JP2005344024A - Star-shape branched polyamide resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for obtaining a star-shaped branched polyamide resin composition having good impact resistance by using a polyester resin as a raw material. <P>SOLUTION: The star-shaped branched polyamide resin composition having the good impact resistance is obtained as follows. (1) A powdery straight-chain polyester resin composed of a dicarboxylic acid component and a bivalent OH component and having ≥0.2 dl/g intrinsic viscosity is subjected to an ester-amide exchange reaction with amine compounds composed of (2)-1 a diamine compound and (2)-2 an amine compound composed of at least a trifunctional or higher polyfunctional amino compound at a temperature not lower than the higher melting point of both the amine compounds and not higher than the melting point of the polyester resin. Thereby, each bivalent OH component (ester group) of the polyester resin is substituted with the amine compound (amide group). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a star-shaped branched polyamide resin composition and a method for producing the same, and more particularly to a star-branched polyamide resin composition having good impact resistance using a polyester resin as a raw material and a method for producing the same. .

  JP-A-11-511771 describes a star-shaped branched polyamide resin that exhibits ductile fracture behavior when formed from a polyfunctional nucleus having an amino group. JP-T-2002-544307 describes a multi-branched polyamide resin made by using a monomer containing a polyfunctional amino-carboxylic acid group. They use monomers (monomers having at least two different functional groups such as α, ω-amino acids and lactams) as raw materials to adjust star-shaped or branched polyamide resins by the existing polycondensation method.

  The present inventor previously performed an ester-amide exchange reaction via a polyester resin, which is completely different from the conventional polycondensation method in Japanese Patent No. 027545, Japanese Patent Laid-Open No. 11-106504, and Japanese Patent Laid-Open No. 2001-11175. A novel production method for synthesizing a polymer from a polymer for obtaining a polyamide resin and a polyesteramide resin was proposed. In particular, Japanese Patent Application Laid-Open No. 2001-11175 proposed that a high-molecular weight polyamide resin and a polyesteramide resin can be obtained efficiently by reacting a polyester resin with a diamine compound under a specific condition without a solvent. This method is a very attractive method for producing a polyamide resin and a polyesteramide resin because the production cost is greatly reduced due to the absence of solvent.

Japanese National Patent Publication No. 11-511771 Special Table 2002-544307 Japanese Patent No. 027545 JP-A-11-106504 JP 2001-11175 A

  However, the polyamide resin and the polyesteramide resin obtained by such a method have a problem that the impact resistance is lower than materials obtained by the existing polycondensation method from a dicarboxylic acid compound and a diamine compound having the same structure. It was.

Therefore, as a result of intensive investigations to solve such problems, the present inventor has reached the present invention. That is, in the present invention, (1) a linear polyester resin having an intrinsic viscosity of 0.2 dl / g or more comprising a dicarboxylic acid component and a divalent OH component, (2) -1 a diamine compound, (2) -2 It has been found that a star-shaped branched polyamide resin composition obtained from an amine compound composed of a polyfunctional amino compound having at least three functionalities through an ester / amide substitution reaction has good impact resistance.
And these resin compositions are (1) a diamine compound, a powdery linear polyester resin having an intrinsic viscosity of 0.2 dl / g or more comprising a dicarboxylic acid component and a divalent OH component, (2) -2 By performing an ester-amide exchange reaction with an amine compound composed of at least a trifunctional or higher polyfunctional amino compound and a temperature higher than the higher melting point of the both amine compounds and lower than the melting point of the polyester resin. It has been found that the polyester resin can be obtained by substituting the divalent OH component (ester group) of the polyester resin with the amine compound (amide group).
Furthermore, it has also been found that a polyamide-based resin composition having higher impact resistance can be obtained by melt-kneading the ester-amide exchange reaction product.
It has also been found that the polyester resin is a thermoplastic polyalkylene terephthalate resin and that the thermoplastic polyalkylene terephthalate resin is preferably a polyethylene terephthalate resin.

  From the results of the table, it is understood that according to the method of the present invention, a star-shaped branched polyethylene terephthalamide resin composition having improved impact strength can be obtained from a polyethylene terephthalate resin.

The present invention is described in detail below.
First, the powdered linear polyester resin as a raw material used in the present invention is generally a dicarboxylic acid component composed of an organic dicarboxylic acid or a derivative thereof and a divalent OH component composed of a dihydric alcohol compound or a dihydric phenol compound. And obtained by a polycondensation reaction. Such organic dicarboxylic acids or derivatives thereof include, for example, terephthalic acid, isophthalic acid, phthalic acid, dimethyl terephthalate, terephthalic acid dichloride, diphenyldicarboxylic acid, naphthalenedicarboxylic acid and other derivatives thereof, oxalic acid, Aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, maleic acid, fumaric acid and their derivatives. Examples of the dihydric alcohol compound include ethylene glycol, propylene glycol, butane-1,3-diol, butane-1,4-diol, alkylene glycol compounds such as tetramethylene glycol, cyclohexanediol, and the like. Furthermore, the dihydric phenol compound is bisphenol-A or the like. These dicarboxylic acid components and divalent OH components may be used alone or in combination of two or more compounds without any problem.

  Among such linear polyester resins, thermoplastics obtained mainly using terephthalic acid as the dicarboxylic acid and mainly using alkylene glycol such as ethylene glycol and butane-1,4-diol as the dihydric alcohol. The polyalkylene terephthalate resin is preferred. Among these, polyethylene terephthalate resin is particularly preferable. Two or more kinds of linear polyester resins may be mixed and used, and there is no problem even if other organic polymers or inorganic compounds are mixed in the polyester resin.

  Further, the intrinsic viscosity of the linear polyester resin used as such a raw material is 0.2 dl / g or more, preferably 0.3 dl, as measured at a temperature of 30 ° C. using hexafluoroisopropanol as a solvent. / G or more. When the intrinsic viscosity is less than 0.2 dl / g, the intrinsic viscosity of the reaction product obtained by the present invention becomes small, and an industrially useful high molecular weight polyamide resin composition cannot be obtained. Furthermore, it is important that the polyester resin used here has a powdery form with an average particle size of 3 mm or less, preferably 1 mm or less. If the average particle size exceeds 3 mm, it takes more time than necessary for the ester-amide exchange reaction. The water content is 500 ppm or less, preferably 100 ppm or less.

  On the other hand, the diamine compound that reacts with the polyester resin includes ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, octamethylene diamine, dodecamethylene diamine, trimethylene-1,6-hexamethylene diamine, and the like. An aliphatic diamine compound: p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, m-toluylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4'-diaminobiphenyl, 3,3 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiph Nylsulfone, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminobenzanilide, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane 4,4'-diaminoanthraquinone, 3,3'-dimethoxybenzidine, α, α'-bis (4-aminophenyl) -p-isopropylbenzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, etc. 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, piperazine, 2,5-dimethylpiperazine, bis (4-aminocyclohexyl) Methane, bis (4-aminocyclohexyl) propane, 4, '-Diamino-3,3'-dimethyldicyclohexylmethane, α, α'-bis (4-aminocyclohexyl) -p-diisopropylbenzene, α, α'-bis (4-aminocyclohexyl) -m-diisopropylbenzene, menthane An alicyclic diamine compound such as diamine. Moreover, it is a polymer such as aminopolyorganosiloxane at both ends or polyalkylene ether. In addition, these diamine compounds can be used by mixing two or more kinds in addition to being used alone.

The amount of the diamine compound used is appropriately set so that the desired polyamide resin composition can be advantageously obtained. Generally, 1 mol of the repeating unit of the linear polyester resin is used. The amount is 0.001 to 1.5 mol, preferably 0.005 to 1.3 mol, and more preferably 0.01 to 1.2 mol. When the amount of the diamine compound used is less than 0.001 mol, the reaction product is not different from the raw material polyester resin, and when it exceeds 1.5 mol, the molecular weight of the reaction product obtained is reduced. Further, the water content of the diamine compound is 500 ppm or less, preferably 100 ppm or less.
Next, the polyfunctional amino compound having at least three functionalities that reacts with the above polyester resin as well as the diamine compound includes 2,2 ′, 2 ″ -triaminotriethylamine, 3,3 ′, 3 ″ -trimethylamine. Polyethyleneimine derivatives such as aminotripropylamine, N, N-bis (2-aminoethyl) -N ′, N′-bis [2- [bis (2-aminoethyl) amino] ethyl] -1,2-ethylenediamine Aliphatic triamine compounds such as 4-aminomethyl-1,8-octanediamine, aromatic triamine compounds such as 3,4,4'-triaminodiphenyl ether, heterocyclic triamine compounds such as melamine, 3,3'- And aromatic tetramine compounds such as diaminobenzidine. Among these, 2,2 ′, 2 ″ -triaminotriethylamine and 4-aminomethyl-1,8-octanediamine are preferable. These polyfunctional amine compounds are used alone or in combination of two or more. In addition, the water content of the polyfunctional amine compound is 500 ppm or less, preferably 100 ppm or less.

  The amount of these polyfunctional amino compounds is appropriately set so that the desired polyamide resin composition can be advantageously obtained. Generally, (2) -1, diamine compound / (2)- 2, The molar ratio of at least trifunctional or higher polyfunctional amino compound is (5-200) × n (n is the number of functional groups of at least trifunctional or higher polyfunctional amino compound), preferably (10 to 150). ) × n, more preferably (15-100) × n. When the molar ratio is less than 5n, the reaction product is easily gelled, and when it exceeds 200n, the branching effect does not appear in the reaction product. The water content of such a polyfunctional amine compound is 500 ppm or less, preferably 100 ppm or less.

  And in order to obtain the target polyamide-type resin composition, the linear polyester resin as said reaction raw material, a diamine compound, the polyfunctional amino compound more than trifunctional at least is made to react on specific conditions, and this linear When all divalent OH components (ester groups) of the polyester resin are replaced with the diamine compound and the polyfunctional amino compound (amide group) having at least three functionalities, a star-shaped branched polyamide resin and a straight chain When only a part of the resin composition of the linear polyamide resin is exchanged, a resin composition of a star-shaped branched polyesteramide resin and a linear polyesteramide resin is obtained.

  In order to produce the polyamide-based resin composition, the linear polyester resin, the diamine compound, and the polyfunctional amino compound having at least three functionalities as the respective reaction raw materials are dried to a predetermined moisture content or less, and the respective requirements Charge the amount into a suitable reaction vessel with pressurization, decompression and stirring functions, completely replace the inside of the reaction vessel with an inert gas, pressurize or seal, and then use the higher of both amine compounds used. The linear polyester resin and both amine compounds are prereacted by heating and stirring to a temperature not lower than the melting point of the linear polyester resin and not higher than the melting point of the linear polyester resin. That is, by this preliminary reaction, some ester groups in the polyester resin react with both amino compounds. As the reaction proceeds, the divalent OH component of the polyester resin is released from the polyester chain and is by-produced, so it is important to remove it from the reaction system. Removal of the divalent OH component is easily carried out by reducing the pressure in the reactor or passing an inert gas at an appropriate time when the reaction has proceeded.

  The reaction temperature for reacting the linear polyester resin and both amine compounds is a temperature not lower than the higher melting point of both amine compounds used and not higher than the melting point of the linear polyester resin. Adopted. On the other hand, the reaction time depends on the shape and size (powder state) of the linear polyester resin, but is usually 0.5 to 50 hours, preferably 1 to 40 hours, more preferably 2 to 30. It's time.

  The reaction vessel used for such ester / amide exchange reaction has a raw material inlet and a reaction product outlet, and the inside thereof is replaced with an inert gas, pressurized, decompressed, heated and If it can stir, various well-known things are used. For example, there are various metal reactors such as a vertical type, a horizontal type, and a rotary type, a powder mixer, and a dryer.

  The intrinsic viscosity of the polyamide resin composition as a preliminary reaction product produced by the ester / amide exchange reaction of the present invention is usually about 0.3 to 2.0 dl / g.

  In the present invention, the ester / amide exchange reaction product (preliminary reaction product) is further charged into an appropriate kneading apparatus and melt-kneaded to completely advance the ester / amide exchange reaction. Both the amino compounds thus obtained are completely exchanged with the divalent OH component in the polyester resin to obtain a high molecular weight polyamide resin composition. It is important that such melt-kneading is performed by completely replacing the inside of the kneading apparatus with an inert gas. When melt-kneading in a state where air and moisture are mixed in the apparatus, the polyamide-based resin as a product deteriorates or gels, and is remarkably colored.

  The temperature for such melt kneading varies depending on the kind and amount of the raw material and the reaction degree of the preliminary reaction product, but is generally set in the range of 150 to 400 ° C, preferably 200 to 350 ° C. When the reaction temperature is less than 150 ° C., the preliminary reaction product is not melted. On the other hand, when the temperature exceeds 400 ° C., thermal decomposition occurs vigorously by melt-kneading, and a useful polyamide-based resin composition cannot be obtained.

  The melt kneading time depends on many factors like the temperature, but is usually 0.1 to 10 minutes. When the melt kneading time is less than 0.1 minutes, the melting does not proceed sufficiently, while when the melt kneading time exceeds 10 minutes, the obtained polyamide resin tends to deteriorate or gel.

As the melt-kneading apparatus, various known apparatuses can be used as long as they can knead a highly viscous polymer under heating conditions. For example, rolls, extruders, kneaders and the like. Among these, a single-screw or multi-screw extruder with a vent that is easy to knead at a high temperature and easily collects a product and removes a by-product is desirable.
The polyamide-based resin composition obtained by melt-kneading has an intrinsic viscosity of about 0.6 to 5.0 dl / g, which further improves the molecular weight and becomes a useful resin composition.

  In each stage of the ester / amide exchange reaction of the present invention (preliminary reaction stage and melt kneading stage), a known carboxylic acid activator (triphenyl phosphite, triphenyl phosphate, etc.) Phosphites, phosphates), molecular weight regulators (monoamino compounds such as triethylamine, toluidine, benzylamine, cyclohexylamine, 1,2-epoxyhexane, 1,2-epoxyethylbenzene, 1,2-epoxycyclohexane It is also within the scope of the present invention to adjust the molecular weight (anti-gelling) of the reaction product by adding a monoepoxy compound such as n-butyl isocyanate, cyclohexyl isocyanate, or phenyl isocyanate.

Furthermore, various compounding agents such as known heat stabilizers, light stabilizers, colorants, lubricants, reinforcing agents, fillers and the like are blended alone or in combination depending on the purpose. The polyamide resin composition of the present invention finally obtained through such a procedure is molded into a desired molded article by various known methods such as ordinary melt molding methods such as compression molding, injection molding, and extrusion molding. The Moreover, these resin compositions are dissolved in a solvent and formed into a film or a coating layer by a casting method.
Hereinafter, some examples of the present invention will be shown and the present invention will be more specifically clarified, but it is needless to say that the present invention is not limited by the description of such examples. The present invention is not limited to the following examples, and other than the above-described specific description, various changes, modifications, and improvements can be made based on the knowledge of those skilled in the art without departing from the spirit of the present invention. It should be understood that these can be added.

(Examples 1-3, Comparative Examples 1-4)
A commercially available linear polyethylene terephthalate resin, Novapex GS300 (manufactured by Mitsubishi Chemical Corporation, intrinsic viscosity, 0.65 dl / g, hexafluoroisopropanol, 30 ° C.) was pulverized to obtain a wire mesh pass product of 1000 μm (1 mm). Subsequently, this powdery polyethylene terephthalate resin was dried at 150 ° C. for 5 hours to adjust the water content (measured with a moisture meter manufactured by Mitsubishi Chemical Corporation) to 80 ppm.
Commercially available hexamethylenediamine, HMD (Wako Pure Chemical Industries, Ltd., reagent grade 1) was mixed with molecular sieves 4A 1/16 (Wako Pure Chemical Industries, Ltd.) at 60 ° C. and dehydrated under reduced pressure under nitrogen. And purified. Ethylenediamine, EDA (manufactured by Wako Pure Chemical Industries, Ltd.), 2,2 ', 2 "-triaminotriethylamine, and TATEA (manufactured by Wako Pure Chemical Industries, Ltd.) are mixed and dehydrated with molecular sieves 4A 1/16 at room temperature. And purified by distillation under nitrogen.
The above-mentioned dry raw materials were charged at a ratio shown in the table in a 10 liter reactor having a double spiral ribbon stirring blade inside, avoiding mixing of moisture under a nitrogen atmosphere. While pressurizing the inside of the reactor with nitrogen gas, the mixture was stirred at 10 rpm and reacted at 0.5 MPa and 150 ° C. for 5 hours. Thereafter, the inside was reacted while reducing the pressure to 200 to 1 mbar at 200 ° C. for 5 hours, and ethylene glycol as a by-product was removed from the reaction system to obtain a white preliminary reaction product. The amount of removed ethylene glycol was approximately 90% of the theoretical amount. The pre-reaction product amidation rate and intrinsic viscosity were measured. The results are shown in Table 1. Incidentally, amidation ratio was determined from the absorbance of 1720 cm ^-1 and 1540 cm ^-1 in the infrared chart according to the following equation. Amidation ratio = 1540 cm ^-1 absorbance / (Absorbance + 1720 cm absorbance ^-1 1540 cm ^-1).

  Next, the preliminary reaction product was melt kneaded. As a kneading apparatus, a 40 mm twin screw extruder, ZE40AX40D, manufactured by Belstolf, was used. The kneading conditions were temperature setting, 280 to 300 ° C. in the die direction from the bottom of the hopper, 50 rotations / minute, and a resin supply amount of 6 kg / hour. Except for Comparative Example 4, the rest from the resin supply section (hopper) to the extruder was completely shut off from the outside and replaced with nitrogen gas. The vent was depressurized in the range of 200 to 10 mbar from the bottom of the hopper to the die direction. The extruded strand was cooled and cut into pellets. The amidation rate, intrinsic viscosity, impact strength of the injection-molded test piece, and coloring state of the obtained melt-kneaded product were examined. The results are shown in Table 1.

  In Comparative Example 3, since there were many polyfunctional amine compounds of (2) -2, it gelled in the preliminary reaction stage and melt kneading was impossible. Further, Comparative Example 4 was the same raw material composition and preliminary reaction product as Example 2, but nitrogen gas substitution was not performed during melt kneading. The melt-kneaded product was markedly colored.

Claims (6)

(1) A linear polyester resin composed of a dicarboxylic acid component and a divalent OH component and having an intrinsic viscosity of 0.2 dl / g or more is converted into (2) -1, a diamine compound, (2) -2, at least 3 A star obtained by substituting the amine compound (amide group) of the polyester resin with an amine compound composed of a polyfunctional amino compound having higher functionality than the divalent OH component (ester group) of the polyester resin by an ester / amide exchange reaction Type branched polyamide resin composition. (1) A powdered linear polyester resin composed of a dicarboxylic acid component and a divalent OH component and having an intrinsic viscosity of 0.2 dl / g or more is represented by (2) -1, a diamine compound, (2) -2, An amine compound composed of a polyfunctional amino compound having at least trifunctionality and a polyester resin having an ester-amide exchange reaction at a temperature not lower than the higher melting point of both amine compounds and not higher than the melting point of the polyester resin. A method for producing a star-shaped branched polyamide-based resin composition, comprising substituting the valence OH component (ester group) with the amine compound (amide group). In the ester-amide exchange reaction, the molar ratio of both amine compounds (2) -1 / (2) -2 is (5-200) × n (n is a function of a polyfunctional amino compound having at least trifunctionality or more). The method for producing a star-branched polyamide-based resin composition according to claim 2, wherein the reaction is performed based on the number of groups. 4. The method for producing a star-branched polyamide-based resin composition according to claim 2, wherein the ester-amide exchange reaction product is further melt-kneaded to further advance the ester-amide exchange reaction. The said polyester resin is polyalkylene terephthalate resin, The manufacturing method of the star-shaped branched polyamide-type resin composition in any one of Claims 2-4. The method for producing a star-shaped branched polyamide resin composition according to claim 5, wherein the polyalkylene terephthalate resin is a polyethylene terephthalate resin.