DIOL COMPOUND, POLYCARBONATE, AND PREPARATION METHOD OF THE SAME

Abstract

Provided is a diol compound of the following Chemical Formula 1, a polycarbonate comprising the diol compound, and a method of producing the polycarbonate.

##STR00001##

Claims

1. A diol compound of Chemical Formula 1: ##STR00019## wherein in Chemical Formula 1: R is a divalent group derived from benzene, biphenyl, terphenyl, or naphthalene; C.sub.3-20 cycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl; or C.sub.3-20 heterocycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl; and n and m are each independently an integer from 1 to 1,000.

2. The diol compound of claim 1, wherein R is a divalent group of one of the following formulae: ##STR00020##

3. A polycarbonate, comprising a diol compound of the following Chemical Formula 1, a compound of the following Chemical Formula 2, and a repeating unit derived from a carbonate precursor: ##STR00021## wherein in Chemical Formula 1: R is a divalent group derived from benzene, biphenyl, terphenyl, or naphthalene; C.sub.3-20 cycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl; or C.sub.3-20 heterocycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl, and n and m are each independently an integer from 1 to 1,000, ##STR00022## wherein in Chemical Formula 2: R.sub.1 to R.sub.4 are each independently hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen; and Z is C.sub.1-10 alkylene unsubstituted or substituted with phenyl, C.sub.3-15 cycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl, O, S, SO, SO.sub.2, or CO.

4. The polycarbonate of claim 3, p1 wherein R is a divalent group of one of the following formulae: ##STR00023##

5. The polycarbonate of claim 3, wherein R.sub.1 to R.sub.4 are each independently hydrogen, or C.sub.1-4 alkyl.

6. The polycarbonate of claim 3, wherein a molar ratio of a repeating unit derived from the compound of Chemical Formula 1 and a repeating unit derived from the compound of Chemical Formula 2 is 99:1 to 1:99.

7. The polycarbonate of claim 3, wherein the polycarbonate has a weight average molecular weight (Mw) of 15,000 to 50,000 g/mol, measured by GPC using PS Standard.

8. The polycarbonate of claim 3, comprising a repeating unit of the following Chemical Formula 3: ##STR00024## wherein in Chemical Formula 3: R is a divalent group derived from benzene, biphenyl, terphenyl, or naphthalene; C.sub.3-20 cycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl; or C.sub.3-20 heterocycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl, and n and m are each independently an integer from 1 to 1,000.

9. The polycarbonate of claim 3, comprising a repeating unit of the following Chemical Formula 4: Chemical Formula 4 ##STR00025## wherein in Chemical Formula 4: R.sub.1 to R.sub.4 are each independently hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen; and Z is C.sub.1-10 alkylene unsubstituted or substituted with phenyl, C.sub.3-15 cycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl, O, S, SO, SO.sub.2, or CO.

10. The polycarbonate of claim 3, wherein the polycarbonate has an Izod impact strength at room temperature of 100 to 1,000 J/m, measured at 23° C. in accordance with ASTM D256 (⅛ inch, Notched Izod).

11. The polycarbonate of claim 3, wherein the polycarbonate has a glass transition temperature (Tg) of 153 to 190° C.

12. The polycarbonate of claim 3, wherein the polycarbonate has pencil hardness of B or HB, measured at a 45 degree angle with a load of 50 g in accordance with ASTM D3363.

13. A method of preparing a polycarbonate, comprising a step of polymerizing a composition containing a compound of the following Chemical Formula 1, an aromatic diol compound of the following Chemical Formula 2 and a carbonate precursor: ##STR00026## wherein in Chemical Formula 1: R is a divalent group derived from benzene, biphenyl, terphenyl, or naphthalene; C.sub.3-20 cycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl; or C.sub.3-20 heterocycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl; and n and m are each independently an integer from 1 to 1,000, ##STR00027## wherein in Chemical Formula 2: R.sub.1 to R.sub.4 are each independently hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen; and Z is C.sub.1-10 alkylene unsubstituted or substituted with phenyl, C.sub.3-15 cycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl, O, S, SO, SO.sub.2, or CO.

14. The method of claim 13, wherein R is a divalent group of one of the following formulae: ##STR00028##

15. The method of claim 13, wherein the aromatic diol compound of Chemical Formula 2 is at least one compound selected from the group consisting of 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, and 1,1-bis(4-hydroxyphenyl)-1-phenylethane.

16. The method of claim 13, wherein the polymerization is carried out by a melt polymerization method.

17. The method of claim 16, wherein a carbonic acid diester compound is used as a carbonate precursor during the melt polymerization.

18. A molded article, comprising the polycarbonate of claim 3.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0090] FIG. 1 is a .sup.1H-NMR graph of the compound prepared in Example 1.

[0091] FIG. 2 is a .sup.1H-NMR graph of the copolycarbonate prepared in Example 1.

[0092] FIG. 3 is a .sup.1H-NMR graph of the compound prepared in Example 2.

[0093] FIG. 4 is a .sup.1H-NMR graph of the copolycarbonate prepared in Example 2.

[0094] FIG. 5 is a .sup.1H-NMR graph of the compound prepared in Example 3.

[0095] FIG. 6 is a .sup.1H-NMR graph of the copolycarbonate prepared in Example 3.

[0096] FIG. 7 is a .sup.1H-NMR graph of the compound prepared in Example 4.

[0097] FIG. 8 is a .sup.1H-NMR graph of the copolycarbonate prepared in Example 4.

[0098] The present disclosure can provide a polycarbonate with a novel structure having improved flame retardance, heat resistance, impact strength, and hardness while exhibiting excellent mechanical properties, and a preparation method of the same.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0099] The present disclosure will be described in more detail through the following embodiments. However, the following embodiments are provided only for the purpose of illustrating the present disclosure, and thus the present disclosure is not limited thereto.

EXAMPLES

Example 1

[0100] (1) Preparation of monomer 4,4′-(((1,4-phenylenebis(oxy))bis(2,6-dimethyl-4,1-phenylene))bis(oxy))bis(2,6-dimethylphenol)

##STR00012##

[0101] In a 1.5 L round bottom flask, 300 ml of toluene (solvent) and 40 ml of pyridine were added to 0.6 g of copper bromide (CuBr), followed by stirring at room temperature for about 5 hours while injecting oxygen. Then, 40.1 g of 2,6-dimethylphenol and 2.6 g of hydroquinone were added to 40 ml of toluene in the flask, followed by an overnight reaction at about 30° C. while injecting oxygen. Then, the reactants were placed in a separation funnel, and 200 ml of toluene and 200 ml of water were further added to separate organic layer reactants. The obtained organic substance was added to a mixed solvent of 1500 ml of methanol and 5 ml of a 35% HCl solution to precipitate the reactants. The precipitated reactants were placed in a 110° C. vacuum drying oven to completely remove the solvent to obtain a compound with the above structure in the form of about 34.2 g of white powder (Mw=2,000 g/mol, n,m=14˜18).

[0102] .sup.1H-NMR of the compound is shown in FIG. 1.

[0103] (2) Preparation of Copolycarbonate

[0104] 1784 g of water, 385 g of NaOH, and 233 g of BPA (bisphenol A) were added to a 2 L polymerization reactor which is equipped with a nitrogen purge and a condenser and might be kept at room temperature with a circulator, and then mixed and dissolved in a nitrogen atmosphere. 4.3 g of PTBP (para-tert butylphenol) and 26.3 g of 4,4′-(((1,4-phenylenebis(oxy))bis(2,6-dimethyl-4,1-phenylene))bis(oxy))bis(2,6-dimethylphenol) prepared in step (1) were separately dissolved in MC (methylene chloride) and added to the polymerization reactor. Then, 130 g of TPG (triphosgene) was dissolved in MC, and the solution was slowly added thereto for 1 hour while maintaining the pH at 11 or more with 20% aqueous NaOH solution. After 10 minutes, 46 g of TEA (triethylamine) was added to carry out a coupling reaction. After 1 hour and 20 minutes in total, TEA was removed by lowering the pH to 4 or less with 35% HCl solution, and washed 3 times with distilled water to adjust the pH of the produced polymer to 6 to 7 (neutral). The polymer thus produced was obtained by reprecipitation in a mixed solution of methanol and hexane, and then dried at 120° C. to prepare a final copolycarbonate (molar ratio of Chemical Formula 1: Chemical Formula 2=about 10: 90).

[0105] .sup.1H-NMR of the copolycarbonate thus prepared is shown in FIG. 2.

Example 2

[0106] (1) Preparation of monomer 4,4′-((([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(2,6-dimethyl-4,1-phenylene))bis(oxy))bis(2,6-dimethylphenol)

##STR00013##

[0107] A compound with the above structure was prepared in the form of about 32.1 g of yellow powder in the same manner as in Example 1, except that 4.5 g of (1,1′-biphenyl)-4,4′-diol was used instead of 1.3 g of hydroquinone in the above (1) Preparation of monomer of Example 1 (Mw=2,200 g/mol, n,m=12˜18).

[0108] .sup.1H-NMR of the compound is shown in FIG. 3.

[0109] (2) Preparation of Copolycarbonate

[0110] A copolycarbonate resin was prepared in the same manner as in Example 1, except that 26.3 g of 4,4′-((([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(2,6-dimethyl-4,1-phenylene))bis(oxy))bis(2,6-dimethylphenol) was used instead of 26.3 g of 4,4′-(((1,4-phenylenebis(oxy))bis(2,6-dimethyl-4,1-phenylene))bis(oxy))bis(2,6-dimethylphenol) in the above (2) Preparation of copolycarbonate of Example 1 (molar ratio of Chemical Formula 1: Chemical Formula 2=about 10:90).

[0111] .sup.1H-NMR of the copolycarbonate thus prepared is shown in FIG. 4.

Example 3

[0112] (1) Preparation of monomer 4,4′-(((naphthalene-2,6-diylbis(oxy))bis(2,6-dimethyl-4,1-phenylene))bis(oxy))bis(2,6-dimethylphenol)

##STR00014##

[0113] A compound with the above structure was prepared in the form of about 32.9 g of yellow powder in the same manner as in Example 1, except that 1.9 g of naphthalene-2,6-diol was used instead of 1.3 g of hydroquinone in the above (1) Preparation of monomer of Example 1 (Mw=2,100 g/mol, n,m=14˜18).

[0114] .sup.1H-NMR of the compound is shown in FIG. 5.

[0115] (2) Preparation of Copolycarbonate

[0116] A copolycarbonate resin was prepared in the same manner as in Example 1, except that 26.3 g of 4,4′-(((naphthalene-2,6-diylbis(oxy))bis(2,6-dimethyl-4,1-phenylene))bis(oxy))bis(2,6-dimethylphenol) was used instead of 26.3 g of 4,4′-(((1,4-phenylenebis(oxy))bis(2,6-dimethyl-4,1-phenylene))bis(oxy))bis(2,6-dimethylphenol) in the above (2) Preparation of copolycarbonate of Example 1 (molar ratio of Chemical Formula 1: Chemical Formula 2=about 10:90).

[0117] .sup.1H-NMR of the copolycarbonate thus prepared is shown in FIG. 6.

Example 4

[0118] (1) Preparation of monomer 4,4′-((((hexahydrofuro[3,2-b]furan-3,6-diyl)bis(oxy))bis(2,6-dimethyl-4,1-phenylene))bis(oxy))bis(2,6-dimethylphenol)

##STR00015##

[0119] A compound with the above structure was prepared in the form of about 35.3 g of white powder in the same manner as in Example 1, except that 1.8 g of isosorbide (roquette, POLYSORB®) was used instead of 1.3 g of hydroquinone in the above (1) Preparation of monomer of Example 1 (Mw=2,000 g/mol, n,m=14˜18).

[0120] .sup.1H-NMR of the compound is shown in FIG. 7.

[0121] (2) Preparation of Copolycarbonate

[0122] A copolycarbonate resin was prepared in the same manner as in Example 1, except that 26.3 g of 4,4′-((((hexahydrofuro[3,2-b]furan-3,6-diyl)bis(oxy))bis(2,6-dimethyl-4,1-phenylene))bis(oxy))bis(2,6-dimethylphenol) was used instead of 26.3 g of 4,4′-(((1,4-phenylenebis(oxy))bis(2,6-dimethyl-4,1-phenylene))bis(oxy))bis(2,6-dimethylphenol) in the above (2) Preparation of copolycarbonate of Example 1 (molar ratio of Chemical Formula 1: Chemical Formula 2=about 10:90).

[0123] .sup.1H-NMR of the copolycarbonate thus prepared is shown in FIG. 8.

Comparative Example 1

[0124] 90 wt % of commercialized polycarbonate (LUPOY PC P1300-10, manufactured by LG Co.) and 10 wt % of general PPO (polyphenylene oxide, Mw=2,000 g/mol) of the following Chemical Formula 5 were mixed and pelletized using a HAAKE Mini CTW extruder.

##STR00016##

Comparative Example 2

[0125] A copolycarbonate resin was prepared in the same manner as in Example 1, except that 26.3 g of general PPO (polyphenylene oxide) of the following Chemical Formula 5 was used instead of 26.3 g of 4,4′-(((1,4-phenylenebis(oxy))bis(2,6-dimethyl-4,1-phenylene))bis(oxy))bis(2,6-dimethylphenol) in the above (2) Preparation of copolycarbonate of Example 1.

##STR00017##

Comparative Example 3

[0126] (1) Preparation of monomer 4,4′-((((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(2,6-dimethyl-4,1-phenylene))bis(oxy))bis(2,6-dimethylphenol)

##STR00018##

[0127] A compound with the above structure was prepared in the form of about 37.8 g of white powder in the same manner as in Example 1, except that 2.7 g of bisphenol A (BPA) was used instead of 1.3 g of hydroquinone in the above (1) Preparation of monomer of Example 1 (Mw=2,300 g/mol, n,m=14˜18).

[0128] (2) Preparation of Copolycarbonate

[0129] A copolycarbonate resin was prepared in the same manner as in Example 1, except that 26.3 g of 4,4′-((((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(2,6-dimethyl-4,1-phenylene))bis(oxy))bis(2,6-dimethylphenol) was used instead of 26.3 g of 4,4′-(((1,4-phenylenebis(oxy))bis(2,6-dimethyl-4,1-phenylene))bis(oxy))bis(2,6-dimethylphenol) in the above (2) Preparation of copolycarbonate of Example 1.

EXPERIMENTAL EXAMPLES

Evaluation of Physical Properties of Polycarbonate

[0130] 0.050 part by weight of tris(2,4-di-tert-butylphenyl) phosphite, 0.010 part by weight of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and 0.030 part by weight of pentaerythritol tetrastearate were added to 100 parts by weight of each polycarbonate resin prepared in Examples and Comparative Examples, and pelletized using HAAKE Mini CTW with a vent. Then, it was injection molded at a cylinder temperature of 300° C. and a mold temperature of 120° C. using a HAAKE Minijet injection molding machine to prepare a specimen.

[0131] The characteristics of injection-molded specimens or copolycarbonates were measured by means of the following method, and the results are shown in Table 1.

[0132] *Repeating unit: Measured by .sup.1H-NMR using Varian 500 MHz.

[0133] *Weight average molecular weight (g/mol): Measured using Agilent 1200 series and calibrated with polystyrene standard (PS standard).

[0134] *Flowability (MI): Measured in accordance with ASTM D1238 (300° C., 1.2 kg condition).

[0135] *Izod impact strength (J/m): Measured at 23° C. in accordance with ASTM D256 (⅛ inch, Notched Izod).

[0136] *Glass transition temperature (Tg, ° C.): Measured using DSC (manufactured by TA Instrument).

[0137] *Pencil hardness: Measured using a pencil hardness tester (manufactured by Cometech) with a pencil of 2B, B, HB strength at a 45 degree angle with a load of 50 g in accordance with ASTM D3363.

TABLE-US-00001 TABLE 1 Izod impact Mw MI strength Tg Pencil (g/mol) (g/10 min) (J/m) (° C.) hardness Example 1 30,800 10.1 330 155 B Example 2 31,300 9.4 280 153 B Example 3 31,000 9.9 350 161 B Example 4 30,500 10.6 250 156 HB Comparative 31,100 9.7 340 147 2B Example 1 Comparative 28,300 14.7 230 149 2B Example 2 Comparative 30,800 10.1 320 152 2B Example 3

[0138] Referring to Table 1, it was confirmed that the polycarbonate including the repeating unit derived from the diol compound of Chemical Formula 1 of the present disclosure exhibited very high glass transition temperature of 153° C. or higher, and thus had significantly improved heat resistance compared to Comparative Example 1 in which general PPO was simply blended and Comparative Example 2 prepared using simple PPO that does not include a substituent R.

[0139] In addition, although Comparative Examples 1 to 3 had the pencil hardness of 2B, the polycarbonate of the present disclosure exhibited high hardness of B or HB.

[0140] Accordingly, it can be confirmed that the polycarbonate including the repeating unit derived from the diol compound of Chemical Formula 1 of the present disclosure could achieve improved heat resistance, impact resistance, and increased hardness at the same time compared to compounds obtained by blending or polymerizing general PPO with a polycarbonate.