JPS6234778B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an amide group-containing copolyester. More specifically, aromatic dicarboxylic acids and/or
4,4'-dicarboxybenzanilide and/or its polyester-formable derivative is used as a parallel component in a copolyester made from alkylene glycol and a compound capable of forming a polyester with a derivative thereof. The present invention relates to a novel linear copolymerized polyester characterized by the following. It is well known that thermoplastic polyesters obtained from terephthalic acid and aliphatic diols, such as polyethylene terephthalate and polybutylene terephthalate, have been industrialized on an economic scale. Although these polyesters have excellent properties in terms of physical properties, heat resistance, chemical resistance, weather resistance, etc., they also have certain limitations. In other words, the strength and elastic modulus of fibers and films can be improved by uniaxially or biaxially oriented, but even higher strength and elastic modulus are desired for tire cords, magnetic tapes, etc. Summer. Furthermore, when used as an electrical insulating material, improvements in heat resistance at higher temperatures, dielectric constant, dielectric loss, and dielectric strength are required. Furthermore, when used for resin applications, the glass transition temperature or glass transition temperature range, which is one of the indicators for determining the dimensional stability and usable range of the molded product, is generally low, resulting in loss of rigidity of the molded product. Since this occurs at relatively low temperatures, there is a desire to improve the glass transition temperature or glass transition region. Efforts have been made to improve the disadvantages of polyesters for some time, and for example, the use of dicarboxylic acids containing amide groups as an acid component to obtain useful copolymers has been reported in US Pat.
This is disclosed in Japanese Patent Application Laid-open No. 111190/1983. However, all of these use diamide dicarboxylic acid derivatives derived from diamines, and in order to sufficiently modify the polyester, it is necessary to use a large amount of diamide dicarboxylic acid in combination, making it economically difficult. This is hardly an advantageous method. On the other hand, as a method using monoamide dicarboxylic acid, for example, J.Amer.Chem.Soc 82 , 3640
(1960) for 4,4′-dicarboethoxybenzanilide. is publicly known. However, in this method, ethylene glycol, 1,3-propanediol and 1,
It is stated that a polymer cannot be obtained by melt polymerizing 4-butanediol as a glycol component. As a result of intensive studies on polyesters made from relatively small amounts of easily available raw materials, the present inventors found that by using 4,4'-dicarboxybenzanilide or a derivative thereof capable of forming an ester as an acid component, have discovered a new polyester that can significantly improve the glass transition temperature or glass transition region without reducing or even improving the inherently advantageous mechanical properties of polyester, and have achieved the present invention. did. That is, the present invention provides −[CO−X−COO(CH ₂ ) mO]− _x and It is an amide group-containing copolymerized polyester having repeating units of and having an intrinsic viscosity of 0.3 or more. (However, X is an aromatic residue, m and n are each 2 to 6
, x and y are each positive integers of 1 or more, and 0.01≦y/(x+y)≦0.9. ) Such polyesters have higher glass transition temperatures and lower melting points than polyesters such as polyalkylene terephthalate and polyalkylene 2,6-naphthalate. Therefore, it is possible to provide a linear copolyester having excellent mechanical properties and processability. The polyester of the present invention is composed of an aromatic dicarboxylic acid and/or a derivative thereof, a compound capable of forming a polyester, an alkylene glycol, and the following formula: A novel amide group-containing copolymerized polyester obtained by condensation polymerization with a _{4,4' -} dicarboxybenzanilide derivative represented by be. Compounds capable of forming polyesters using aromatic dicarboxylic acids and/or their derivatives that are used in the synthesis of the polyesters of the present invention include terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, and 4,4'-dicarboxylic acid. biphenyl,
Dicarboxylic acids such as bis-(P-carboxyphenyl) sulfone and bis-(P-carboxyphenyl) propane, and mainly di(lower alkyl) esters of these acids can be mentioned,
Dimethyl ester is easily available and is preferred.
Particularly preferred compounds include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and dimethyl esters thereof. In addition, alkylene glycols used for forming glycol residues include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-
Examples include hexanediol. Among these, ethylene glycol, 1,4-
Butanediol is particularly preferred. The 4,4'-dicarboxybenzanilide derivative used as the amide group-containing monomer constituting the new polyester is described, for example, in J.Amer.Chem SOe
82 , 3640-3642 (1960). That is, P-aminobenzoic acid ester and terephthalic acid monoester acid chloride were mixed in a molar ratio of 1:
It can be obtained by reacting at a ratio of 1:1. Suitable derivatives include 4,4'-dicarboxybenzanilide, or its dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, methyl ethyl ester, methyl propyl ester, methyl butyl ester, ethyl propyl ester, ethyl butyl Examples include lower alkyl esters such as esters, diesters such as diphenyl esters, methyl phenyl esters, and ethyl phenyl esters, and half esters thereof. Among these, dimethyl ester and methyl ethyl ester are preferred because they are easily available. The amount of the 4,4′-dicarboxybenzanilide derivative used as a copolymerization component is determined by the general formula −[CO−X−COO(CH ₂ ) mO]− _x and In terms of the physical properties of the resulting polymer, such as the glass transition temperature or glass transition region and mechanical strength in the repeating unit, x and y are integers of 1 or more, and y/
(x+y) must be between 0.01 and 0.90, and between 0.05 and
0.80 is preferred; when the alkylene glycol is ethylene glycol or 1,4-butanediol, y/(x+
It is more preferable that y) is 0.05 to 0.45. In order to obtain the novel copolymerized polyester of the present invention, various known methods such as solution condensation polymerization method, melt condensation polymerization method, intrinsic polymerization method, etc., or a method using a combination of these methods can be employed. can. A particularly preferred method involves an esterification or transesterification reaction of aromatic dicarboxylic acids and/or their di(lower alkyl) esters, preferably dimethyl esters, with 4,4'-dicarboxybenzanilide derivatives and alkylene glycols. Preferably in the presence of a suitable catalyst such as lithium acetate, calcium acetate, magnesium acetate, manganese acetate, etc. in an inert atmosphere.
It is carried out at a temperature of 150 to 250°C while removing the water or alcohol produced, followed by the addition of a suitable polycondensation catalyst such as antimony compounds, germanium compounds, titanium compounds, silicon compounds, more specifically antimony trioxide, dioxide. In this method, polycondensation is carried out in the presence of germanium, tetraalkyl titanate, etc. under reduced pressure at 200 to 300°C until the viscosity of the polycondensate reaches a desired value. When producing a copolyester by this method, it is preferable to use alkylene glycol in excess. The novel copolymerized polyester may also be produced by melting the raw material compounds, subjecting them to condensation polymerization until a certain viscosity is reached, and then solid-state polymerizing the resulting condensation product at a temperature lower than the melting point. According to this method, it is also possible to obtain a copolyester with even higher viscosity. Polycondensation reactions are not only continuous, but also
It can also be done discontinuously. In this method, an inert filler, a flame retardant,
Additions of pigments, stabilizers, plasticizers and other additives, or all treatments other than those listed here may be carried out. These treatments can be carried out at the final stage of polycondensation, for example during solid phase polymerization or even at the end of melt polycondensation. Any type of additive may be used as an additive to the reaction mixture as long as it has a small effect on the reactants. Examples include reinforcing materials such as fillers, especially glass fibers, inorganic or organic pigments, optical brighteners, matting agents and flame retardants. These additives can be added not only in the post-treatment stage of the molten polyester but also in the stage before the polycondensation reaction. The novel copolymerized polyester of the present invention has an intrinsic viscosity of 0.3 when measured in orthochlorophenol at 25°C.
The above materials are preferably used, and unless colored additives are added, the thermoplastic resin is colorless or pale yellow and can be molded into fibers, films, and plastics. The fibers, films, and plastics thus obtained are highly crystalline and extremely useful molded products with improved mechanical properties and heat resistance. The present invention will be explained in further detail below using reference examples and examples for producing raw material compounds. In addition, in the examples, the intrinsic viscosity is a value measured at 25° C. in orthochlorophenol. In addition, the melting point or glass transition temperature of a polymer can be measured in one minute using a differential calorimeter (Perkin-Elmer DSC-IB model).
This value was obtained by increasing the temperature at a rate of 16°C, and the melting point of the polymer is the maximum value of the endothermic peak. Reference example (manufacture of 4,4'-dicarbomethoxybenzanilide) 2l equipped with a thermometer, dropping funnel and stirring device
Add methyl P-aminobenzoate to a 4-necked flask.
Charge 151 g (1.0 mol) and 600 ml of chloroform and dissolve while stirring. While cooling from the outside with ice water and keeping the internal temperature below 5°C, add an aqueous sodium hydroxide solution in which 40 g (1 mol) of sodium hydroxide is dissolved in 400 ml of water. Subsequently, the mixture was stirred vigorously while being externally cooled with ice water, and a solution of 198.5 g (1.0 mol) of terephthalic acid monomethyl ester monochloride dissolved in 400 ml of chloroform was added dropwise over 1.5 hours. The rate of addition was adjusted so that the temperature of the reaction mixture did not rise below 15°C during the addition. After the addition was complete, the mixture was stirred at room temperature for 2 hours. Next, the reaction mixture was filtered under suction to separate the precipitate. The resulting colorless powdery solid was suspended in 1 liter of water and stirred vigorously for 30 minutes to remove residual sodium chloride. Next, the product was separated and dried under reduced pressure, and the resulting crude product was recrystallized using 2 liters of dimethylformamide as a solvent. The crystals were washed with a small amount of cold methanol, and then dried under reduced pressure again to produce 235 g of white powder ( 65.2% of the theoretical yield) was obtained. The melting point of this powder is 223-224
℃, and the microanalysis results were as follows.

[Table] The obtained 4,4'-dicarbomethoxy-benzanilide is expressed by the following formula: It is a compound having the structure represented by Example 1 (25 mol% copolymerized polyethylene terephthalate) 81.9 g (0.422 mol) of dimethyl terephthalate (hereinafter referred to as DMT), 44 g of 4,4'-dicarbomethoxybenzanilide produced in Reference Example
(0.141 mol, 25 mol% of total acid amount) A mixture consisting of 25 mg of tetrabutoxy titanate, 100 mg of calcium acetate, and 69.4 g (1.12 mol) of ethylene glycol was stirred while passing nitrogen gas over the mixture to distill off methanol. At the same time, heating was continued for 4 hours at a temperature of 160 to 200°C. Next, change the temperature to 2
It took a while to reach 230°C, but during this time more methanol was distilled out, and a total of 35g of methanol was distilled out. Subsequently, the pressure was increased to 0.5 mm from normal pressure for 1 hour.
The dose was gradually reduced to Hg. During this time the temperature was also 270
The temperature was raised to ℃. Finally 270~275℃ pressure 0.5mm
After stirring the mixture for an additional 4 hours under Hg, the polymer was removed. In this way, a pale yellow transparent copolyester was obtained, but this copolyester had an intrinsic viscosity of
It was 0.65. Further, the glass transition temperature (Tg, hereinafter referred to as Tg) of this copolymerized polyester was 102°C, and the melting point (Tm, hereinafter referred to as Tm) was 220°C. Example 2 (5 mol% copolymerized polyethylene terephthalate) DMT50g (0.257 mol), 4 produced in the reference example,
4'-dicarbomethoxybenzanilide 4.24g
(0.0136 mol), 12 mg of tetrabutoxy titanate and 35 g (0.56 mol) of ethylene glycol were charged, and transesterification and polycondensation were carried out in the same manner as in Example 1 to obtain a colorless transparent polymer. The intrinsic viscosity of this copolyester is 0.60, and Tg
The temperature was 84℃, and the Tm was 251℃. Example 3 (40 mol% copolymerized polyethylene terephthalate) DMT50g (0.257 mol) and 4,4'-dicarbomethoxybenzanilide produced in Reference Example
53.63g (0.171mol), ethylene glycol 53g
(0.86 mol) and tetrabutoxy titanate 18
mg was charged, and the reaction was carried out in the same manner as in Example 2.
The intrinsic viscosity of the obtained polymer was 0.62, and Tg
was 112℃ and Tm was 210℃. Comparative example 1 DMT52.6g (0.27mol), ethylene glycol
34g (0.55mol) Tetrabutoxy Titanate 12mg
was charged, and transesterification and polycondensation reactions were carried out in the same manner as in Example 2. At this time, the condensation polymerization reaction was completed in 3 hours. The intrinsic viscosity of this polyethylene terephthalate is 0.65,
Tg was 77°C and Tm was 260°C. Example 4 A sheet was made from the polymer obtained in Example 1 and the polymer obtained in Comparative Example 1. Regarding this sheet, the breaking strength and Young's modulus were measured using Tensilon manufactured by Toyo Sokki Co., Ltd., and the results shown in Table 1 were obtained.

[Table] Example 5 (10 mol% copolymerized polytetramethylene terephthalate) DMT 40.8 g (0.21 mol), 4,4'-dicarbomethoxybenzanilide produced in Reference Example 29.48 g
(0.09 mol), 54 g (0.6 mol) of 1,4-butanediol, and 12 mg of tetrabutquin titanate were charged, and a transesterification reaction was carried out in the same manner as in Example 1. Subsequently, after adding 12 mg of tetrabutoxy titanate, the pressure was increased from normal pressure to 0.5 mmHg over 1 hour.
It gradually decreased to . During this time, the temperature was also 250
The temperature was raised to ℃. Finally temperature 250-255℃, pressure
After stirring the mixture for an additional 4 hours at 0.5 mmHg,
I took out the polymer. In this way, a colorless and transparent copolymerized polyester was obtained, and the intrinsic viscosity of this copolymerized polyester was 0.6. In addition, the Tg of this copolyester is 53℃Tm
The temperature was 207℃. Furthermore, the Tg and Tm of polytetramethylene terephthalate, which was not copolymerized, was 24°C and 227°C. Example 6 (30 mol% copolymerized polyethylene isophthalate) Transesterification and polycondensation reactions were carried out in exactly the same manner as in Example 3, except that 77.5 g (0.4 mol) of dimethyl isophthalate was used instead of DMT. . The intrinsic viscosity of the obtained polymer was 0.57, and the Tg was
It was 90 degrees Celsius. On the other hand, polyethylene isophthalate obtained without copolymerization had an intrinsic viscosity of 0.55 and a Tg of 60°C. Example 7 (10 mol% copolymerized polyethylene-2,6-naphthalate) 19.5 g (10.09
mole) ethylene glycol 11.2g (10.18 mole),
0.003 g of lithium acetate was charged and an esterification reaction was carried out at 230° C. for 6 hours while removing generated water.
Next, 3.13 g (10.01 mol) of 4,4'-dicarbomethoxybenzanilide produced in Reference Example, 27 g of ethylene glycol, and 0.0066 g of manganese acetate were added.
After heating and holding at 215℃ for 3 hours, the pressure was gradually reduced to 30mmHg over 1 hour. Next, 2.9 mg of trimethyl phosphate was added and stirred for 10 minutes under normal pressure, and then 10 mg of tetrabutoxy titanate was added while raising the temperature to 270°C.
The pressure was reduced to 1 mmHg in 30 minutes. Another 1mmHg
After stirring the mixture for 2.5 hours at ~0.2 mm Hg, the polymer was removed. The copolymerized polyester thus obtained had an intrinsic viscosity of 0.65 and a Tg of 125°C. The Tg of the non-copolymerized polymer was 124°C.

Claims (1)

[Claims] 1 - [CO-X-COO (CH ₂ ) mO] - _x and An amide group-containing copolyester having repeating units and an intrinsic viscosity of 0.3 or more. (however,
X represents an aromatic residue, m and n each represent a positive integer of 2 to 6, x and y each represent a positive integer of 1 or more, and 0.01≦y/(x+y)≦0.09. 2. The amide group-containing copolyester according to claim 1, wherein m and n are each positive integers of 2 or 4, and x and y satisfy 0.05≦y/(x+y)≦0.45.