JPH0427269B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to improving the heat resistance, water resistance, etc. of a polyester type block copolymer having rubber-like elasticity obtained by reacting a crystalline aromatic polyester with a lactone. The above-mentioned polyester type block copolymer has excellent rubber-like elastic properties and excellent light resistance, but has the disadvantage that strength and elongation decrease when exposed to high temperatures for a long time. In addition, it is easily hydrolyzed by water, so it cannot be put to practical use as fibers, films, or various molding materials as it is. In order to overcome these drawbacks, a method of adding polycarbodiimide, etc., which is a hydrolysis-resistant agent to polyester, has been known for a long time, but although this method improves the durability against hydrolysis, it However, it is expensive, and has drawbacks such as discoloration of the polymer when heated for a long time. Also, in order to improve heat resistance, it may be possible to add hindered phenol or nitrogen stabilizers, but if these heat stabilizers are simply added to the polyester block copolymer, the heat resistance will hardly be improved. No effect on sexual improvement was observed. However, the present inventors have discovered that heat resistance can be significantly improved by blending a monofunctional or more functional epoxy compound and a heat stabilizer together, and have thus arrived at the present invention. That is, the present invention provides a polyester-type block copolymer obtained by reacting a crystalline aromatic polyester and lactones with a monofunctional or more functional epoxy compound tertiary phosphine and a heat stabilizer. It is a block copolymer composition. The present inventors have already found that heat resistance and hydrolysis resistance can be improved by blending an epoxy compound into the polyester type block copolymer, but if used in combination with a heat stabilizer as in the present invention, The heat resistance is further improved dramatically compared to the case where the epoxy compound is blended alone. The polyester type block copolymer in the present invention is obtained by reacting a crystalline aromatic polyester with a lactone. In the present invention, a crystalline aromatic polyester is a polymer mainly composed of ester bonds or ester bonds and ether bonds, which has at least one aromatic group as a main repeating unit, and has a hydroxyl group at the end of the molecule. be. The crystalline aromatic polyester is preferably a polyester having a melting point of 150° C. or higher when a high degree of polymerization is formed. The molding material preferably has a molecular weight of 5,000 or more, but adhesives and coating agents may have a molecular weight of 5,000 or less.
Further, those having an acid value of 1.5 equivalent/mol or less are preferable. Preferred specific examples include polyethylene terephthalate, polytetramethylene terephthalate,
Homopolyesters such as poly-1,4-cyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalate, polyester ethers such as polyethyleneoxybenzoate, poly-p-phenylene bisoxyethoxy terephthalate, or mainly tetramethylene terephthalate units or Consisting of ethylene terephthalate units, and also tetramethylene isophthalate units, ethylene isophthalate units, tetramethylene adipate units, ethylene adipate units, tetramethylene sebacate units, ethylene sebacate units, 1,4-cyclohexylene dimethylene terephthalate units, Examples include copolymerized polyesters or copolymerized polyester ethers having copolymerized components such as tetramethylene-p-oxybenzoate units and ethylene-p-oxybenzoate units. In addition, in the case of a copolymer, the tetramethylene or ethylene terephthalate unit is 60 mol%.
It is preferable that the above is included. On the other hand, as the lactone, ε-caprolactone is most preferred, but enantlactone, caprylolactone, etc. can also be used. Moreover, two or more of the above lactone species can also be used. The copolymerization ratio of the aromatic polyester and lactones is 97/3 to 5/95, especially 95/5 by weight.
~30/70 is preferred. Further, the crystalline aromatic polyester and the lactones are reacted by adding a catalyst as necessary and heating and mixing them. The structure of the epoxy compound used in the present invention is not particularly limited as long as it has one or more epoxy groups in the same molecule. Specifically, compounds represented by the following general formulas () and () can be exemplified, but the invention is not limited to these compounds. (In the formula, R ₁ is a hydrocarbon group having 1 to 4 carbon atoms with or without a side chain, R ₂ is an alkyl group with or without a side chain, and R ₃ is a divalent carbonized group with or without a side chain. hydrogen group, m is a positive number from 0 to 20) More specifically, the following compounds are exemplified. Methyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol monophenyl monoglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, etc. The epoxy compound of the present invention preferably has an epoxy value of 0.9 to 14 equivalents/Kg. The amount of the epoxy compound used varies depending on the required amount of terminal groups in the polyester type block copolymer, but is usually 0.2 to 10% by weight, preferably 0.5 to 4% by weight, based on the block copolymer. If it is less than 0.2% by weight, the effect of heat resistance and water resistance will be reduced.
If the amount exceeds % by weight, the surface condition of the molded product tends to become rough due to the influence of unreacted epoxy compound. The epoxy compound and the polyester type block copolymer are usually mixed by melt mixing, and a tertiary phosphine such as tributylphosphine or triphenylphosphine is used as a catalyst. The melt-mixing temperature is preferably from 3°C higher than the crystalline melting point of the block copolymer to 280°C. The mixing time is approximately 30 seconds to 120 minutes, and is appropriately selected depending on the mixing method and temperature. The heat stabilizers used in the present invention include hindered phenol compounds, sulfur compounds, diphenylamine compounds, and the like. Examples of hindered phenol compounds include those of the following general formula. Or (In the formula, R is -COO-, -OCO-, -NHCO-,
-CONH-,

A hydrocarbon group having 1 to 18 carbon atoms having one or more of the formulas in the molecular chain or at the end of the molecule, or as a substituent, or -S-,
−NHCO−, −CONH−,

[Formula], R' represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a hydroxyl group, R ₁ ,
R ₂ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, which may be the same or different, and l
is an integer of 0 to 2, m is an integer of 1 to 4, n is an integer of 0 to 1, and l+m is equal to the total valence of R. ) Examples of compounds represented by the above general formula (1) are:
Examples include: 3,5-ditertiary butyl-4-hydroxyhydrocinnamic acid octyl ester, 3,5-ditertiary butyl-4-hydroxyhydrocinnamic acid nonyl ester, ethylene glycol bis(3,5-ditertiary butyl-4-hydroxyhydrocinnamic acid) ester, glycerin tris(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid) ester, pentaesthritol tetrakis (3,5-di-tert-butyl-4) -hydroxyhydrocinnamic acid) ester, pentaerythritol tetrakis [3(3,5-ditertiary butyl-4
-Hydroxyphenyl)propionate], 3.
5-ditert-butyl-4-hydroxycinnamic acid-4
-Tertiary butyl phenyl ester, N-[3-
(3,5-ditert-butyl-4-hydroxyphenyl)propionyl]-4-aminophenol,
N-[3-(4-hydroxyphenyl)acryloyl]-4-aminophenol, N-stearoyl-2,6-di-tert-butyl-4-aminophenol, N-[3-(3,5-di-tert-butyl)-4-aminophenol, tertiary butyl-4-hydroxyphenyl)propionyl]-2,6-ditertiary butyl-4-aminophenol, N-stearoyl-4-hydroxy-3,5-ditertiary butylbenzylamine, N- Stearoyl-4-hydroxy-3,5-ditertiary-butylphenethylamine, N-[3-(4-hydroxy-3,5-ditertiary-butylphenol)propionyl]-4-hydroxy-3,5 -ditertiary butylbenzylamine, N・N′-bis(4-hydroxy-3・5-
ditertiary butylphenethyl) adipate amide,
2,2'-thiobis(4-tertiary butylphenol), 2,2'-thiobis(4,6-ditertiary butylphenol), 4,4'-thiobis(2,6-ditertiary butylphenol) butylphenol), distearyl-3.
5-ditertiary-butyl-4-hydroxybenzylphosphonate, diphenyl-3,5-ditertiary-butyl-4-hydroxybenzylphosphonate, distearyl-3,5-ditertiary-butyl-4-hydroxyphenyl Phosphonate, stearyl-bis(3,5-ditris(3,5-di-tert-butyl-
4-Hydroxyphenyl)phosphate. Further, examples of the compound represented by the above general formula (2) include the following. 2,6-ditert-butyl-4-methylphenol, 2,6-
Ditert-butyl-4-octylphenol, 2-
Methyl-6-tert-butyl-4-methylphenol, 2,2'-methynelenbis(4-tityl-6-
tertiary butylphenol), 2,2'-methylenebis(4,6-ditertiary butylphenol), 4.
4'-methylenebis(2,6-ditertiary bisphenol), 2,2'-ethylidenebis(4,6-ditertiary butylphenol), 4,4'-isopropylidenebis(2,6- ditertiary butylphenol,
1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 2.
4,6-tris(3,5-ditert-butyl-4-
hydroxybenzyl) mesitylene. Examples of sulfur-based compounds include those having the following general formula. (R ₃ )(-S-R ₄ )p (3) (wherein, R ₃ is a hydrocarbon group having 1 to 18 carbon atoms, or -COO-, -OCO-, -CONH in the molecular chain)
-, -NHCO- bond with 2 carbon atoms
~23 hydrocarbon groups, R ₄ is a hydrogen atom or the same hydrocarbon group as R ₃ , and the carbon atom of R ₃ and
(The total number of carbon atoms in R ₄ is 7 or more.) Specific examples of the compound represented by the above general formula (3) include the following. di-n-hexyl sulfide, distearyl sulfide, dibenzyl sulfide, diphenyl sulfide,
Dioctylthiodipropionate, dilaurylthiodipropionate, thiodiethanol dilaurate, bis(dedocylthio)methane, 1,1-bis(stearylthio)ethane, phenyl-bis(laurylthio)methane, dodecylmercaptan,
Thioglycolic acid lauryl ester, 3-mercaptopropionate stearyl ester, 3-mercaptopropionate benzyl ester, 4-mercaptobutyric acid lauryl ester, 6-mercaptocaproic acid stearyl ester, mercaptopropionate ethylene glycol ester, thioglycolic acid benzoquinone ester, Glycerin tris(6-mercaptocaproic acid) ester, N-stearyl-mercaptoglycolic acid amide, thioglycolic acid anilide, 3-mercaptopropionic acid anilide, 4-mercaptobutyric acid anilide, N
-Lauryl-4-mercaptobutyric acid amide, 6-mercaptocaproic acid anilide, NN'-bis(3
-Mercaptopropionyl)xylylenediamine. Furthermore, as the diphenylamine compound,
Examples include the following general formula. (In the formula, R ₅ , R ₆ , R ₇ and R ₈ represent a hydrogen atom or a hydrocarbon group having 1 to 4 oxygen atoms). Examples of compounds of the above general formula (4) include 4.4'-
Bis(α,α-dimethylbenzyl)diphenylamine, 4,4′-bis(α-methylbenzyl)diphenylamine, 4,4′-bis(α,α-dimethylbenzyl)diphenylamine, 4,4′-bis(α
-Methylbenzyl)diphenylamine, 4,4'-
Bis(α-methyl-α-ethylbenzyl)diphenylamine, 4-(α-methylbenzyl)-4′-
(α′-ethylbenzyl)diphenylamine, 4.
Examples include 4'-bisbenzyldiphenylamine. The amount of each heat stabilizer added is 0.05 to 5% by weight, preferably 0.1 to 1.0% by weight, based on the polyester block copolymer. However, if a large amount, for example 5% by weight or more, is used, there is a drawback that the heat stabilizer will precipitate. Note that among the above heat stabilizers, hindered phenol heat stabilizers are the most effective. The mixing may be performed simultaneously with the mixing of the epoxy compounds, or may be performed separately. Additionally, additives such as stabilizers such as pigments and weathering agents, fillers, and modifiers may be added simultaneously or separately during mixing. In the present invention, by blending an epoxy compound and a heat stabilizer, an elastic body with excellent heat resistance and water resistance can be obtained. Hereinafter, the present invention will be explained in more detail with reference to Examples. In the Examples, reduced specific viscosity, tensile strength and elongation, and heat aging resistance were measured according to the following procedures. (1) Reduced specific viscosity Measured under the following conditions. Solvent: phenol/tetrachloroethane = 6/
4 (weight ratio) Concentration: 50 mg/25 ml Temperature: 30℃ (2) Tensile strength and elongation A sample chip was formed into a 2 mm thick flat plate using a heat press, and a dumbbell-shaped No. 3 test piece was punched out. The strength (Kg/cm ² ) is the value obtained by dividing the load (Kg) at the time of elongation and breaking by the initial cross-sectional area (cm ² ), and the ratio of the elongation of the sample until it breaks to the original sample length is Elongation (%). (3) Heat aging resistance The 2 mm thick flat plate sample obtained in (2) above was left in an oven at 150°C for a specified period of time, then taken out and described above.
Tensile strength and elongation were measured according to the procedure in (2). Production example 1 Polytetramethylene terephthalate 70Kg, ε-
30 kg of caprolactone was placed in a reaction vessel, and after purging with _N2 , a melt reaction was performed at 230°C for 2 hours with stirring, and unreacted ε-caprolactone was removed under vacuum. The polyester block copolymer obtained had a reduced specific viscosity of 1.163. Tensile breaking strength is 371
Kg/cm ² and tensile elongation at break was 708%. Production Example 2 1.5 kg of the polyester type block copolymer chips obtained in Production Example 1, 30.0 g of phenyl glycidyl ether, and 1.3 g of triphenyl phosphine were placed in a drum tumbler, stirred at room temperature for 30 minutes, and then heated to 40 mmO/2. The mixture was mixed and extruded at 230°C using a screw extruder, cooled with water, and then cut into chips. The reduced specific viscosity of the obtained chips was 1.044, and the tensile strength at break was 354.
Kg/cm ² and tensile elongation at break was 680%. Production Example 3 1.5 kg of the polyester type block copolymer chips obtained in Production Example 1, 22.0 g of diethylene glycol diglycidyl ether, and 1.3 g of triphenyl phosphine were placed in a drum tumbler, mixed by stirring, and then mixed in the same manner as in Production Example 1. Manufactured chips. The resulting chips had a reduced specific viscosity of 1.540, a tensile strength at break of 397 Kg/cm ² , and a tensile elongation at break of 478%. Example 1 When making chips of the polyester type block copolymer composition of Production Example 2, "Irganox 1010" manufactured by Ciba Geigy [pentaerythritol-tetrakis] [3 (3.5- Chips were prepared by adding 4.5 g of di-tert-butyl-4-hydroxyphenyl propionate. Example 2 Chips were manufactured by adding 4.5 g of "Lasmit" (dilauryl thiodipropionate) manufactured by Daiichi Kogyo Yakuhin Co., Ltd. in place of "Irganox 1010" in Example 1. Example 3 In place of “Irganox 1010” in Example 1, Uniroyal’s “Naugard 445” [4.
Chips were prepared by adding 4.5 g of 4'-bis(α,α-dimethylbenzyl)diphenylamine. Example 4 When making chips of the polyester type block copolymer composition of Production Example 3, 4.5 g of the aforementioned "Irganox 1010" was added together with triphenylphosphine and diethylene glycol diglycidyl ether to produce chips. Example 5 Chips were manufactured by adding 4.5 g of the above-mentioned "Lasmit" instead of "Irganok 1010" in Example 4. Example 6 Chips were manufactured by adding 4.5 g of the above-mentioned "Naugard 445" in place of "Irganox 1010" in Example 4. Comparative Example 1 4.5 g of the above “Irganox 1010” was added to 1.5 kg of the polyester block copolymer obtained in Production Example 1.
After mixing in a drum tumbler, heat at 230℃.
It was melted and extruded using a 40 mmO/twin-screw extruder, cooled with water, and then cut into chips. Comparative Example 2 In Comparative Example 1 above, “Irganox 1010”
Chips were produced in the same manner as in Comparative Example 1 except that 4.5 g of "Naugard 445" was blended instead. The heat aging resistance of the chips obtained in Examples 1 to 6, Production Examples 2 and 3, and Comparative Examples 1 and 2 was measured and the results are shown in Tables 1 and 2 below. The oven leaving time was 16 days and 28 days (150°C).

【table】

[Table] As is clear from Tables 1 and 2, the composition of the present invention was produced when only an epoxy compound was blended (Production Examples 2 and 3) or when only a heat stabilizer was blended (Comparative Examples 1 and 2). ) shows significantly superior heat aging resistance. Comparative Example 3 “Irganox 1010” in Example 1 above
Instead, use the phosphorus antioxidant trilauryl thiophosphite (JPS-312 manufactured by Johoku Kagaku Kogyo Co., Ltd.).
Table 3 shows the results of making chips using 4.5 g and measuring the heat aging resistance in the same manner as in Example 1. Comparative Example 4 In Example 4 above, “Irganox 1010”
Chips were manufactured in the same manner as in Comparative Example 3, except that the same trilauryl thiophosphite as in Comparative Example 3 was used in place of the chips, and the heat aging resistance was measured. Table 3 shows the results.

[Table] Comparative Example 5 Chips were manufactured in exactly the same manner as in Example 1 except that triphenylphosphine was not used. Comparative Example 6 Chips were produced in exactly the same manner as in Example 1, using triphenylphosphine instead of triphenylphosphine. Table 4 shows the results of measuring the heat aging resistance of the chips of Comparative Examples 5 and 6.

[Table] It can be seen that the use of tertiary phosphines is particularly effective in the reaction between the polyester type block copolymer of the present invention and epoxy.

Claims (1)

[Claims] 1. A polyester block copolymer obtained by reacting a crystalline aromatic polyester with lactones, a monofunctional or more functional epoxy compound, a heat stabilizer shown in () below, and a tertiary phosphine. A polyester type block copolymer composition. () One or more compounds selected from the group consisting of hindered phenol compounds, sulfur compounds, and phenylamine compounds.