KR102229664B1 - Polycarbonate and method for preparing the same - Google Patents

Abstract

The present invention relates to a polycarbonate having a novel structure and a method for producing the same, which exhibits excellent weather resistance.

Description

Polycarbonate and its manufacturing method {POLYCARBONATE AND METHOD FOR PREPARING THE SAME}

The present invention relates to a polycarbonate and a method for producing the same. More specifically, it relates to a polycarbonate of a novel structure showing improved weather resistance while maintaining excellent impact strength characteristics, and a method of manufacturing 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.

However, polycarbonate exhibits a high absorption rate up to 380 nm in the ultraviolet region, but has a disadvantage in that the structure is deformed, resulting in weakening of physical properties and coloring phenomena, resulting in poor weather resistance.

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, or by changing a molecular weight modifier. However, most of the technologies have limitations in that the production cost is high, and when chemical resistance, weather resistance, and impact strength increase, the transparency decreases, and when transparency is improved, chemical resistance or impact strength decreases.

On the other hand, as the outdoor market grows in recent years, there is a trend of increasing customer demand for materials with excellent weather resistance while maintaining excellent impact strength characteristics.

Accordingly, there is still a need for research and development on a new structure of polycarbonate with improved weather resistance while maintaining excellent physical properties of the polycarbonate itself.

The present invention is to provide a polycarbonate and a method for producing the same, while maintaining excellent impact strength characteristics and exhibiting improved weather resistance.

The present invention provides a polycarbonate containing a repeating unit represented by Formula 1.

In addition, the present invention provides a method for producing the polycarbonate, comprising polymerizing a composition comprising a compound represented by Chemical Formula 3 and a carbonate precursor.

In addition, the present invention provides a molded article made of the polycarbonate.

Hereinafter, a polycarbonate according to a specific embodiment of the present invention, a method of manufacturing the same, and a molded article will be described in more detail.

According to one embodiment of the invention, there is provided a polycarbonate comprising a repeating unit represented by the following formula (1):

[Formula 1]

In Formula 1,

Cy is unsubstituted or _{substituted with C 1-10} alkyl, C _1-10 alkoxy, or halogen, C _5-20 cycloalkylene,

m and n are the same as or different from each other, and are each independently an integer of 0 to 50, provided that m+n is an integer of 2 or more.

The polycarbonate containing the repeating unit of the above structure has high hardness, so while maintaining excellent impact strength characteristics, it can exhibit improved weather resistance.

Specifically, the oligomeric repeating unit represented by Chemical Formula 1 can change its structure by the fries rearrangement of the ester groups located between the benzene structures, so that it has a better weather resistance improvement effect than the conventional polycarbonate. According to the content (n, m) and structural isomers of the hydroxybenzoate repeating units contained in the structure of Formula 1, the weather resistance improvement effect of the polycarbonate may be further increased. In addition, since a rigid chain is formed including a cycloalkylene (Cy) linker such as cyclohexylene, the hardness characteristics can be further improved.

In the present specification, the cycloalkylene having 5 to 20 carbon atoms (C _5-20 ) may be a monocyclic or polycyclic cycloalkylene group. Specifically, the cycloalkylene having 5 to 20 carbon atoms is monocyclic or polycyclic cycloalkylene having 6 to 18 carbon atoms; Or it may be a monocyclic or polycyclic cycloalkylene having 6 to 12 carbon atoms. More specifically, the cycloalkylene having 5 to 20 carbon atoms may be a divalent group derived from an alicyclic hydrocarbon such as cyclopentylene, cyclohepylene, or cycloheptylene as a monocyclic cycloalkylene, and as polycyclic cycloalkylene Adamantane-diyl, norbonane-diyl, and the like. However, it is not limited thereto. In addition, the cycloalkylene having 3 to 20 carbon atoms may be one or more substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy having 1 to 10 carbon atoms, or a halogen.

In addition, in the present specification, the alkyl may be a linear or branched alkyl group having 1 to 10 carbon atoms or 1 to 5 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl- Propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, alkylene is a divalent group derived from an aliphatic hydrocarbon having 1 to 10 carbon atoms or 1 to 5 carbon atoms, and specific examples of the alkylene group include methylene, ethylene, n-propylene, butylene, etc., but these It is not limited to

In the present specification, alkoxy may be an alkoxy group having 1 to 10 carbon atoms or 1 to 5 carbon atoms. Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, 1-methyl-butoxy, 1-ethyl- Butoxy, or pentoxy, and the like, but are not limited thereto.

In the present specification, halogen is a fluoro, chloro, bromo, or iodo group.

Specifically, in Chemical Formula 1, Cy is an unsubstituted or substituted C _6-12 cycloalkylene, and considering the excellent polymerization stability improvement and molecular weight control effect of the polycarbonate through structure stabilization, the Cy is more Specifically, it may be unsubstituted or substituted cyclohexylene. In addition, when the Cy is substituted, it may be substituted with one or more substituents selected from the group consisting of _{C 1-10} alkyl, C _{1-10 alkoxy, and halogen, and more specifically, methyl, ethyl, isopropyl, etc.} It may be substituted with straight or branched C _{1-4 alkyl.}

또는

일 수 있다. More specifically, the Cy is

or

Can be

In addition, in Formula 1, each of the phenylene groups may each independently be substituted with 1 to 4, more specifically 1 or 2, substituents. In this case, each of the substituents may be independently C _1-10 alkyl, C _1-10 alkoxy, or halogen, and more specifically, may be linear or branched C _1-4 alkyl such as methyl, ethyl, isopropyl, and the like.

In addition, in Formula 1, the weather resistance of the polycarbonate may be further increased depending on the content (m and n) of the repeating units derived from hydroxybenzoate. Specifically, m and n are each an integer of 0 or more, or 1 or more, or 2 or more, and may be an integer of 50 or less, or 20 or less, or 15 or less, or 10 or less, or 5 or less, The value of m+n is an integer of 2 or more, and may be an integer of 50 or less, or 20 or less, or 10 or less, or 5 or less. When included in the above content range, it may exhibit better weather resistance.

Specific examples of the repeating unit represented by Formula 1 may include the following Formula 1a or 1b, but are not limited thereto:

[Formula 1a]

[Formula 1b]

In Formulas 1a and 1b, m and n are as defined in Formula 1, and more specifically, m and n are each an integer of 0 or more, or 1 or more, or 2 or more, and 50 or less, or 20 or less, or Under conditions satisfying an integer of 15 or less, or 10 or less, or 5 or less, the value of m+n is an integer of 2 or more, and may be an integer of 50 or less, or 20 or less, or 10 or less, or 5 or less.

In addition, the repeating unit represented by Formula 1 is 5% by weight or more, or 10% by weight or more, or 15% by weight or more, 50% by weight or less, or 30% by weight or less, or 25% by weight based on the total weight of the polycarbonate. It may be included in the following amounts. When included in the above content range, while maintaining the excellent impact strength of the polycarbonate may exhibit more improved weather resistance.

The polycarbonate according to an embodiment of the present invention may consist of only the repeating unit represented by Formula 1, or may further include a repeating unit derived from another aromatic diol compound in addition to the repeating unit represented by Formula 1 have.

Specifically, the polycarbonate may further include a repeating unit represented by the following formula (2), together with the repeating unit represented by the formula (1):

[Formula 2]

In Chemical Formula 2,

R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy or halogen,

Z is an unsubstituted or beach, or a phenyl C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, CO or substituted.

Specifically, in Formula 2, R ₁ to R ₄ may each independently be hydrogen, C _1-4 alkyl or halogen, and more specifically, R ₁ to R ₄ may each independently be hydrogen, methyl, chloro, or bro Can be gathered.

In addition, in Formula 2, Z may be each independently unsubstituted or phenyl-substituted linear or branched C _1-10 alkylene, and more specifically methylene, ethane-1,1-diyl, propane -2,2-diyl, butane-2,2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene.

Since the repeating unit represented by Formula 1 has excellent weather resistance, and the repeating unit represented by Formula 2 has excellent transparency and impact resistance, the molar ratio of the repeating units represented by Formulas 1 and 2 is adjusted. Thus, a polycarbonate of desired physical properties can be prepared.

When the polycarbonate according to an embodiment of the present invention further includes a repeating unit represented by Formula 2 in addition to the repeating unit represented by Formula 1, the weight ratio thereof is not particularly limited, for example, represented by Formula 1 The weight ratio of the repeating unit to the repeating unit represented by Formula 2 may be 99:1 to 1:99.

For example, when the weight ratio of the repeating unit represented by Formula 1 to the repeating unit represented by Formula 2 is 50:50 to 1:99, excellent transparency and impact resistance may be maintained, while more improved polymerization stability and weather resistance may be exhibited. And, when the weight ratio of the repeating unit represented by Formula 1 to the repeating unit represented by Formula 2 is greater than 50:50 to 99:1 or less, excellent weather resistance may be exhibited, and more improved effects in terms of transparency and impact resistance may be exhibited. . In consideration of the remarkable effect of improving weather resistance, the weight ratio of the repeating unit represented by Formula 1 to the repeating unit represented by Formula 2 may be 30:70 to 10:90.

On the other hand, in the present invention, the content of the repeating structures contained in the polycarbonate can be calculated according to a conventional method from the results after nuclear magnetic resonance (NMR) analysis of the polycarbonate, and the specific measurement method is carried out below. As described in the example.

In addition, the polycarbonate according to an embodiment of the present invention can properly adjust the weight average molecular weight (Mw) according to the purpose and use, and can exhibit improved weatherability while maintaining excellent properties of the polycarbonate itself, such as transparency and impact strength. When considering the weight average molecular weight of the polycarbonate is 40,000 g/mol or more, or 45,000 g/mol or more, or 48,000 g/mol or more, and 60,000 g/mol or less, or 55,000 g/mol or less, or 50,000 g/mol It can be below.

Meanwhile, in the present invention, the weight average molecular weight (Mw) of the polycarbonate and the oligomer used in its preparation was determined by gel permeation chromatography (GPC) using a polystyrene standard (PS standard) using the Agilent 1200 series. Can be measured. Specifically, it can be measured using an Agilent 1200 series instrument using a Polymer Laboratories PLgel MIX-B 300mm length column, at which time the measurement temperature is 160°C, the solvent used is 1,2,4-trichlorobenzene, and the flow rate Is 1 mL/min. Samples of polycarbonate or oligomer were prepared at a concentration of 10 mg/10 mL, respectively, supplied in an amount of 200 μL, and the Mw value was derived using a calibration curve formed using a polystyrene standard. At this time, the molecular weight (g/mol) of the polystyrene standard is 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

In addition, the melt index (MI) of the polycarbonate measured according to ASTM D1238 (300℃, 1.2kg condition) can also be appropriately adjusted according to the purpose and use, and excellent properties of the polycarbonate itself such as transparency and impact strength. Considering that the polycarbonate can exhibit improved weatherability while maintaining the melt index of the polycarbonate is 5 g / 10 min or more, 7 g / 10 min or more, or 10 g / 10 min or more, 20 g / 10 min or less, or 15 g It may be less than /10min, or less than 12 g/10min.

Polycarbonate according to an embodiment of the present invention that satisfies the above configuration and physical property conditions exhibits improved weather resistance. Specifically, L, a, and b values were measured by the ASTM D7869 method for a 1/8 inch thick specimen manufactured using the polycarbonate, and then the specimen was left in a weather-resistant condition for 2250 hours using a ^{Weather-Ometer ® machine.} From the L', a'and b'values measured again afterwards, the weather resistance (ΔE) under the condition of 2250 hr calculated according to Equation 1 below is 18 or less or 16 or less. The lower the weather resistance, the more preferable, so the lower limit is not particularly limited, but may be more specifically 1 or more or 2 or more.

[Equation 1]

(In Equation 1, L, a and b are values measured by the ASTM D7869 method for a 1/8 inch thick specimen made of a polycarbonate resin, and L', a'and b'are the corresponding specimens under 2250 hr weather resistance conditions. It is the value measured again after leaving it unattended)

In addition, the polycarbonate exhibits improved hardness properties with excellent weatherability as described above. Specifically, as described in the experimental examples to be described later, when evaluating the scratch resistance according to KS D 3520 using a simple transfer pencil hardness tester (No.221D, Yoshimitsu), it exhibits a high pencil hardness of HB or higher or F or higher. .

On the other hand, according to another embodiment of the present invention, there is provided a method for producing the polycarbonate, comprising polymerizing a composition comprising a compound represented by the following formula (3) and a carbonate precursor:

[Formula 3]

In Chemical Formula 3, Cy, m and n are as defined in Chemical Formula 1, and specifically, Cy is unsubstituted or _{substituted with C 1-10} alkyl, C _1-10 alkoxy, or halogen, C _{5- 20} cycloalkylene, m and n are the same as or different from each other, and each independently an integer of 0 to 50, provided that m+n is an integer of 2 or more.

In Formula 3, m and n represent the molar ratio of each repeating unit, and can be calculated from the weight average molecular weight of the compound represented by Formula 3. More specifically, in the compound of Formula 3, the content m and n of each repeating unit are each independently an integer of 0 or more, or 1 or more, or 2 or more, and 50 or less, or 20 or less, or 15 or less, or 10 or less , Or an integer of 5 or less, and the value of m+n may be an integer of 2 or more, and may be an integer of 50 or less, or 20 or less, or 10 or less, or 5 or less.

The weight average molecular weight of the compound of Formula 3 can be appropriately adjusted to suit the purpose and use, and is 700 g/mol or more, 800 g/mol or more, 2,000 g/mol or less, 1,000 g based on standard polystyrene (PS standard). May be less than or equal to /mol. When it has a weight average molecular weight in the above range, it may exhibit the effect of improving weather resistance and hardness.

Specific examples of the compound represented by Formula 3 may include compounds of Formula 3a or 3b, but the present invention is not limited thereto:

[Formula 3a]

[Formula 3b]

In Formulas 3a and 3b, m and n are as defined in Formula 3, and more specifically, may be determined under conditions satisfying the above-described weight average molecular weight range.

The compound represented by Formula 3 may be synthesized according to Reaction Scheme 1 as follows, and may be further specified in Examples to be described later.

[Scheme 1]

In Reaction Scheme 1, Cy, m and n are as defined in Chemical Formula 3.

In addition, according to one embodiment of the present invention, the polycarbonate may be polymerized by further comprising an aromatic diol compound represented by the following formula (4):

[Formula 4]

In Formula 4, R ₁ to R ₄ , and Z are as defined in Formula 2, specifically R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen, C _1-10 alkyl, C _{1 -10} alkoxy or halogen, Z is substituted with a C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by unsubstituted or phenyl Beach C _3-15 cycloalkylene, O, S, SO, SO ₂ , or CO.

Specific examples of the aromatic diol compound represented by Chemical Formula 4, 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)cyclohexane (bisphenol Z), 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 or 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and any one of them or a mixture of two or more thereof may be used.

Meanwhile, the carbonate precursor serves to link the compound represented by Formula 3 and the compound represented by Formula 4, 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) carbonate or bishaloformate, etc. And any one or a mixture of two or more of them may be used.

When the composition contains only the compound represented by Chemical Formula 3 and the carbonate precursor as monomers, the compound represented by Chemical Formula 3 is 5% by weight or more, or 10% by weight or more, or 15% by weight based on 100% by weight of the composition. % Or more, 90% by weight or less, or 60% by weight or less, or 30% by weight or less. In addition, the carbonate precursor is used in an amount of 3% by weight or more, or 5% by weight or more, or 10% by weight or more, 40% by weight or less, or 35% by weight or less, or 30% by weight or less based on 100% by weight of the composition. I can.

On the other hand, when the composition comprises a compound represented by Formula 3 as a monomer, an aromatic diol compound represented by Formula 4, and a carbonate precursor, the compound represented by Formula 3 is 1 based on 100% by weight of the composition. It may be used in an amount of at least 5% by weight, or at least 10% by weight, and at most 90% by weight, or at most 80% by weight, or at most 70% by weight. In addition, the aromatic diol compound represented by Formula 4 is 5% by weight or more, 30% by weight or more, or 50% by weight or more, 95% by weight or less, 90% by weight or less, or 80% by weight based on 100% by weight of the composition. % Or less can be used. In addition, the carbonate precursor may be used in an amount of 3% by weight or more, or 5% by weight or more, or 10% by weight, and 20% by weight or less, or 15% by weight or less, or 12% by weight or less based on 100% by weight of the composition. have.

The polymerization is preferably performed by interfacial polymerization, and during interfacial polymerization, a polymerization reaction is possible at normal pressure and low temperature, and molecular weight control is easy.

In addition, 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.

In addition, the solvent that can be used for the polymerization is not particularly limited as long as it is a solvent used for polymerization of polycarbonate 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 control the molecular weight of the polycarbonate during the polymerization, it is preferable to perform polymerization in the presence of a molecular weight control agent. _{C 1-20} alkylphenol may be used as the molecular weight control agent, and specific examples thereof are p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eico Silphenol, docosylphenol, or triacontylphenol. The molecular weight modifier may be added before starting, during or after starting 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 diol compound, and a desired molecular weight may be obtained within this range.

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 another embodiment of the invention, a molded article made of the polycarbonate may be provided. As described above, the polycarbonate including the repeating structure represented by Chemical Formula 1 exhibits improved weather resistance while maintaining the excellent physical properties of the polycarbonate itself. wide. In addition, when the polycarbonate further includes a repeating unit represented by Chemical Formula 2, the desired physical properties may be realized by adjusting the weight ratio of the repeating units represented by Chemical Formulas 1 and 2, so that the field of application can be further expanded. have.

In addition to the above-described polycarbonate, the molded article may additionally include at least one selected from the group consisting of antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, optical brighteners, ultraviolet absorbers, pigments, and dyes, if necessary. Can include.

As an example of the manufacturing method of the molded article, the polycarbonate and other additives are well mixed using a mixer, and then extruded with an extruder to produce pellets, dried the pellets, and then injected with an injection molding machine. can do.

According to the present invention, it is possible to provide a polycarbonate having a novel structure and a method for producing the same, while maintaining excellent impact strength characteristics and exhibiting improved weather resistance.

^{1 is a 1} H-NMR graph of 1,4-cyclohexanediol bis(4-hydroxybenzoate) oligomer prepared in Example 1. FIG.
^{2 is a 1} H-NMR graph of 1,4-cyclohexanediol bis(4-hydroxybenzoate) used in the preparation of 1,4-cyclohexanediol bis(4-hydroxybenzoate) oligomer.

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.

[Production of polycarbonate]

Example One

(1) Preparation of 1,4-Cyclohexanediol 4-HB oligomer

(I)

(I)

After 5 g of 1,4-cyclohexanediol _{was added dropwise to 200 ml of a methylene chloride (MeCl 2} ) solvent in a round flask, 25.1 g of 4-hydroxybenzoic acid was added dropwise. To the resulting mixed solution, 23 g of oxalyl chloride and 0.01 g of dimethylformamide (DMF) were added dropwise at room temperature, stirred at room temperature for about 4 hours, and then the solvent was removed through a reduced pressure rotary evaporator. Diol bis(4-hydroxybenzoate) oligomer (Cyclohexanediol bis(4-hydroxybenzoate) oligomer; 1,4-Cyclohexanediol 4-HB oligomer) was obtained.

For the obtained 1,4-Cyclohexanediol 4-HB oligomer, an acid group worked up through 1N NaOH and 1N HCl aqueous solution and a methylene chloride solvent, and 1,4-Cyclohexanediol 4-HB oligomer was crude without a separate purification process. It was obtained in 95% yield. As a result of GPC analysis using PS standard for the obtained 1,4-Cyclohexanediol 4-HB oligomer, the weight average molecular weight (Mw) was 826 g/mol.

In addition, 1H-NMR analysis (in DMSO-d6, 500MHz) was performed on 1,4-Cyclohexanediol 4-HB oligomer, and the results are shown in FIG. 1 (m+n=2). In addition, 1H-NMR analysis (in DMSO-d6, 500MHz) results for 1,4-Cyclohexanediol 4-HB, a monomer used in the preparation of the 1,4-Cyclohexanediol 4-HB oligomer, for comparison between monomers and oligomers. It is shown in Figure 2.

(2) Preparation of polycarbonate resin

Water 620g, bisphenol A (BPA) 113.45g, 1,4-Cyclohexanediol 4-HB oligomer 11.30 prepared in (1) above in a 2L main reactor equipped with a nitrogen purge and a condenser and capable of maintaining room temperature with a circulator. g, NaOH 102.5g, MeCl ₂ 200ml was added and stirred for several minutes.

Stop purging with nitrogen, add 62 g of triphosgene and _{120 g of MeCl 2} to a 1L round bottom flask to dissolve triphosgene, then slowly add the dissolved triphosgene solution to the main reactor in which the BPA solution is dissolved, and when the addition is complete, PTBP (p. -tert-butylphenol) 2.66g was added and stirred for 10 minutes. After the stirring was completed, 97 g of 40 wt% NaOH aqueous solution was added, and then 1.16 g of triethylamine (TEA) as a coupling agent was added. At this time, the reaction pH was maintained between 11 and 13. HCl was added to terminate the reaction after a period of time for sufficient reaction to occur, and the pH was dropped to 3-4. Then, the agitation was stopped to separate the polymer layer and the water layer, and then the water layer was removed, and pure H ₂ O was added again to perform washing with water 3 to 5 times.

When washing with water was completed, only the polymer layer was extracted, and polymer crystals were obtained by reprecipitation using a non-solvent using _{methanol, H 2 O, or the like.}

As a result of GPC analysis using PS standard, the prepared polycarbonate had a weight average molecular weight of 48,200 g/mol. In addition, ¹ H-NMR (in DMSO-d6, 500MHz) analysis showed that the content of the repeating unit derived from 1,4-Cyclohexanediol 4-HB oligomer in the polycarbonate was 10% by weight.

Example 2

In Example 1, a polycarbonate resin was prepared in the same manner as in Example 1, except that 22.17 g of 1,4-Cyclohexanediol 4-HB oligomer and 110.53 g of BPA were used.

^{As a result of 1} H-NMR (in DMSO-d6, 500MHz) analysis, the content of repeating units derived from 1,4-Cyclohexanediol 4-HB (oligomer) in the polycarbonate was 20% by weight.

Comparative Example 1

_{620 g of water, 116.47 g of BPA, 102.5 g of 40 wt% NaOH aqueous solution, and 200 ml of MeCl 2} were added to a 2 L main reactor equipped with a nitrogen purge and a condenser and capable of maintaining room temperature with a circulator, and stirred for several minutes.

Stop purging nitrogen, add 62 g of triphosgene and _{120 g of MeCl 2} to a 1 L round bottom flask to dissolve triphosgene, and then slowly add the dissolved triphosgene solution to the main reactor containing the BPA solution, and when the addition is complete, PTBP (p -tert butylphenol) 2.66g was added and stirred for 10 minutes. After the stirring was completed, 97 g of 40 wt% NaOH aqueous solution was added, and 1.16 g of TEA was added as a coupling agent. At this time, the reaction pH was maintained between 11 and 13. HCl was added to terminate the reaction after a period of time for sufficient reaction to occur, and the pH was dropped to 3-4.

Then, the agitation was stopped to separate the polymer layer and the water layer, and then the water layer was removed, and the process of washing with water by re-injecting _{pure H 2 O was repeated 3 to 5 times.}

When washing with water was completed, only the polymer layer was extracted, and polymer crystals were obtained by reprecipitation using a non-solvent using _{methanol and H 2 O.}

As a result of GPC analysis using PS standard, the prepared polycarbonate had a weight average molecular weight of 48,000 g/mol.

Comparative Example 2

In Example 1, 10.97g of 1,4-Cyclohexanediol bis(4-hydroxybenzoate) (1,4-Cyclohexanediol 4-HB) and 109.66g of BPA were used instead of 1,4-Cyclohexanediol 4-HB oligomer. Then, a polycarbonate resin was prepared by performing the same method as in Example 1.

^{As a result of 1} H-NMR (in DMSO-d6, 500MHz) analysis, the content of the repeating unit derived from 1,4-Cyclohexanediol 4-HB in the polycarbonate was 10% by weight.

Comparative Example 3

In Example 1, in place of 1,4-Cyclohexanediol 4-HB oligomer, 1,4-Cyclohexanediol 4-HB was used in the same manner as in Example 1, except that 20.63 g of 1,4-Cyclohexanediol 4-HB and 103.66 g of BPA were used. A polycarbonate resin was prepared.

^{As a result of 1} H-NMR (in DMSO-d6, 500MHz) analysis, the content of the repeating unit derived from 1,4-Cyclohexanediol 4-HB in the polycarbonate was 20% by weight.

Comparative Example 4

In Example 1, 1,4-Cyclohexanediol 4-HB was used instead of 1,4-Cyclohexanediol 4-HB (oligomer) in the same manner as in Example 1, except that 29.45 g of 1,4-Cyclohexanediol 4-HB and 98.19 g of BPA were used. To prepare a polycarbonate resin.

^{As a result of 1} H-NMR (in DMSO-d6, 500MHz) analysis, the content of the repeating unit derived from 1,4-Cyclohexanediol 4-HB in the final polycarbonate resin was 30% by weight.

Experimental example

For the polycarbonate prepared in the above Examples and Comparative Examples, the types and contents of the repeating units in the polycarbonate resin were analyzed, and the weight average molecular weight and melting index were measured by the method described below. The results are shown in Table 1 below.

^{*Type and content of repeating units: 1} H NMR analysis was performed on the polycarbonates prepared in Examples and Comparative Examples, and 1,4-Cyclohexanediol 4-HB (oligomer) or 1,4- contained in the polycarbonate The content of the repeating unit derived from Cyclohexanediol 4-HB was calculated.

¹ H NMR analysis was performed using a Bruker DRX 500 MHz spectrometer (500 MHz) in DMSO-d6 with trimethylsilane (TMS) added as an internal standard.

* Weight average molecular weight (g/mol): The weight average molecular weight (Mw) of the oligomers and polycarbonates prepared in Examples and Comparative Examples was measured using gel permeation chromatography. Specifically, it was measured using an Agilent 1200 series instrument using a Polymer Laboratories PLgel MIX-B 300 mm length column, at which time the measurement temperature was 160°C, the solvent used was 1,2,4-trichlorobenzene, and the flow rate was 1 mL. /min. The sample was prepared at a concentration of 10 mg/10 mL, then supplied in an amount of 200 μL, and the Mw value was derived using a calibration curve formed using a polystyrene standard. The molecular weight (g/mol) of the polystyrene standard was 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

*Melt index (MI): It was measured according to ASTM D1238 (300°C, 1.2kg condition).

In addition, an injection specimen was prepared using the polycarbonate prepared in the above Examples and Comparative Examples, and weather resistance and pencil hardness were measured. The results are shown in Table 1 below.

* Preparation of injection specimen: 0.050 parts by weight of tris(2,4-di-tert-butylphenyl)phosphite, and pentaerythritol tetrastearate per 1 part by weight of each of the polycarbonates prepared in the above Examples and Comparative Examples After adding 0.030 parts by weight, pelletizing using a Φ30mm twin screw extruder with a vent, using a JSW N-20C injection molding machine at a cylinder temperature of 300°C and a mold temperature of 80°C. The specimen was injection molded.

* Weather resistance (△E): After measuring the L, a, and b values for 1/8 inch thick specimens by ASTM D7869 method, the specimens are left to weather-resistant conditions for 2250 hours using a ^{Weather-O meter ® (Ci 5000) machine.} After the L', a'and b'values were measured again. From this, weather resistance (ΔE) was calculated according to Equation 1 below.

[Equation 1]

(In Equation 1, L, a and b are values measured by the ASTM D7869 method for a 1/8 inch thick specimen made of a polycarbonate resin, and L', a'and b'are the corresponding specimens under 2250 hr weather resistance conditions. This is the value measured again after leaving it unattended)

* Pencil hardness: Scratch resistance evaluation was performed in accordance with KS D 3520 using a simple pencil hardness tester (No.221D, Yoshimitsu). A Mitsubishi pencil was inclined at 45° to the surface of the polycarbonate specimen, and a line of 20 mm or more was drawn with a load of 9.8 N to evaluate the resistance to scratching. The marks produced by the pencil lead were defined as permanent crushing or visually observed scratch marks on the polycarbonate surface. The pencil hardness was gradually increased until these marks appeared on the surface. It was judged that the hardness of the used pencil was satisfied if no scratches occurred more than three times by testing five times for one specimen.

Type and content of repeating units of formula 1 Weight average molecular weight
(g/mol) MI
(g/10min) Weather resistance
(△E, 2250hr) Pencil hardness Example 1 1,4-Cyclohexanediol 4-HB oligomer, 10% by weight 48,200 12 18 HB Example 2 1,4-Cyclohexanediol 4-HB oligomer, 20% by weight 48,400 12 16 F Comparative Example 1 - 48,000 15 32 2B Comparative Example 2 1,4-Cyclohexanediol 4-HB, 10% by weight 48,200 14 22 2B Comparative Example 3 1,4-Cyclohexanediol 4-HB, 20% by weight 48,200 13 21 B Comparative Example 4 1,4-Cyclohexanediol 4-HB, 30% by weight 48,500 12 19 HB

In Table 1, Comparative Examples 2, 3, and 4 are not repeating units of Formula 1, but the types of repeating units corresponding thereto are described, and the content of the repeating units is a value based on the total weight of the polycarbonate.

As a result of the experiment, the polycarbonates of Examples 1 and 2 and Comparative Examples 1 to 4 have the same weight average molecular weight and melt index, but an embodiment containing an oligomer-type repeating unit represented by Formula 1 derived from Compound (I) The polycarbonates of Examples 1 and 2 exhibited significantly improved weatherability and hardness characteristics compared to Comparative Example 1 that does not contain the repeating unit represented by Chemical Formula 1. In addition, it was similar to Compound (I), but showed more improved weatherability and hardness characteristics as compared to Comparative Examples 2 to 4 including a single molecular repeating unit.

Claims (13)

Polycarbonate containing a repeating unit represented by the following formula (1):
[Formula 1]

In Formula 1,
Cy is unsubstituted or _{substituted with C 1-10} alkyl, C _1-10 alkoxy, or halogen, C _5-20 cycloalkylene,
m and n are the same as or different from each other, and each independently is an integer of 0 to 50, provided that m+n is an integer of 2 or more.
The method of claim 1,
The repeating unit represented by Formula 1 has a structure represented by the following Formula 1a or 1b, polycarbonate:
[Formula 1a]

[Formula 1b]

In Formulas 1a and 1b, m and n are as defined in Formula 1.
The method of claim 1,
The repeating unit represented by Formula 1 is contained in an amount of 5 to 50% by weight or less based on the total weight of the polycarbonate, polycarbonate.
The method of claim 1,
Polycarbonate further comprising a repeating unit represented by the following formula (2):
[Formula 2]

In Chemical Formula 2,
R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,
Z is an unsubstituted or beach, or a phenyl C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, CO or substituted.
The method of claim 4,
The R ₁ to R ₄ are each independently hydrogen, or C _1-4 alkyl, polycarbonate.
The method of claim 4,
The weight ratio of the repeating unit represented by Formula 1 and the repeating unit represented by Formula 2 is 99:1 to 1:99, polycarbonate.
The method of claim 1,
The polycarbonate has a weight average molecular weight of 40,000 to 60,000 g/mol, and a melt index measured according to ASTM D1238 (300° C., 1.2 kg condition) is 5 to 20 g/10 min, and is calculated according to Equation 1 below. Polycarbonate, which has a weather resistance (ΔE) of 18 or less under conditions of 2250 hr
[Equation 1]

(In Equation 1, L, a and b are values measured by the ASTM D7869 method for a 1/8 inch thick specimen made of a polycarbonate resin, and L', a'and b'are the corresponding specimens under 2250 hr weather resistance conditions. It is the value measured again after leaving it unattended)
A method for producing the polycarbonate of claim 1, comprising polymerizing a composition comprising a compound represented by the following Formula 3 and a carbonate precursor:
[Formula 3]

In Chemical Formula 3,
Cy is unsubstituted or _{substituted with C 1-10} alkyl, C _1-10 alkoxy, or halogen, C _5-20 cycloalkylene,
m and n are the same as or different from each other, and each independently is an integer of 0 to 50, provided that m+n is an integer of 2 or more.
The method of claim 8,
The compound represented by Formula 3 is a compound represented by the following Formula 3a or 3b, a method of producing a polycarbonate:
[Formula 3a]

[Formula 3b]

In Formulas 3a and 3b, m and n are as defined in Formula 3.
The method of claim 8,
The weight average molecular weight of the compound of Formula 3 is 700 g/mol or more and 2,000 g/mol or less.
The method of claim 8,
The composition further comprises an aromatic diol compound represented by the following formula (4), a method for producing a polycarbonate.
[Formula 4]

In Chemical Formula 4,
R ₁ to R ₄ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,
Z is an unsubstituted or beach, or a phenyl C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, CO or substituted.
The method of claim 11,
The aromatic diol compound represented by Formula 4 is bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide Side, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)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 and 1,1-bis A method for producing a polycarbonate selected from the group consisting of (4-hydroxyphenyl)-1-phenylethane.
A molded article made of the polycarbonate of any one of claims 1 to 7.

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