KR20230166901A - Polycarbonate copolymer - Google Patents

Abstract

The present invention is intended to provide a polycarbonate copolymer, and can provide a polycarbonate copolymer with particularly improved heat resistance by including repeating units of a specific structure.

Description

Polycarbonate copolymer {Polycarbonate copolymer}

The present invention relates to polycarbonate copolymers and articles comprising them.

Polycarbonate resin is manufactured by condensation polymerization of aromatic diols such as bisphenol A and carbonate precursors such as phosgene, and has excellent impact strength, dimensional stability, heat resistance, and transparency, and is used as exterior materials for electrical and electronic products, automobile parts, building materials, and optical components. Applies to a wide range of fields.

Recently, in order to apply this polycarbonate resin to a wider range of fields, many studies have been attempted to obtain desired physical properties by copolymerizing two or more types of aromatic diol compounds with different structures and introducing units with different structures into the main chain of polycarbonate. .

In particular, as the application field of polycarbonate resin has expanded recently, it is necessary to improve heat resistance while maintaining the inherent physical properties of polycarbonate resin. Accordingly, attempts have been made to introduce repeating units of various structures as repeating units of polycarbonate resin. It is increasing.

Accordingly, the present inventors completed the present invention by confirming that heat resistance is particularly improved in a polycarbonate copolymer containing repeating units of a specific structure, as will be described later.

The present invention is intended to provide a polycarbonate copolymer with improved heat resistance by including repeating units of a specific structure.

Additionally, the present invention is to provide an article containing the polycarbonate copolymer.

In order to solve the above problems, the present invention provides a polycarbonate copolymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2) or (3):

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,

n1 and n2 are each independently integers from 0 to 4,

[Formula 2]

[Formula 3]

.

The polycarbonate copolymer according to the present invention includes a repeating unit represented by Formula 1 and a repeating unit represented by Formula 2 or Formula 3, and in particular, a polycarbonate copolymer with significantly increased heat resistance can be provided. Formula 1 is similar to the structure of bisphenol A, which has been widely used in the past, but has a structure in which four rings are fused, so the molecule has a rigid structure compared to bisphenol A, and also contains nitrogen inside the molecule, Heat resistance can be improved through stabilization. In addition, Formula 2 and Formula 3 are also similar to the structure of bisphenol A, but have a cyclohexane structure (Formula 2) and a structure in which two rings are fused (Formula 3), and these repeating units are added to the copolymer to form the structure. Heat resistance can be further improved through stabilization.

Hereinafter, the present invention will be described in more detail.

(Repeating unit represented by Formula 1)

In Formula 1, preferably, R ₁ is hydrogen.

Preferably, R ₂ is each independently hydrogen, C _1-4 alkyl, C _1-4 alkoxy, or halogen. More preferably, R ₂ is each independently hydrogen, methyl, or chloro.

Preferably, Formula 1 is any one selected from the group consisting of:

Meanwhile, the repeating unit represented by Formula 1 is derived from a monomer compound represented by Formula 1-1 below.

[Formula 1-1]

The meaning of 'derived from a monomeric compound' means that the hydroxyl group of the compound represented by Formula 1-1 reacts with the carbonate precursor to form a repeating unit represented by Formula 1.

The carbonate precursors include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis(chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate, One or more types selected from the group consisting of bis(diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and bishaloformate may be used. Preferably, triphosgene or phosgene can be used.

Additionally, the compound represented by Chemical Formula 1-1 can be prepared by the method shown in Scheme 1 below.

[Scheme 1]

In Scheme 1, the definitions of R ₁ , R ₂ , n1 and n2 are as previously defined. The reaction is preferably performed under acidic conditions, and the preparation method can be specified in the examples below.

(Repeating unit represented by Formula 2 or 3)

The polycarbonate copolymer according to the present invention includes a repeating unit represented by Formula 2 or Formula 3, and in this case, it may include only one type or a combination of two types.

Meanwhile, the repeating unit represented by Formula 2 or Formula 3 is derived from a monomer compound represented by Formula 2-1 or Formula 3-1, respectively.

[Formula 2-1]

[Formula 3-1]

The meaning of 'derived from a monomeric compound' is that the hydroxyl group of the compound represented by Formula 2-1 or Formula 3-1 reacts with the carbonate precursor to form a repeating unit represented by Formula 2 or Formula 3. it means.

The carbonate precursors include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis(chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate, One or more types selected from the group consisting of bis(diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and bishaloformate may be used. Preferably, triphosgene or phosgene can be used.

Preferably, the polycarbonate according to the present invention contains 0.01 to 80% by weight of the repeating unit represented by Formula 1, and 0.01 to 80% by weight of the repeating unit represented by Formula 2 or Formula 3. Preferably, the weight ratio of the repeating unit represented by Formula 1 and the repeating unit represented by Formula 2 or Formula 3 is 1:999 to 999:1, more preferably 1:99 to 99:1, Most preferably it is 1:9 to 9:1.

(Repeating unit represented by Chemical Formula 4)

In addition, the polycarbonate copolymer of the present invention may, if necessary, additionally include a repeating unit represented by the following formula (4):

[Formula 4]

In Formula 4 above,

_{and _ _ _}

R' ₁ to R' ₄ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen.

By additionally including a repeating unit represented by Formula 4, the physical properties of the polycarbonate copolymer can be adjusted along with the repeating unit represented by Formula 1 and the repeating unit represented by Formula 2 or 3. For example, the repeating unit represented by Formula 1 can improve heat resistance compared to the repeating unit represented by Formula 4, and thus the desired heat resistance properties can be adjusted by adjusting the content of each repeating unit.

In the above formula (4), preferably _, 2-diyl, butane-2,2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene. Also preferably, X is cyclohexane-1,1-diyl, O, S, SO, SO ₂ , or CO.

Also preferably, R' ₁ to R' ₄ are each independently hydrogen, methyl, chloro, or bromo.

Preferably, the repeating unit represented by Formula 4 is 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-hyde) Roxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)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, 1,1-bis(4-hydroxyphenyl)-1 -It may be derived from any one or more monomer compounds selected from the group consisting of phenylethane, and bis(4-hydroxyphenyl)diphenylmethane.

The meaning of 'derived from a monomer compound' means that the hydroxyl group of the monomer compound reacts with the carbonate precursor to form a repeating unit represented by the formula (4).

For example, when bisphenol A as a monomer compound and triphosgene as a carbonate precursor are polymerized, the repeating unit represented by Formula 4 has the structure below.

[Formula 4-1]

.

The carbonate precursor is the same as described above in the carbonate precursor that can be used to form the repeating unit represented by Formula 1.

polycarbonate copolymer

As described above, the polycarbonate copolymer according to the present invention includes a repeating unit represented by Formula 1 and a repeating unit represented by Formula 2 or 3, and in this case, it is a substantially random copolymer.

In addition, the polycarbonate copolymer according to the present invention, in addition to the repeating unit represented by Formula 1 and the repeating unit represented by Formula 2 or 3, further includes a repeating unit represented by Formula 4, and in this case, random aerial become amalgamated. Preferably, the weight ratio of (1) the repeating unit represented by Formula 1 and the repeating unit represented by Formula 2 or 3, and (2) the repeating unit represented by Formula 4 is 10:90 to 90:10. , more preferably 15:85 to 85:15, and most preferably 20:80 to 80:20.

Preferably, the polycarbonate copolymer according to the present invention has a weight average molecular weight (g/mol) of 10,000 to 100,00. More preferably, the polycarbonate copolymer according to the present invention has a weight average molecular weight (g/mol) of at least 15,000, at least 20,000, at least 25,000, at least 30,000, or at least 35,000; It 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.

Preferably, the glass transition temperature of the polycarbonate copolymer according to the present invention is 155 to 245°C. More preferably, the glass transition temperature of the polycarbonate copolymer according to the present invention is 156°C or higher, 157°C or higher, 158°C or higher, 159°C or higher, or 160°C or higher; It is 240℃ or lower, or 235℃ or lower.

Preferably, the tensile strength of the polycarbonate copolymer according to the present invention is 67 to 95 MPa. More preferably, the tensile strength of the polycarbonate copolymer according to the present invention is 68 MPa or more, 69 MPa or more, 70 MPa or more, 71 MPa or more, 72 MPa or more, 73 MPa or more, 74 MPa or more, 75 MPa or more, 76 MPa or more. MPa or greater, 77 MPa or greater, 78 MPa or greater, 79 MPa or greater, or 80 MPa or greater; It is 94 MPa or less, 93 MPa or less, 92 MPa or less, 91 MPa or less, or 90 MPa or less.

On the other hand, the polycarbonate copolymer according to the present invention includes the step of polymerizing a composition containing the monomer compound represented by Formula 1-1, the monomer compound represented by Formula 2-1 or 3-1, and the carbonate precursor described above. It can be manufactured by the following manufacturing method, and when it is desired to include a repeating unit represented by Formula 4, it can be manufactured by including a monomer compound related to the repeating unit represented by Formula 4 described above in the composition.

As the polymerization method, for example, an interfacial polymerization method can be used. In this case, the polymerization reaction is possible at normal pressure and low temperature, and the molecular weight is easy to control. The interfacial polymerization is preferably performed in the presence of an acid binder and an organic solvent. In addition, the interfacial polymerization may include, for example, adding a coupling agent after pre-polymerization, and then polymerizing again.

The materials used in the interfacial polymerization are not particularly limited as long as they can be used in the polymerization of polycarbonate copolymer, and the amount used can also be adjusted as needed.

For example, the acid binder may be an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine.

The organic solvent is not particularly limited as long as it is a solvent commonly used in the polymerization of polycarbonate, and for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene can be used.

In addition, the interfacial polymerization involves reactions such as tertiary amine compounds such as triethylamine, tetra-n-butylammonium bromide, and tetra-n-butylphosphonium bromide, quaternary ammonium compounds, and quaternary phosphonium compounds to promote the reaction. Additional accelerators may be used.

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

Additionally, the interfacial polymerization may be performed by further including a molecular weight regulator. The molecular weight regulator may be added before, during, or after polymerization.

Mono-alkyl phenol can be used as the molecular weight regulator, and examples of the mono-alkyl phenol include p-tert-butyl phenol, p-cumyl phenol, decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol, and octadecyl. It is at least one selected from the group consisting of phenol, eicosylphenol, docosylphenol and triacontylphenol, preferably p-tert-butylphenol, in which case the molecular weight control effect is great.

Additionally, the present invention provides an article comprising the polycarbonate copolymer described above.

Preferably, the article is injection molded. In addition, the above product may contain, for example, one or more selected from the group consisting of antioxidants, heat stabilizers, light stabilizers, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent whitening agents, ultraviolet absorbers, pigments and dyes. It can be included as .

The manufacturing method of the product includes mixing the polycarbonate copolymer according to the present invention and additives such as antioxidants using a mixer, extruding the mixture with an extruder to produce pellets, drying the pellets, and then extruding the mixture. It may include the step of injection into a molding machine.

As described above, the present invention can provide a polycarbonate copolymer with particularly improved heat resistance by including repeating units of a specific structure.

Figure 1 shows ¹ H NMR (DMSO-d ₆ ) data of the compound prepared in Preparation Example 1 of the present invention.
Figure 2 shows ¹ H NMR (DMSO-d ₆ ) data of the compound prepared in Preparation Example 2 of the present invention.
Figure 3 shows ¹ H NMR (DMSO-d ₆ ) data of the compound prepared in Preparation Example 3 of the present invention.

Hereinafter, embodiments of the present invention will be described in more detail in the following examples. However, the following examples only illustrate embodiments of the present invention, and the content of the present invention is not limited by the following examples.

Each physical property was measured as follows.

1) Weight average molecular weight (g/mol): Measured using Agilent 1200 series and calibrated with PC standard.

2) Glass transition temperature (℃): Measured with DSC Q100 (TA instrument).

[Manufacturing example]

Preparation Example 1-1: Preparation of monomer 1-1

o-phenylenediamine (13 g; 120 mmol) and 35% HCl (3.3 mL) were added to a round bottom flask, purged with nitrogen gas for 30 minutes, and stirred for 1 hour. PP compound (10 g, 31.4 mmol) was added and the temperature was slowly raised to 154°C, followed by reaction for 22 hours. After cooling to 120°C, distilled water (30 mL) and 35% HCl (15.4 mL) were added and stirred for 1 hour. After cooling to room temperature, it was filtered, washed with distilled water, and dried. This was dissolved in NaOH solution, adsorbed and filtered with charcoal, precipitated in HCl, and the precipitate was recovered to prepare monomer 1-1. NMR data of the prepared monomer 1-1 is shown in Figure 1, and MS data is as follows.

MS: [M+H] ⁺ = 391

Preparation Example 1-2: Preparation of monomer 1-2

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

MS: [M+H] ⁺ = 405

Preparation Example 1-3: Preparation of monomer 1-3

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

MS: [M+H] ⁺ = 419

Preparation Example 1-4: Preparation of monomer 1-4

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

MS: [M+H] ⁺ = 425

Manufacturing Examples 2-1 and 2-2

The following monomers were respectively purchased and used from Deepak Novochem Technologies Limited.

Example 1: Preparation of polycarbonate copolymer

In a 2 L main reactor equipped with a nitrogen purge and condenser and capable of maintaining room temperature with a circulator, water (620 g), bisphenol A (BPA; 98.18 g), monomer 1-3 (4.19 g), 40 wt. % NaOH aqueous solution (102.5 g) and MeCl ₂ (200 mL) were added, and the monomer 2-1 (36.41 g) was further added, and then stirred for about 10 minutes. Stop nitrogen purging, add triphosgene (62 g) and MeCl ₂ (120 g) to a 1 L round bottom flask to dissolve triphosgene, then slowly add the dissolved triphosgene solution into the main reactor, and when the addition is complete, PTBP (p-tert-butylphenol; 2.84 g) was added and stirred for about 10 minutes. Afterwards, a 40% by weight NaOH aqueous solution (97 g) was added, and then TEA (triethylamine; 1.16 g) was added as a coupling agent. At this time, the reaction pH was maintained between 11 and 13. After 30 minutes, HCl was added to terminate the reaction and the pH was lowered to 3-4.

Then, stirring was stopped to separate the organic layer and the water layer, and then the water layer was removed and pure water was added again, and the washing process was repeated 3 to 5 times. When the water was completely washed, only the organic layer was extracted and polycarbonate copolymer crystals were obtained by reprecipitation using a non-solvent using methanol. At this time, the prepared polycarbonate copolymer had a weight average molecular weight of 47,000 g/mol. As a result of analyzing the prepared polycarbonate copolymer by NMR, it was confirmed that repeating units derived from compounds 2-1 and 1-3 were contained in 18 wt% and 2 wt%, respectively, based on the weight of the total repeating units. The remaining examples and comparative examples were analyzed in the same manner.

Examples 2 to 12: Preparation of polycarbonate copolymers

Prepared in the same manner as Example 1, but adjusting the amounts of monomer 1-3, monomer 2-1, and BPA (Examples 2 to 6), or using monomer 2-2 instead of monomer 2-1 and monomer 1-3 , polycarbonate copolymers were prepared by adjusting the amounts of monomer 2-2 and BPA (Examples 7 to 12). At this time, the amount of PTBP (p-tert-butylphenol), a terminal terminator, was adjusted so that the weight average molecular weight of the produced polycarbonate copolymer was 47,000.

Comparative Examples 1 to 3: Preparation of polycarbonate

Polycarbonate was prepared in the same manner as in Example 1, but without using monomer 1-3 and by adjusting the amount of monomer 2-1 and BPA. At this time, the amount of PTBP (p-tert-butylphenol), a terminal terminator, was adjusted so that the weight average molecular weight of the produced polycarbonate copolymer was 47,000.

Comparative Examples 4 to 6: Preparation of polycarbonate

Polycarbonate was prepared in the same manner as in Example 1, except that monomer 1-3 was not used, monomer 2-2 was used instead of monomer 2-1, and the amounts of monomer 2-2 and BPA were adjusted. At this time, the amount of PTBP (p-tert-butylphenol), a terminal terminator, was adjusted so that the weight average molecular weight of the polycarbonate copolymer was 47,000.

Comparative Example 7: Preparation of polycarbonate

Polycarbonate was prepared in the same manner as in Example 1, but without using monomer 1-3 and monomer 2-1. The amount of PTBP (p-tert-butylphenol), a terminal terminator, was adjusted so that the weight average molecular weight of the polycarbonate copolymer was 47,000.

Experiment example

For the polycarbonate copolymers prepared in the above examples and comparative examples, the glass transition temperature and tensile strength were measured, and the tensile strength was measured according to ISO 527. The results are shown in Table 1 below. In Table 1 below, the content of each monomer refers to the monomer content relative to the total weight of the polycarbonate copolymer.

Monomer 1-3 content Monomer 2-1 content Monomer 2-2 content BPA content Tg tensile strength unit wt% wt% wt% wt% ℃ MPa Example 1 2.0 18.0 0 80.0 160 68 Example 2 0.2 19.8 0 80.0 159 67 Example 3 6.0 54.0 0 40.0 193 77 Example 4 0.6 59.4 0 40.0 191 74 Example 5 8.0 72.0 0 20.0 214 81 Example 6 0.8 79.2 0 20.0 212 78 Example 7 2.0 0 18.0 80.0 163 69 Example 8 0.2 0 19.8 80.0 162 68 Example 9 6.0 0 54.0 40.0 203 79 Example 10 6.0 0 59.4 40.0 201 76 Example 11 8.0 0 72.0 20.0 233 86 Example 12 0.8 0 79.2 20.0 231 82 Comparative Example 1 0 20.0 0 80.0 159 66 Comparative Example 2 0 60.0 0 40.0 190 73 Comparative Example 3 0 80.0 0 20.0 211 76 Comparative Example 4 0 0 20.0 80.0 161 67 Comparative Example 5 0 0 60.0 40.0 200 75 Comparative Example 6 0 0 80.0 20.0 230 80 Comparative Example 7 0 0 0 100.0 147 63

As shown in Table 1, it was confirmed that the polycarbonate copolymer containing the repeating unit according to the present invention had an increased glass transition temperature compared to the polycarbonate of the comparative example. Therefore, it can be confirmed that heat resistance is improved as the repeating unit according to the present invention is included in the structure of polycarbonate.

Claims (13)

A repeating unit represented by Formula 1 below, and
Containing a repeating unit represented by Formula 2 or Formula 3 below,
Polycarbonate copolymer:
[Formula 1]

In Formula 1,
R ₁ and R ₂ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,
n1 and n2 are each independently integers from 0 to 4,
[Formula 2]

[Formula 3]
.
According to paragraph 1,
R ₁ is hydrogen,
Polycarbonate copolymer.
According to paragraph 1,
R ₂ is each independently hydrogen, C _1-4 alkyl, C _1-4 alkoxy, or halogen,
Polycarbonate copolymer.
According to paragraph 1,
R ₂ is each independently hydrogen, methyl, or chloroin,
Polycarbonate copolymer.
According to paragraph 1,
Formula 1 is any one selected from the group consisting of:
Polycarbonate copolymer:

According to paragraph 1,
Containing 0.01 to 80% by weight of the repeating unit represented by Formula 1,
Containing 0.01 to 80% by weight of the repeating unit represented by Formula 2 or Formula 3,
Polycarbonate copolymer.
According to paragraph 1,
The polycarbonate copolymer further includes a repeating unit represented by the following formula (4):
Polycarbonate copolymer:
[Formula 4]

In Formula 4 above,
_{and _ _ _}
R' ₁ to R' ₄ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen.
In clause 7,
The formula 4 is expressed as follows,
Polycarbonate copolymer:
.
In clause 7,
Containing 20 to 80% by weight of the repeating unit represented by Formula 4,
Polycarbonate copolymer.
According to paragraph 1,
The weight average molecular weight of the polycarbonate copolymer is 10,000 to 100,000,
Polycarbonate copolymer.
According to paragraph 1,
The glass transition temperature of the polycarbonate copolymer is 155 to 245 ° C.
Polycarbonate copolymer.
According to paragraph 1,
The tensile strength of the polycarbonate copolymer is 67 to 95 MPa,
Polycarbonate copolymer.
An article comprising the polycarbonate copolymer of any one of claims 1 to 12.