to 100% by weight of the composition. have.

The carbonate precursor may be used in an amount of 10 wt% or more, 20 wt% or more, or 30 wt%, 60 wt% or less, 50 wt% or less, or 40 wt% or less, based on 100 wt% of the composition.

At this time, the polymerization is preferably carried out by interfacial polymerization, the polymerization reaction can be carried out at normal pressure and low temperature during the interfacial polymerization and the molecular weight can be easily controlled. The polymerization temperature is 0 ^° C to 40 ^° C, reaction time is preferably 10 minutes to 5 hours. In addition, it is preferable to keep pH in reaction of 9 or more or 11 or more.

As a solvent which can be used for the said superposition | polymerization, if it is a solvent used for superposition | polymerization of copolycarbonate in the art, it will not specifically limit, For example, halogenated hydrocarbons, such as methylene chloride and chlorobenzene, can be used.

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

In addition, to control the molecular weight of the copolycarbonate during the polymerization, it is preferable to polymerize in the presence of a molecular weight regulator. As the molecular weight modifier, d-20 alkylphenol may be used, and specific examples thereof include p-tert-butylphenol, P-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, nuxadecylphenol, octadecylphenol, and eicosyl. Phenol, docosylphenol, or triacontyl phenol is mentioned. The molecular weight regulator may be added before the start of the polymerization, during the start of the polymerization or after the start of the polymerization. The molecular weight modifier may be used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 6 parts by weight, based on 100 parts by weight of the aromatic di compound, to obtain a desired molecular weight within this range.

Also, in order to promote the polymerization reaction, reactions such as tertiary amine compounds such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compounds, and quaternary phosphonium compounds Accelerators may additionally be used. According to another embodiment of the invention, a molded article made of the copolycarbonate may be provided. As described above, the copolycarbonate including the repeating unit represented by Chemical Formula 1 has excellent mechanical properties, and also has improved weather resistance, and thus has a wide field of use as compared to a molded article made of copolycarbonate.

The molded article may be one or more selected from the group consisting of antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, layer enhancers, fluorescent brighteners, ultraviolet absorbers, pigments and dyes, if necessary, in addition to copolycarbonates according to the present invention. It may further include.

As an example of the method for producing the molded article, the copolycarbonate and other additives according to the present invention are well mixed by using a mixer, and then extruded into an extruder to produce pellets, and the pellets are dried and then injected into an injection molding machine. It may include a step.

[Brief Description of Drawings]

1 is a graph of the working curve of the compound prepared in Example 1. FIG.

Figure 2 is a ¹ "NMR graph of the copolycarbonate prepared in Example 1. [Effect of the invention]

According to the present invention, a copolycarbonate having excellent mechanical properties and excellent weather resistance and a method of manufacturing the same can be provided.

[Specific contents to carry out invention]

The invention is explained in more detail in the following examples. However, the following examples are only for exemplifying the present invention, and the contents of the present invention are not limited to the following examples. Example: Preparation of Copolycarbonate

Example 1 (1) bi s- (4- (2- (4-hydroxyphenyl) propan-2-yl) pheny 1) 3, 3'- thiodip

After dissolving 5 g of 3,3'-Thiodipropionic acid in 50 ml of methylene chloride solvent in a back flask, 7.47 g of oxalyl chloride and DMF O.OOlg were added dropwise at room temperature and stirred at room temperature for about 4 hours. 3,3-Thiodipropionic chloride was obtained by removal. Then, the obtained 3,3'- Thiodipropionic chloride was dissolved in 50 ml of dichloromethane without any other purification process, and then slowly added to 13.12 g of Bisphenol A, 2.3 g of NaOH, and 50 ml of water, followed by stirring at room temperature for 24 hours. 50 ml of HC1 was added to terminate the reaction, followed by washing with water and dichloromethane. A final compound, bis- (4- (2- (4—hydroxyphenyl) propan-2-yl) phenyl) 3,3'-thiodipropionate, was obtained with a final yield of 85%.

¹ NMR of the compound is shown in FIG. 1.

(2) Preparation of Copolycarbonate Resin

2L main reactor equipped with a nitrogen purge and a condenser and capable of maintaining a room temperature with a circulator, 620g of water, 116.24g of BPA, bis- (4- (2- (4-hy dr) Oxypheny 1) propan-2-yl) phenyl) 3, 0.6 g of 3'-thiodi proionate, 102.5 g of NaOH, and 200 ml of MeCl ₂ were added and stirred for several minutes.

Stop nitrogen purging, add 62 g of Triphosgene and 120 g of MeCl ₂ in a 1 L isometric bottom flask, dissolve the Triphosgen, and slowly add the dissolved Triphosgen solution to the main reactor in which the BPA solution is dissolved. 2.28 g of tert-butylphenol) were added and stirred for about 10 minutes. After stirring was completed, 97 g of 40 wt% NaOH aqueous solution was added thereto, and then 1.16 g of TEA was added as a coupling agent. At this time, the reaction pH maintained 11-13. In order to complete the reaction, the pH was dropped to 3-4 by adding HC1 to terminate the reaction. And, Stop the stirring and separate the polymer and water layers, then remove the water layer and

¾0 was added again and washed three to five times.

After complete washing with water, only the polymer layer was extracted and polymer crystals were obtained by reprecipitation using a nonsolvent using methanol, ¾0, and the like. At this time, the produced polycarbonate had a weight average molecular weight of 31,000 g / mol.

^I NMR of the copolycarbonate thus prepared is shown in FIG. 2. Example 2

Except for changing the amount of BPA to 115.5g and the amount of bis- (4- (2- (4-hydroxyphenyl) propan-2-yl) phenyl) 3 and 3'-thiodi propionate to 2.4g Polycarbonate was prepared in the same manner as in Example 1. Example 3

Change the amount of BPA to 114.2 g, and change the amount of bi s_ (4- (2- (4-hydroxyphenyl) propan-2-yl) phenyl) 3,3'-thiodipropionate

A polycarbonate was prepared in the same manner as in Example 1 except for changing to 5.8 g. Example 4

Change the amount of BPA used to 111.6g and the amount of bi s- (4- (2- (4-hydroxyoxyy 1) prop an-2-y 1) phenyl) 3 and 3'-thiodipropionate to 12.6g Except that polycarbonate was prepared in the same manner as in Example 1. Example 5

Polycarbonate was prepared in the same manner as in Example 1, except that the PTBP was changed to 1.97 g. Example 6 Polycarbonate was prepared in the same manner as in Example 1, except that the amount of PTBP was changed to 3.41 g. Comparative Example 1

Except for using bis- (4- (2- (4-hydr oxypheny 1) propan-2-yl) phenyl) 3,3'-thiodipropionate and 116.47 g of BPA, the same procedure as in Example 1 Polycarbonate was prepared. Comparative Example 2

Except not using bi s- (4- (2- (4-hydr oxypheny 1) propan-2-yl) henyl) 3,3'- thiodipropionate, 116.47 g of BPA, and 1.97 g of PTBP Was prepared in the same manner as in Example 1. Comparative Example 3

Except for using bis- (4- (2- (4-hydroxyoxyy 1) propan-2-yl) henyl) 3,3'-thiodipropionate, 116.47g of BPA, and 3.41g of PTBP Was prepared in the same manner as in Example 1. Experimental Example: Evaluation of Physical Properties of Copolycarbonate

The characteristics of the injection specimens of the polycarbonate prepared in Example 1 and Comparative Example 1 were measured by the following method, the results are shown in Table 1.

* Weight average molecular weight (g / mol): Agilent 1200 series was measured by calibration with PC standard.

* Flowability (MI): measured according to ASTM D1238 (300 ^° C., 1.2 kg conditions).

* Glass transition temperature (, ^° C): Differential Scanning Calorimetry (DSC)

* Lamellar strength (IMP, J / m): measured at 23 ^° C according to ASTM D256 (l / 8 inch, Notched Izod). * Weather resistance (dYI, 500t ime): The change amount (dYI) of the yellow low index (dYI) of the specimen was measured according to ASTM G155 using a Zenon Whether or Zero meter. Table 1

Referring to Table 1, it can be seen that the copolycarbonate prepared in Example 1 shows not only the level of laminar strength equivalent to that of Comparative Example 1, which is a general polycarbonate, but also very excellent flowability. In addition, the copolycarbonate of this embodiment is very excellent in weatherability, which is a property that withstands various climates while maintaining the inherent properties of polycarbonate resin, it is easy to apply to various fields such as exterior materials, automotive parts, building materials of electrical and electronic products.

Claims

[Patent Claims]

[Claim 1]

It includes a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2),

Copolycarbonates having a weight average molecular weight of from 1,000 to 100, 000 g / mol:

In Chemical Formula 1,

Ri to ¾ are each independently hydrogen or Cwo alkyl,

Y is Cwo alkylene,

Z is a bond, -0C0- or -C00-,

Xi to ¾ are each independently unsubstituted phenyl, or a d- _lc alkylene, unsubstituted or substituted with a C ₃ alkyl substituted with - and ₁₅ cycloalkylene, 0, S, SO, S0 _2, or CO ,

[Formula 2]

In Chemical Formula 2,

¾ to R ₁₂ are each independently hydrogen, d-ω alkyl, d- ₁₀ alkoxy or halogen,

₁₅ cycloalkylene, 0, ^ SO, S0 _2, or C0 - ¾ is unsubstituted or Fe ^"Nilo Cwo substituted alkylene, unsubstituted or substituted with c- ₁₀ alkyl C _3.

[Claim 2] The method of claim 1,

Y is d- ₅ alkylene, copolycarbonate.

[Claim 3]

The method of claim 1,

Wherein ¾ to ¾ are each independently hydrogen or d- ₄ alkyl, copolycarbonate.

[Claim 4]

The method of claim 1,

The molar ratio of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) is 1: 0.001 to 1: 1, copolycarbonate.

[Claim 5]

The method of claim 1,

The copolycarbonate whose yellowness change (dYI) measured according to ASTM G155 is 20 or less.

[Claim 6]

A method for producing a copolycarbonate according to claim 1 comprising the step of polymerizing a composition comprising a compound represented by the following formula (3), an aromatic di compound and a carbonate precursor:

[Formula 3]

In Chemical Formula 3,

Ri to ¾ are each independently hydrogen or d- ₁₀ alkyl,

Y is du) alkylene, z is a combination, -oco—or—coo-

Let ₁₅ cycloalkylene, 0, S, SO, S0 _2, CO or - Xi to X ₂ is a du) alkylene, substituted or unsubstituted Cwo alkyl, or C ₃ substituted with unsubstituted or phenyl beach.

[Claim 7]

The method of claim 6,

Compound represented by the formula (3) is characterized in that the use of 0.01% by weight or more and 20% by weight or less with respect to 100% by weight of the composition, a method for producing a copolycarbonate.

[Claim 8]

A molded article made of the copolycarbonate of any one of claims 1 to 5.