JP2532169B2 - Polycarbonate resin - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate resin having improved heat resistance.

[0002]

2. Description of the Related Art Polycarbonate has been conventionally used as an engineering plastic because it is tough, has particularly high impact strength, and has excellent creep resistance and dimensional stability. However, the heat distortion temperature of this resin alone is about 135 ° C., and the heat resistance is not particularly high as compared with other engineering plastics.

So far, polyester carbonates have been copolymerized with terephthalic acid dichloride or isophthalic acid dichloride for the purpose of improving the heat resistance, thickness dependence of impact strength, impact resistance at low temperature and solvent resistance of polycarbonate. Studies on synthesis have been conducted (for example, JP-A-55-38824 and JP-A-53-102399,
JP-A-60-179421, JP-A-58-15529).

[0004]

However, even by the techniques disclosed in the above publications, the heat resistance of polycarbonate does not reach the heat resistance of polyarylate, polysulfone, etc., and further heat resistance is desired.

The present invention has been made in view of the above situation, and by further improving the heat resistance, it can be used in various fields such as various molded articles, fibers, films, sheets, adhesives, etc. which have high heat resistance requirements. An object is to provide a possible polycarbonate resin.

[0006]

According to the present invention, the monohydroxy compound represented by the formula (1) has an extremely high melting point among existing low molecular weight compounds, and this compound is introduced at the molecular terminal of polycarbonate. It is based on the finding that a polycarbonate resin with heat resistance can be obtained.

Namely, the polycarbonate resin of the present invention, the monohydroxy compound represented by the following general formula (1), are produced using as a molecular weight modifier, a repeating unit represented by the following formula (2) Configuration The unit is a polycarbonate resin having a viscosity average molecular weight of 9,000 to 50,000, and the above object is achieved thereby.

[0008]

Embedded image (In the formula, R represents an ethylene group or a propylene group , and l
Is 2 or 3, m is 0 or 1)

Embedded image

(In the formula, R ¹ is a straight chain having 1 to 10 carbon atoms,
Branched or cyclic alkylidene group, aryl-substituted alkyl
Xylene group, arylene group, -O-, -CO-, -S-,
Represents --SO-- or --SO _2- , and R ^{2 to} R ⁵ are independently
Indicates hydrogen, halogen or an alkyl group) .

The polycarbonate resin of the present invention can be produced by reacting one or more bisphenol compounds and the monohydroxy compound (1) with a carbonic acid ester such as phosgene or diphenyl carbonate.

To allow the monohydroxy compound (1) used as a terminal stopper to coexist with the bisphenol compound, for example, the monohydroxy compound (1) is allowed to coexist with the bisphenol compound from the beginning of the reaction, and during the reaction, for example, an oligomer is prepared by using the bisphenol compound. There is an arbitrary method such as coexisting when the polymer is made to have a higher molecular weight.

The viscosity average molecular weight of the polycarbonate resin of the present invention thus obtained is 9,000 to 50,000. Here, the viscosity average molecular weight (M) is 20 ° C. using a 6.0 g / l methylene chloride solution of polycarbonate resin.
It is calculated by the following formula from η _sp measured in.

Η_SP/ C = [η] + κ ′ [η]²c [η] = 1.23 × 10^-FourM^0.83  c: Polymer concentration (g / 1) [η]: Intrinsic viscosity κ ′ = 0.45 M: Viscosity average molecular weight In the present invention, a repeating unit represented by the following formula:ConstructSuccess
It is preferable to use the rank.

[0014]

Embedded image

(In the formula, R ¹ is a linear, branched or cyclic alkylidene group having 1 to 10 carbon atoms, an aryl-substituted alkylene group, an arylene group, -O-, -CO-, -S-, -SO-.
Or —SO ₂ — and R ^{2 to} R ⁵ independently represent hydrogen, halogen or an alkyl group). Examples of the bisphenol compound include bis- (4-hydroxyphenyl) methane, 1,1-bis- (4-hydroxyphenyl) ethane,
1,1-bis- (4-hydroxyphenyl) propane, 2,2-bis-
(4-hydroxyphenyl) propane (bisphenol A), 2,2-bis- (4-hydroxyphenyl) butane, 2,2-bis- (4-hydroxyphenyl) pentane, 2,2-bis- (4-hydroxy Phenyl) -3-methylbutane, 2,2-bis- (4-hydroxyphenyl) hexane, 2,2-bis- (4-hydroxyphenyl) -4-methylpentane, 1,1-bis- (4-hydroxyphenyl) ) Cyclopentane, 1,1-bis- (4-hydroxyphenyl) cyclohexane, bis- (4-hydroxy-3-methylphenyl) methane, 1,1-bis- (4-hydroxy-3-methylphenyl) ethane, 2,2-bis- (4-hydroxy-3-methylphenyl) propane, 2,2-bis- (4-hydroxy-3-ethylphenyl) propane, 2,2-bis- (4-hydroxy-3-iso Propylphenyl) propane, 2,2-bis- (4-hydroxy-3-sec butylphenyl) propane, bis- (4-hydroxyphenyl)
Phenylmethane, 1,1-bis- (4-hydroxyphenyl) -1-
Phenylethane, 1,1-bis- (4-hydroxyphenyl) -1-
Phenylpropane, bis- (4-hydroxyphenyl) diphenylmethane, bis- (4-hydroxyphenyl) dibenzylmethane, 4,4'-dihydroxydiphenylether, 4,
4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, phenolphthalein and the like can be mentioned.

Further, the monohydroxy compound represented by the above formula (1) is a rigid low molecular compound having a paraphenylene skeleton, and the melting point of these compounds is extremely high reflecting the characteristic molecular structure. Furthermore, it is known that the paraphenylene skeleton is effective as a mesogen of a low-molecular liquid crystal compound. It shows. Therefore, when the above-mentioned monohydroxy compound (1) is incorporated into the polymer terminal, the heat resistance of the polymer is improved.

[0017] In the monohydroxy compound represented by the above formula (1), R is an ethylene or propylene group der
Ri, m is 0 or 1. Examples of the monohydroxy compound (1) include 4-hydroxy-p-terphenyl, 4-hydroxy-p-quaterphenyl, 4- (2-hydroxyethoxy) -p-terphenyl and 4- (2-hydroxyethoxy). ) -p-Quarterphenyl and the like. The monohydroxy compounds (1) may be used alone or in combination.

The amount of the monohydroxy compound (1) used is
It is determined by the desired molecular weight of the polycarbonate resin. Preferably, with respect to the bisphenol compound used, 1.0-10 mol% is preferred, more preferably 2.0
~ 8.0 mol%. If it is less than 1.0 mol%, a high-molecular weight polycarbonate resin can be obtained, but the effect of improving heat resistance is small because the proportion of the monohydroxy compound (1) bonded to the terminal is too small. If it exceeds 10 mol%, the proportion of the monohydroxy compound (1) bonded to the terminal increases, but the molecular weight of the obtained polycarbonate resin is too small, so that only a molded product having low mechanical strength can be obtained.

If necessary, a heat stabilizer, an antioxidant, a light stabilizer, a colorant, an inorganic filler, a glass fiber, a carbon fiber or the like may be added to the polycarbonate resin as appropriate. I can give you something.

(I) Inorganic fibers: glass fibers, carbon fibers, boron fibers, silicon carbide fibers, alumina fibers, amorofus fibers, silicon / titanium / carbon fibers, etc.

(Ii) Organic fibers: aramid fibers and the like.

(Iii) Inorganic filler: calcium carbonate, titanium oxide, mica, talc, etc.

(Iv) Flame retardant: hexabromocyclododecane, tris- (2,3-dichloropropyl) phosphate,
Pentabromophenyl allyl ether, etc.

(V) UV absorber: p-tert-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4,5-trihydroxybutyrophenone etc.

(Vi) Antioxidants: butylhydroxyanisole, butylhydroxytoluene, distearylthiodipropionate, dilaurylthiodipropionate, hindered phenolic antioxidants and the like.

(Vii) Antistatic agent: N, N-bis (hydroxyethyl) alkylamine, alkylallyl sulfonate, alkyl sulfanate, etc.

(Viii) Inorganic substance: barium sulfate, alumina,
Silicon oxide, etc.

(Ix) Higher fatty acid salt: sodium stearate, barium stearate, sodium palmitate, etc.

(X) Other organic compounds: benzyl alcohol, benzophenone, etc.

(Xi) Crystallization accelerator; highly crystallized polyethylene terephthalate, polytrans-cyclohexanedimethanol terephthalate, etc.

[0031]

EXAMPLES The present invention will be described below based on examples.

Example 1 2,2-Bis- (4-hydroxyphenyl) propane 45.6 g Diphenyl carbonate 47 g 4-Hydroxy-p-quarterphenyl 3.3 g The above mixture was charged into a reactor equipped with a stirrer and further oxidized as a catalyst. 0.04 g of zinc and 0.04 g of lead oxide were added. After replacing the inside of the reactor with nitrogen, the temperature inside the reactor was raised. Inner temperature 180
Esterification started at 0 ° C, and phenol began to distill from the reactor. The pressure inside the reactor was adjusted to 50 mmHg and the reaction was carried out for 30 minutes at the same temperature, and most of the phenol was distilled off. Next, the temperature of the reactor was raised to 220 ° C., and the reaction was carried out for 30 minutes while the pressure inside the reactor was reduced to 1 mmHg. Then, the temperature was raised to 250 ° C. and the reaction was carried out for 1 hour, and finally the reaction was carried out at 310 ° C. for 1 hour to complete the polycondensation. A very viscous liquid formed which was cooled to give a clear, tough polycarbonate resin.

The viscosity average molecular weight of this polycarbonate resin was 20,200. Also, the flow value "Q value" of polycarbonate resin is measured at 280 ° C and 160 kg using a flow tester.
The amount of molten resin (cc / sec) distilled from a die having a diameter of 1 mm and a length of 10 mm was measured under a pressure of / cm ² . The measurement is 3
The measurements were repeated, and the average value was used as the measured value.

A Vicat softening temperature test piece was prepared by molding the above resin into a plate having a thickness of 3 mm at 280 ° C. by a pressing method. The Vicat softening test temperature of the obtained test piece is JIS K
The test was performed according to 7206 (load 1 kg / cm ² ). Table 1 shows the above results.

Example 2 2,2-Bis- (4-hydroxyphenyl) propane 46 g Diphenyl carbonate 48 g 4-Hydroxy-p-quaterphenyl 2.0 g The same as in Example 1 except that the above charge composition was used. A polycarbonate resin was obtained.

The viscosity average molecular weight of this polycarbonate resin was 23,000. The amount of molten resin and the Vicat softening temperature of the polycarbonate were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 A polycarbonate resin was obtained in the same manner as in Example 1 except that p-tert-butylphenol was used in place of 4-hydroxy-p-quaterphenyl and the composition was as follows. It was

2,2-bis- (4-hydroxyphenyl) propane 50 g Diphenyl carbonate 53 g p-Tertiary butylphenol 1.6 g The viscosity average molecular weight of the obtained polycarbonate resin is
It was 19,500. The amount of molten resin and the Vicat softening temperature of the polycarbonate resin were measured in the same manner as in Example 1.
The results are shown in Table 1.

Comparative Example 2 A polycarbonate resin was obtained in the same manner as in Comparative Example 1 except that the amount of p-tert-butylphenol charged was 1.0 g.

The viscosity average molecular weight of the obtained polycarbonate resin was 23,500. The amount of molten resin and the Vicat softening temperature of the polycarbonate resin were measured in the same manner as in Example 1. The results are shown in Table 1.

[0041]

[Table 1]

[0042]

The polycarbonate resin of the present invention has a molecular weight almost equal to that of the conventional polycarbonate resin.
Heat resistance is improved and molding processability is the same as before.
Therefore, various molded products, fibers, films, which have high heat resistance requirements,
It can be used in the field of sheets, adhesives, etc. without any problems.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Daishiro Kishimoto 2-11-20 Mishimaoka, Ibaraki City, Osaka Prefecture

Claims (1)

(57) [Claims] The method according to claim 1] monohydroxy compound represented by the following general formula (1), a polycarbonate resin produced by using as a molecular weight modifier, configuration unit a repeating unit represented by the following formula (2) And a polycarbonate resin having a viscosity average molecular weight of 9,000 to 50,000: (In the formula, R represents an ethylene group or a propylene group, and l
Is 2 or 3 and m is 0 or 1) (In the formula, R ¹ is a linear, branched or cyclic alkylidene group having 1 to 10 carbon atoms, an aryl-substituted alkylene group, an arylene group, —O—, —CO—, —S—, —SO— or —SO. _2- , and R ^{2 to} R ⁵ independently represent hydrogen, halogen or an alkyl group).