Polycarbonate copolymer

Abstract

The present invention aims to provide a polycarbonate copolymer including a repeating unit represented by Chemical Formula 1 in the present specification, and can provide a polycarbonate copolymer improved by including a repeating unit having a specific structure of Chemical Formula 1, particularly in terms of heat resistance.

Description

Technical Field

[0001] Cross-references to related applications

[0002] This application claims the benefit of Korean Patent Application No. 10-2021-0104783, filed with the Korean Intellectual Property Office on August 9, 2021, the entire contents of which are incorporated herein by reference.

[0003] This disclosure relates to a polycarbonate copolymer and articles comprising the thereof. Background Technology

[0004] Polycarbonate resin is prepared by polycondensation of aromatic glycols such as bisphenol A and carbonate precursors such as phosgene. It possesses excellent impact strength, dimensional stability, heat resistance, and transparency. Therefore, polycarbonate resin has a wide range of applications, including exterior materials for electrical and electronic products, automotive parts, building materials, and optical components.

[0005] In recent years, in order to apply this polycarbonate resin to more diverse fields, many studies have been conducted by copolymerizing two or more aromatic diol compounds with different structures and introducing units with different structures into the main chain of polycarbonate to obtain the desired physical properties.

[0006] In particular, in recent years, with the expansion of the application fields of polycarbonate resins, it has become necessary to improve heat resistance while maintaining the inherent physical properties of polycarbonate resins. Therefore, attempts to introduce repeating units with various structures as repeating units in polycarbonate resins are increasing.

[0007] Therefore, the inventors have demonstrated that polycarbonate copolymers containing repeating units having a specific structure have particularly improved heat resistance, as described below, and have thus completed this disclosure. Summary of the Invention

[0008] Technical issues

[0009] One object of this disclosure is to provide a polycarbonate copolymer comprising repeating units having a specific structure, and thus achieving particularly improved heat resistance.

[0010] Another object of this disclosure is to provide an article comprising the polycarbonate copolymer.

[0011] Technical solution

[0012] To achieve the above objectives, according to this disclosure, a polycarbonate copolymer comprising repeating units represented by the following chemical formula 1 is provided:

[0013] [Chemical Formula 1]

[0014]

[0015] In chemical formula 1,

[0016] R1 and R2 are independently hydrogen and C, respectively. 1-10 Alkyl, C 1-10 Alkoxy, or halogen, and

[0017] n1 and n2 are each independent integers from 0 to 4.

[0018] The polycarbonate copolymer according to this disclosure comprises repeating units represented by Formula 1, and in particular, can provide a polycarbonate copolymer with significantly increased heat resistance. Formula 1 is similar in structure to bisphenol A, which has been widely used in the past, but has a four-ring fused structure, thus possessing a more rigid molecular structure compared to bisphenol A, and may also include nitrogen in the molecule, thereby improving heat resistance through structural stabilization.

[0019] This disclosure will now be described in more detail.

[0020] (Repeating unit represented by chemical formula 1)

[0021] In chemical formula 1, preferably, R1 is hydrogen.

[0022] Preferably, each R2 is independently hydrogen, C 1-4 Alkyl, C 1-4 Alkyl or halogen. More preferably, each R2 is independently hydrogen, methyl, or chlorine.

[0023] Preferably, chemical formula 1 is selected from any one of the following:

[0024]

[0025] Meanwhile, the repeating unit represented by chemical formula 1 comes from the monomeric compound represented by chemical formula 1-1 below.

[0026] [Chemical Formula 1-1]

[0027]

[0028] "From monomeric compounds" refers to the reaction of the hydroxyl group of a compound represented by chemical formula 1-1 with a carbonate precursor to form a repeating unit represented by chemical formula 1.

[0029] As a carbonate precursor, at least one selected from dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, dimethyl carbonate, bis(chlorophenyl) carbonate, di-m-methyl carbonate, dinaphthalene carbonate, bis(diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and dihalocarbamates can be used. Preferably, triphosgene or phosgene can be used.

[0030] Furthermore, the compound represented by chemical formula 1-1 can be prepared by the method described in reaction scheme 1 below.

[0031] [Reaction Scheme 1]

[0032]

[0033] In reaction scheme 1, R1, R2, n1, and n2 are defined as above. The reaction is preferably carried out under acidic conditions, and its preparation method can be found in the examples provided below.

[0034] (Repeating unit represented by chemical formula 2)

[0035] Furthermore, if desired, the polycarbonate copolymers of this disclosure may also comprise repeating units represented by the following chemical formula 2:

[0036] [Chemical Formula 2]

[0037]

[0038] In chemical formula 2,

[0039] X is an unsubstituted or phenyl-substituted C. 1-10 Alkylene, unsubstituted or C-substituted 1-10 Alkyl-substituted C 3-15 Cycloalkylene, O, S, SO, SO2, or CO, and

[0040] R′1 to R′4 are each independently hydrogen and C. 1-10 Alkyl, C 1-10 Alkoxy or halogen.

[0041] By also including repeating units represented by Chemical Formula 2, both types of repeating units are incorporated together with repeating units represented by Chemical Formula 1, thereby enabling the adjustment of the physical properties of the polycarbonate copolymer. For example, since repeating units represented by Chemical Formula 1 can improve heat resistance compared to repeating units represented by Chemical Formula 2, the desired heat resistance can be achieved by adjusting the content of each repeating unit.

[0042] In chemical formula 2, preferably, X is an unsubstituted or phenyl-substituted straight-chain or branched C. 1-10The alkylene group is more preferably methylene, ethane-1,1-diyl, propane-2,2-diyl, butane-2,2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene. Additionally, preferably, X is cyclohexane-1,1-diyl, O, S, SO, SO2, or CO.

[0043] Furthermore, preferably, R′1 to R′4 are each independently hydrogen, methyl, chlorine, or bromine.

[0044] Preferably, the repeating unit represented by Formula 2 may be selected from 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, bisphenol A, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxy-3,5-dibromo) At least one monomeric compound selected from the following: 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, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)diphenylmethane.

[0045] "From monomeric compounds" refers to the reaction of the hydroxyl groups of monomeric compounds with carbonate precursors to form repeating units represented by chemical formula 2.

[0046] For example, when bisphenol A, as a monomeric compound, and triphosgene, as a carbonate precursor, are polymerized, the repeating unit represented by chemical formula 2 has the following structure.

[0047] [Chemical Formula 2-1]

[0048]

[0049] The carbonate precursor is the same as that described in the carbonate precursors that can be used to form repeating units represented by the above chemical formula 1.

[0050] polycarbonate copolymer

[0051] As described above, the polycarbonate copolymer according to this disclosure comprises repeating units represented by chemical formula 1, and in this case, it is essentially a homopolymer.

[0052] Furthermore, the polycarbonate copolymer according to this disclosure comprises repeating units represented by Chemical Formula 1 and repeating units represented by Chemical Formula 2, and in this case, it becomes a random copolymer. In this case, preferably, the weight ratio between the repeating units represented by Chemical Formula 1 and the repeating units represented by Chemical Formula 2 is 10:90 to 90:10, more preferably 15:85 to 85:15, and most preferably 20:80 to 80:20.

[0053] Preferably, the polycarbonate copolymer according to this disclosure has a weight-average molecular weight (g / mol) of 10,000 to 100,000. More preferably, the polycarbonate copolymer according to this disclosure has a weight-average molecular weight (g / mol) of 15,000 or more, 20,000 or more, 25,000 or more, 30,000 or more, or 35,000 or more; and is 90,000 or less, 85,000 or less, 80,000 or less, 75,000 or less, 70,000 or less, 65,000 or less, 60,000 or less, or 55,000 or less.

[0054] Preferably, the polycarbonate copolymer according to this disclosure has a glass transition temperature of 150°C to 220°C. More preferably, the glass transition temperature of the polycarbonate copolymer according to this disclosure is 155°C or higher, or 160°C or higher; and is 215°C or lower, or 210°C or lower.

[0055] Furthermore, the polycarbonate copolymer according to this disclosure can be prepared by a preparation method comprising the following steps: polymerizing a composition containing a monomer compound represented by chemical formula 1-1 and the aforementioned carbonate precursor. In the case of containing a repeating unit represented by chemical formula 2, it can be prepared by including a monomer compound associated with the repeating unit represented by chemical formula 2 in the composition.

[0056] As a polymerization method, interfacial polymerization can be used as an example, in which the polymerization reaction can be carried out at atmospheric pressure and low temperature, and the molecular weight can be easily adjusted. Interfacial polymerization is preferably carried out in the presence of an acidic binder and an organic solvent. Furthermore, interfacial polymerization may include, for example, a step of adding a coupling agent after prepolymerization and then performing polymerization again.

[0057] There are no particular limitations on the materials used for the interfacial polymerization, as long as they are applicable to the polymerization of polycarbonate copolymers, and the amount used can be adjusted as needed.

[0058] As the acidic adhesive, for example, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, or amine compounds such as pyridine can be used.

[0059] There are no particular limitations on the organic solvent, as long as it is a solvent commonly used for polycarbonate polymerization, and as an example, halogenated hydrocarbons such as dichloromethane and chlorobenzene can be used.

[0060] In addition, the interfacial polymerization can also use reaction promoters such as tertiary amine compounds, quaternary ammonium compounds, or quaternary phosphine compounds, including triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphine bromide, to promote the reaction.

[0061] The reaction temperature for the interfacial polymerization is preferably between 0°C and 40°C, and the reaction time is preferably between 10 minutes and 5 hours. Additionally, the pH is preferably maintained above 9 or 11 during the interfacial polymerization reaction.

[0062] Furthermore, interfacial polymerization can be carried out by further including a molecular weight regulator. The molecular weight regulator can be added before, during, or after polymerization initiation.

[0063] Monoalkylphenols can be used as molecular weight regulators. Examples of monoalkylphenols are at least one selected from p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, dodecylphenol, triacontylphenol, preferably p-tert-butylphenol, and in this case, the effect of regulating molecular weight is greater.

[0064] Furthermore, this disclosure provides an article comprising the above-described polycarbonate copolymer.

[0065] Preferably, the article is an injection-molded article. Furthermore, the article may also include, for example, at least one selected from antioxidants, heat stabilizers, light stabilizers, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact-enhancing materials, fluorescent whitening agents, UV absorbers, pigments, and dyes.

[0066] A method for preparing the article may include the following steps: mixing the polycarbonate copolymer according to the present disclosure with an additive such as an antioxidant using a mixer, then extruding the mixture into pellets using an extruder, drying the pellets, and then injecting the pellets using an injection molding machine.

[0067] Beneficial effects

[0068] As described above, this disclosure can provide a polycarbonate copolymer with improved heat resistance by comprising repeating units having a specific structure. Attached Figure Description

[0069] Figure 1 The compound prepared in Example 1 of this disclosure is shown. 1 H NMR (DMSO-d6) data.

[0070] Figure 2 The compound prepared in Preparation Example 2 of this disclosure is shown. 1 H NMR (DMSO-d6) data.

[0071] Figure 3 The compound prepared in Preparation Example 3 of this disclosure is shown. 1 H NMR (DMSO-d6) data. Detailed Implementation

[0072] In the following description, embodiments of the present disclosure will be presented in more detail. However, the following embodiments are merely illustrative of embodiments of the present invention, and the scope of the present disclosure is not limited thereto.

[0073] The following physical properties were measured in the following examples and test cases.

[0074] 1) Weight-average molecular weight (g / mol): Calibrated and measured using an Agilent 1200 series according to PC standards.

[0075] 2) Glass transition temperature (°C): Measured using a DSC Q100 (TA Instruments).

[0076] Preparation Example 1: Preparation of Monomer 1

[0077]

[0078] o-Phenylenediamine (13 g; 120 mmol) and 35% HCl (3.3 mL) were added to a round-bottom flask, purged with nitrogen for 30 min, and then stirred for 1 h. PP compound (10 g, 31.4 mmol) was added, and the mixture was slowly heated to 154 °C and reacted for 22 h. After cooling to 120 °C, distilled water (30 mL) and 35% HCl (15.4 mL) were added, and the mixture was stirred for 1 h. The reaction mixture was cooled to room temperature, filtered, washed with distilled water, and dried. It was dissolved in NaOH solution, filtered with charcoal, and precipitated in HCl. The precipitate was recovered to prepare monomer 1. The NMR data of the prepared monomer 1 are shown below. Figure 1 As shown, and the MS data is as follows.

[0079] MS: [M+H] + =391

[0080] Preparation Example 2: Preparation of Monomer 2

[0081]

[0082] Monomer 2 was prepared in the same manner as in Preparation Example 1, except that 3,4-diaminotoluene (15.4 g, 125.6 mmol) was used instead of o-phenylenediamine. The NMR data of the prepared monomer 2 are shown below. Figure 2 As shown, and the MS data is as follows.

[0083] MS: [M+H] + =405

[0084] Preparation Example 3: Preparation of Monomer 3

[0085]

[0086] Monomer 3 was prepared in the same manner as in Preparation Example 1, except that 4,5-dimethylphenyl-1,2-diamine (17 g, 125.6 mmol) was used instead of o-phenylenediamine. The NMR data of the prepared monomer 3 are shown below. Figure 3 As shown, and the MS data is as follows.

[0087] MS: [M+H] + =419

[0088] Preparation Example 4: Preparation of Monomer 4

[0089]

[0090] Monomer 4 was prepared in the same manner as in Preparation Example 1, except that 4-chlorophenyl-1,2-diamine (17 g, 125.6 mmol) was used instead of o-phenylenediamine. The MS data of the prepared monomer 4 are as follows.

[0091] MS: [M+H] + =425

[0092] Example 1: Preparation of polycarbonate copolymer

[0093] In a 2L main reactor equipped with nitrogen purging and a condenser, and maintained at room temperature via a circulator, water (620g), bisphenol A (BPA; 98.34g), monomer 1 (28.05g), 40wt% NaOH aqueous solution (102.5g), and MeCl2 (200mL) were added and stirred for approximately 10 minutes. Nitrogen purging was stopped, and triphosgene (62g) and MeCl2 (120g) were added to a 1L round-bottom flask. After dissolving the triphosgene, the dissolved triphosgene solution was slowly added to the main reactor. After the addition was complete, PTBP (p-tert-butylphenol; 2.66g) was added, and the mixture was stirred for approximately 10 minutes. Then, 40wt% NaOH aqueous solution (97g) was added, followed by TEA (triethylamine; 1.16g) as a coupling agent. At this point, the reaction pH was maintained between 11 and 13. To complete the reaction after 30 minutes, HCl was added and the pH was lowered to between 3 and 4.

[0094] Then, stirring was stopped, the organic and aqueous layers were separated, the aqueous layer was removed, and the washing process with pure water was repeated 3 to 5 times. Upon completion of washing, only the organic layer was extracted, and polycarbonate copolymer crystals were obtained by solvent-free reprecipitation with methanol. At this point, the prepared polycarbonate copolymer had a weight-average molecular weight of 47,000 g / mol.

[0095] Examples 2 to 12: Preparation of polycarbonate copolymers

[0096] Except for adjusting the monomers and amounts shown in Table 1 below to replace monomer 1, the polycarbonate copolymer was prepared in the same manner as in Example 1. This time, the reaction time was adjusted so that the weight-average molecular weight of the prepared polycarbonate copolymer was 47,000.

[0097] Comparative example: Preparation of polycarbonate

[0098] The polycarbonate copolymer was prepared in the same manner as in Example 1, except that monomer 1 was not used. This time, the reaction time was adjusted so that the weight-average molecular weight of the prepared polycarbonate was 47,000.

[0099] The glass transition temperatures of the polycarbonate copolymers prepared in the examples and comparative examples were measured, and the results are shown in Table 1 below.

[0100] [Table 1]

[0101]

[0102] As shown in Table 1, it can be confirmed that the glass transition temperature of the polycarbonate copolymer comprising repeating units represented by Chemical Formula 1 according to the embodiments of the present disclosure is increased compared to the polycarbonate of the comparative examples. Therefore, it can be confirmed that the heat resistance is improved because the structure represented by Chemical Formula 1 according to the present disclosure is included in the structure of the polycarbonate.

Claims

1. A polycarbonate copolymer comprising repeating units represented by the following chemical formula 1: [Chemical Formula 1] In chemical formula 1, R1 and R2 are independently hydrogen and C, respectively. 1-10 Alkyl, C 1-10 Alkoxy or halogen, and n1 and n2 are each independent integers from 0 to 4.

2. The polycarbonate copolymer according to claim 1, wherein, R1 is hydrogen.

3. The polycarbonate copolymer according to claim 1, wherein, Each R2 is independently composed of hydrogen and C. 1-4 Alkyl, C 1-4 Alkoxy or halogen.

4. The polycarbonate copolymer according to claim 1, wherein, Each R2 is independently hydrogen, methyl, or chlorine.

5. The polycarbonate copolymer according to claim 1, wherein, Chemical formula 1 is selected from any of the following:

6. The polycarbonate copolymer according to claim 1, wherein, The polycarbonate copolymer also comprises repeating units represented by the following chemical formula 2: [Chemical Formula 2] In chemical formula 2, X is an unsubstituted or phenyl-substituted C. 1-10 Alkylene, unsubstituted or C-substituted 1-10 Alkyl-substituted C 3-15 Cycloalkylene, O, S, SO, SO2 or CO, and R'1 to R'4 are each independently hydrogen and C. 1-10 Alkyl, C 1-10 Alkoxy or halogen.

7. The polycarbonate copolymer according to claim 6, wherein, Chemical formula 2 is represented by the following:

8. The polycarbonate copolymer according to claim 6, wherein, The weight ratio between the repeating unit represented by chemical formula 1 and the repeating unit represented by chemical formula 2 is 10:90 to 90:

10.

9. The polycarbonate copolymer according to claim 1, wherein, The polycarbonate copolymer has a weight-average molecular weight of 10,000 g / mol to 100,000 g / mol. The weight-average molecular weight was calibrated and measured using an Agilent 1200 series according to PC standards.

10. The polycarbonate copolymer according to claim 1, wherein, The glass transition temperature of the polycarbonate copolymer is 150°C to 220°C. The glass transition temperature was measured using a TA Instruments DSC Q100.

11. An article comprising the polycarbonate copolymer according to any one of claims 1 to 10.

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