KR20170079605A - Polycarbonate-polyamide copolymer, method for preparing the same and article produced therefrom - Google Patents
Polycarbonate-polyamide copolymer, method for preparing the same and article produced therefrom Download PDFInfo
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- KR20170079605A KR20170079605A KR1020150190353A KR20150190353A KR20170079605A KR 20170079605 A KR20170079605 A KR 20170079605A KR 1020150190353 A KR1020150190353 A KR 1020150190353A KR 20150190353 A KR20150190353 A KR 20150190353A KR 20170079605 A KR20170079605 A KR 20170079605A
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- polycarbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Abstract
The polycarbonate-polyamide copolymer of the present invention is a polycarbonate oligomer having a number average molecular weight of 5,000 to 15,000 g / mol and a terminal hydroxyl group concentration of 100 to 400 μeq / g; And a polyamide oligomer having a number average molecular weight of 5,000 to 15,000 g / mol and a terminal carboxyl group concentration of 100 to 400 μeq / g. The polycarbonate-polyamide copolymer is excellent in impact resistance, thermal properties, moisture absorption resistance and the like.
Description
The present invention relates to a polycarbonate-polyamide copolymer, a process for producing the same, and a molded article formed therefrom. More particularly, the present invention relates to a polycarbonate-polyamide copolymer excellent in impact resistance, thermal properties, moisture absorption resistance, etc., a process for producing the same, and a molded article formed from the process.
The polycarbonate resin is excellent in impact resistance, dimensional stability and hygroscopicity, and the polyamide resin is excellent in chemical resistance (solvent resistance), processability, toughness, environmental stress cracking property, etc., Suitable thermoplastic resins.
However, since the compatibility between the polycarbonate resin and the polyamide resin is insufficient, inter-phase peeling may occur during mixing and there is a problem that it is very difficult to mix the polycarbonate resin and the polyamide resin by a general method.
In order to solve such a problem, as a method for improving the compatibility in an amorphous region through the use of amorphous polyamide of a relatively high compatibility type or a melt blend of a polycarbonate resin and a polyamide resin, or as a compatibilizer, A method using a polyester block copolymer, a polyetherimide, a polyurethane, a compatibilizing agent having an epoxy functional group and the like have been developed.
However, the conventional polycarbonate resin has a limitation in increasing the compatibility with the polyamide resin due to a lack of functional devices capable of exhibiting chemical interaction with the compatibilizer and the like.
Accordingly, development of a polycarbonate-polyamide copolymer that can obtain excellent impact resistance, thermal properties, moisture absorption resistance and the like, which are advantages of each resin, is demanded without a problem of compatibility.
The background art of the present invention is disclosed in U.S. Patent No. 4,798,874.
An object of the present invention is to provide a polycarbonate-polyamide copolymer excellent in impact resistance, thermal properties, moisture absorption resistance and the like and a method for producing the same.
Another object of the present invention is to provide a molded article formed from the polycarbonate-polyamide copolymer.
The above and other objects of the present invention can be achieved by the present invention described below.
One aspect of the invention relates to polycarbonate-polyamide copolymers. The polycarbonate-polyamide copolymer is a polycarbonate oligomer having a number average molecular weight of 5,000 to 15,000 g / mol and a terminal hydroxyl group concentration of 100 to 400 μeq / g; And a polyamide oligomer having a number average molecular weight of 5,000 to 15,000 g / mol and a terminal carboxyl group concentration of 100 to 400 μeq / g.
In an embodiment, the polycarbonate oligomer is contained in an amount of 10 to 50% by weight of 100% by weight of the polycarbonate-polyamide copolymer, and the polyamide oligomer is contained in an amount of 50 to 90% % ≪ / RTI > by weight.
In an embodiment, the polycarbonate-polyamide copolymer may have a number average molecular weight of 10,000 to 30,000 g / mol and a weight average molecular weight of 20,000 to 60,000 g / mol.
In an embodiment, the polycarbonate-polyamide copolymer may have two melting temperatures (Tm) and one glass transition temperature (Tg).
In an embodiment, the polycarbonate-polyamide copolymer may have a melting temperature of 200 to 230 캜 and 240 to 300 캜, and a glass transition temperature of 60 to 140 캜.
In embodiments, the polycarbonate-polyamide copolymer may have a notched Izod impact strength of from 15 to 90 kgf / cm / cm for a 1/8 "thick specimen measured according to ASTM D256.
In an embodiment, the polycarbonate-polyamide copolymer may have a water absorption rate (moisture absorption rate) of 8% or less according to the following formula 1:
[Formula 1]
Water absorption rate (%) = (W 1 - W 0 ) / W 0 × 100
W 0 is the initial weight of the specimen of 63.5 mm × 12.5 mm × 5.5 mm and W 1 is the weight of the specimen after immersing the specimen in a beaker containing water at 25 ° C. for 24 hours.
Another aspect of the present invention relates to a method for producing a polycarbonate-polyamide copolymer. The preparation method comprises a polycarbonate oligomer having a number average molecular weight of 5,000 to 15,000 g / mol and a terminal hydroxyl group concentration of 100 to 400 μeq / g, a number average molecular weight of 5,000 to 15,000 g / mol and a terminal carboxyl group concentration of 100 to 400 mu] e / g of the polyamide oligomer.
In an embodiment, the solid state polymerization can be carried out at 150 to 230 캜 in the presence of supercritical carbon dioxide.
In an embodiment, the polycarbonate oligomer and the polyamide oligomer may be pellets or powders having an average particle size of 0.2 to 1 mm.
Another aspect of the present invention relates to a molded article formed from the polycarbonate-polyamide copolymer.
The present invention has the effect of providing a polycarbonate-polyamide copolymer excellent in impact resistance, thermal properties, moisture absorption resistance, etc., a method for producing the same, and a molded article formed therefrom.
Hereinafter, the present invention will be described in detail.
The polycarbonate-polyamide copolymer according to the present invention is a copolymer formed by reaction (polymerization) of a terminal hydroxyl group of a polycarbonate oligomer and a terminal carboxyl group of a polyamide oligomer.
The polycarbonate oligomer of the present invention may have a number average molecular weight as measured by gel permeation chromatography (GPC) of 5,000 to 15,000 g / mol, such as 8,000 to 10,000 g / mol, The terminal hydroxyl group concentration may be 100 to 400 μeq / g (μ eq / g), for example, 120 to 250 μeq / g. When the number average molecular weight of the polycarbonate oligomer is less than 5,000 g / mol, the impact resistance and the like of the polycarbonate-polyamide copolymer may decrease. When the number average molecular weight is more than 15,000 g / mol, the polycarbonate oligomer and the polyamide oligomer , The reaction may not be properly performed. If the terminal hydroxyl group concentration is less than 100 μeq / g, the production time of the polycarbonate-polyamide copolymer may be prolonged, and if it exceeds 400 μeq / g, The residual hydroxyl group concentration of the polycarbonate-polyamide copolymer becomes high, and the moisture absorption resistance and the like may be lowered.
In an embodiment, the polycarbonate oligomer is produced by reacting an aromatic diol compound (diphenol) and a carbonate precursor such as phosgene, halogen formate, carbonic acid diester or the like with the number average molecular weight and terminal hydroxyl group concentration according to a known polymerization method It may be manufactured. Examples of the aromatic diol compound include 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) Propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2-bis (4-hydroxyphenyl) cyclohexane, (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane and the like. Propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl- Hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) cyclohexane. More specifically, bisphenol- 2,2-bis (4-hydroxyphenyl) propane referred to as A can be used. The polycarbonate oligomer may be a commercially available polycarbonate resin having a number average molecular weight and a terminal hydroxyl group concentration.
The polyamide oligomer of the present invention may have a number average molecular weight as measured by gel permeation chromatography (GPC) of 5,000 to 15,000 g / mol, such as 8,000 to 10,000 g / mol, The terminal carboxyl group concentration may be 100 to 400 μeq / g, for example, 120 to 250 μeq / g. If the number average molecular weight of the polyamide oligomer is less than 5,000 g / mol, the impact resistance and the like of the polycarbonate-polyamide copolymer may deteriorate. When the number average molecular weight is more than 15,000 g / mol, the polycarbonate oligomer and the polyamide When the concentration of the terminal carboxyl group is less than 100 μeq / g, the production time of the polycarbonate-polyamide copolymer may be prolonged. When the concentration of the terminal carboxyl group exceeds 400 μeq / g , The residual carboxyl group concentration of the polycarbonate-polyamide copolymer becomes high, and the moisture absorption resistance and the like may be lowered.
In an embodiment, the polyamide oligomer is an aliphatic polyamide resin such as polyamide 66 or polyamide 6 having a number average molecular weight and a terminal carboxyl group concentration; A semiaromatic polyamide resin obtained by polymerizing a diamine component containing a dicarboxylic acid component including an aromatic dicarboxylic acid such as polyamide 6T and an aliphatic diamine; And so on. For example, when the polyamide oligomer is an aliphatic polyamide resin, the thermal stability, moisture absorption resistance and the like of the polycarbonate-polyamide copolymer can be further improved. As the polyamide oligomer, a commercially available polyamide resin having the number average molecular weight and terminal carboxyl group concentration may be used.
The polycarbonate-polyamide copolymer according to one embodiment of the present invention can be prepared by solid phase polymerization of the polycarbonate oligomer and the polyamide oligomer.
In an embodiment, the solid phase polymerization can be carried out in the presence of supercritical carbon dioxide at 150 to 230 ° C, for example 160 to 200 ° C, for 1 to 24 hours, for example 5 to 20 hours. The reactivity of the polycarbonate oligomer and the polyamide oligomer may be high in the above-mentioned temperature range, and the polycarbonate-polyamide copolymer can be obtained in high yield.
The supercritical carbon dioxide is carbon dioxide exceeding a critical point. The temperature and the pressure at which the density of liquid and gas are equal to each other are referred to as critical points, and the fluid at a temperature and pressure exceeding the critical point is referred to as a supercritical fluid. For example, the solid state polymerization may be carried out by flowing supercritical carbon dioxide at 160 to 200 DEG C and 80 to 120 bar at a rate of 0.1 to 2.0 L / min.
In an embodiment, the polycarbonate oligomer may comprise 10 to 50 wt%, for example 20 to 50 wt%, of 100 wt% of the polycarbonate-polyamide copolymer (polycarbonate oligomer and polyamide oligomer) The polyamide oligomer may be contained in an amount of 50 to 90% by weight, for example, 50 to 80% by weight, based on 100% by weight of the polycarbonate-polyamide copolymer. In the above range, the polycarbonate-polyamide copolymer may be excellent in impact resistance, thermal properties, moisture absorption resistance, and physical properties thereof.
In embodiments, the polycarbonate oligomer and the polyamide oligomer may each be a pellet or powder having an average particle size of less than or equal to 1 mm, such as from 0.2 to 1 mm. When the polycarbonate-polyamide copolymer is polymerized in the above range, by-products can be easily removed, and a copolymer having excellent physical properties can be obtained in high yield.
The polycarbonate-polyamide copolymer according to one embodiment of the present invention may have a number average molecular weight of 10,000 to 30,000 g / mol, for example 15,000 to 25,000 g / mol, and a weight average molecular weight of 20,000 to 60,000 g / mol , For example from 30,000 to 50,000 g / mol. In the above range, the polycarbonate-polyamide copolymer may be excellent in impact resistance, thermal properties, moisture absorption resistance, and physical properties thereof.
In an embodiment, the polycarbonate-polyamide copolymer has two melting temperatures (Tm) and one glass transition temperature (Tg) due to solid phase polymerization and crystallization of the polycarbonate, which is a differential scanning calorimeter , DSC), two melting peaks appear when measuring the melting temperature. The polycarbonate-polyamide copolymer has a melt temperature of 200 to 230 캜 (first melting point), for example, 210 to 225 캜 (first melting point) and 240 to 300 캜 (second melting point) 290 deg. C (second melting point), and the glass transition temperature may be 60 to 140 deg. C, for example 60 to 120 deg. In the above range, the polycarbonate-polyamide copolymer may have excellent thermal stability.
In an embodiment, the polycarbonate-polyamide copolymer has a notched Izod impact strength of a 1/8 "thick specimen measured according to ASTM D256 of from 15 to 90 kgf · cm / cm, for example from 20 to 70 kgf · cm / cm. < / RTI >
In an embodiment, the polycarbonate-polyamide copolymer may have a moisture absorption rate (moisture absorptivity) of 8% or less, for example, 1 to 7.5% according to the following formula 1.
[Formula 1]
Water absorption rate (%) = (W 1 - W 0 ) / W 0 × 100
W 0 is the initial weight of the specimen of 63.5 mm × 12.5 mm × 5.5 mm and W 1 is the weight of the specimen after immersing the specimen in a beaker containing water at 25 ° C. for 24 hours.
The molded article according to the present invention can be formed from the polycarbonate-polyamide copolymer. The polycarbonate-polyamide copolymer may be produced alone or in the form of pellets by extrusion in an extruder after mixing with other additives as required. The produced pellets can be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those of ordinary skill in the art to which the present invention pertains. The molded articles are excellent in impact resistance, thermal properties, moisture absorption resistance and physical properties thereof, and can be applied to various fields. For example, they can be used as interior / exterior materials for automobile parts, electric / electronic products and the like.
Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.
Example
Examples 1 to 4 and Comparative Examples 1 to 3
The polycarbonate oligomer pellets and the polyamide oligomer pellets of Tables 1 and 2 were crushed using a pellet crusher so as to have the following average particle sizes, and then crushed polycarbonate oligomers and crushed polycarbonate oligomers were prepared according to the contents of Tables 1 and 2 below. The polyamide oligomer was placed in a batch tumbler type solid phase polymerization reactor and supercritical carbon dioxide (180 DEG C, 100 bar) was flowed at 180 DEG C at a rate of 1 L / min. Carbonate-polyamide copolymer was prepared. The yield, the number average molecular weight, the weight average molecular weight, the melting temperature, the glass transition temperature, the notch Izod impact strength and the moisture absorption rate of the produced polycarbonate-polyamide copolymer were measured according to the following physical property measuring method, 1 and 2, respectively.
Comparative Example 4
The polycarbonate oligomer pellets and the polyamide oligomer pellets of Table 2 were heated (melted) at 280 DEG C for 3 minutes using a hot plate to prepare a polycarbonate-polyamide copolymer. The yield, the number average molecular weight, the weight average molecular weight, the melting temperature, the glass transition temperature, the notch Izod impact strength and the moisture absorption rate of the produced polycarbonate-polyamide copolymer were measured according to the following physical property measuring method, Respectively.
How to measure property
(1) Number average molecular weight (Mn) and weight average molecular weight (Mw) (unit: g / mol): Gel permeation chromatography (GPC, solvent: hexafluoroisopropanol, Standard sample: PMMA).
(2) Melting temperature (Tm) and glass transition temperature (Tg) (unit: 占 폚): Measured using a differential scanning calorimeter (DSC). The DSC used a Q20 measuring device manufactured by TA Corporation, and 5 to 10 mg of a sample was vacuum-dried at 80 DEG C for 4 hours (water content of 1,000 ppm or less), and then heated at 30 DEG C to 350 DEG C at a rate of 10 DEG C / After staying at 350 ° C for 1 minute, the sample was cooled to 30 ° C at a rate of 10 ° C / minute and then held at 30 ° C for 1 minute and then heated to 350 ° C at a rate of 10 ° C / The glass transition temperature and melt temperature were measured from the maximum point of the transition temperature and endothermic graph, respectively.
(3) Notch Izod impact strength (unit: kgf cm / cm): The notched Izod impact strength of a 1/8 "thick specimen was measured based on the evaluation method described in ASTM D256.
(4) Water absorption rate (moisture absorption rate, unit:%): The water absorption rate was measured according to the following formula (1).
[Formula 1]
Water absorption rate (%) = (W 1 - W 0 ) / W 0 × 100
W 0 is the initial weight of the specimen of 63.5 mm × 12.5 mm × 5.5 mm and W 1 is the weight of the specimen after immersing the specimen in a beaker containing water at 25 ° C. for 24 hours.
(55:45)
- polyamide
Copolymer
(kgf · cm / cm)
- polyamide
Copolymer
(kgf · cm / cm)
From the results shown in Table 1, it can be seen that the polycarbonate-polyamide copolymers (Examples 1 to 4) according to the present invention are excellent in impact resistance, thermal properties, moisture absorption resistance and the like.
On the other hand, in the case of Comparative Example 1 in which the number average molecular weight of the polycarbonate oligomer and the polyamide oligomer deviates from the range of the present invention by 4,000 g / mol, the reaction did not proceed sufficiently, crystallization of the polycarbonate did not proceed, 1, and a polycarbonate-polyamide copolymer having a glass transition temperature of 2 was prepared. It was found that the number average molecular weight and the weight average molecular weight of the polycarbonate-polyamide copolymer were small and the impact resistance was greatly lowered. In the case of Comparative Example 2 in which the terminal hydroxyl group concentration and the terminal carboxyl group concentration of the oligomer and polyamide oligomer were 90 μeq / g, respectively, deviating from the scope of the present invention, the terminal hydroxyl group and the terminal carboxyl group which could participate in the reaction were insufficient, , A polycarbonate having a melting temperature of 2 and a glass transition temperature of 2 Polyamide copolymer is produced, the number average molecular weight and the weight average molecular weight of the polycarbonate-polyamide copolymer are small, and the impact resistance is largely decreased. The terminal hydroxyl group concentration and the terminal hydroxyl group concentration of the polycarbonate oligomer and the polyamide oligomer In Comparative Example 3 in which the terminal carboxyl groups were out of the range of 500 μeq / g and 450 μeq / g, respectively, the concentration of terminal hydroxyl groups and terminal carboxyl groups remained after the reaction was high, so that the polycarbonate-polyamide copolymer had low hygroscopicity In Comparative Example 4 prepared by a melt blend, which is not a solid phase polymerization method, the compatibility of the polycarbonate oligomer with the polyamide oligomer was poor during the reaction, and the melting temperature was 2, A polycarbonate-polyamide copolymer having a temperature of 2 is prepared, It can be seen that with.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (11)
[Formula 1]
Water absorption rate (%) = (W 1 - W 0 ) / W 0 × 100
W 0 is the initial weight of the specimen of 63.5 mm × 12.5 mm × 5.5 mm and W 1 is the weight of the specimen after immersing the specimen in a beaker containing water at 25 ° C. for 24 hours.
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| JP2002220456A (en) * | 2000-11-22 | 2002-08-09 | Idemitsu Petrochem Co Ltd | Method for producing polycarbonate |
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