JPS62131019A - Polyester type block copolymer composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having rubber-like elasticity and excellent heat resistance and hydrolysis resistance, by mixing a specified polyester type block copolymer with an oxazoline compound. CONSTITUTION:A polyester type block copolymer (A) is obtained by reacting 95-5wt% crystalline aromatic polyester of a MW>=5,000 and m.p.>=150 deg.C (e.g., polyethylene terephthalate) with 3-95wt% lactone (e.g., epsilon-caprolactone) at 180-260 deg.C in the presence of, optionally, a catalyst (e.g., diamyltin (II)). Component A is melt-mixed with 0.02-10wt% oxazoline compound (B) for 30sec-120 min in the temperature range of from a temperature by 3 deg.C lower than the crystallization temperature of component A to 280 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyester block copolymer composition having rubber-like elasticity. More specifically, the present invention relates to improving the heat resistance and water resistance of a polyester block copolymer obtained by reacting an aromatic polyester with a lactone.

(Prior art) Polymers obtained by reacting aromatic polyester with lactone include a method of reacting crystalline aromatic polyester with lactone (Japanese Patent Publication No. 48-4116), and a method of reacting a deliverable aromatic polyester with lactone. A method (Japanese Patent Publication No. 48-4115) characterized in that a polyfunctional acylating agent is reacted with a Plutz initial polymer to effect chain extension. Method of polymerization in a state (Special Publication No. 52-49037)
It has already been reported that it can be obtained by

(Problems to be Solved by the Invention) These polymers have excellent rubber-like elastic properties and light resistance, but when exposed to island temperature for a long time, the strength and elongation decrease significantly. In addition, it is easily hydrolyzed by water, and as it is, it cannot be used practically as fibers, films, or molding materials.

On the other hand, the method of adding polycarbodiimide, etc. as a hydrolysis stabilizer for polyester has been known for a long time, but although it has an effect on hydrolysis resistance, it is expensive and discolors when heated for a long time. It has drawbacks such as: As a method for improving heat resistance, hindered phenol-based and phosphorus-based stabilizers have been reported for some time. Although these heat-resistant stabilizers were blended into crystalline aromatic polyester lactone elastomers, no effect was observed.

(Means for Solving the Problems) The present inventors have conducted intensive studies on a method for obtaining good heat resistance and hydrolysis resistance, and as a result, have discovered the use of an oxazoline compound, and have arrived at the present invention. be. That is, the present invention is a polyester type block copolymer composition characterized in that an oxazoline compound is mixed with a polyester type block copolymer obtained by a reaction between a crystalline aromatic polyester and a lactone.

In the present invention, a polyester elastic body having excellent heat resistance and hydrolysis resistance can be obtained.

The polyester block copolymer used in the present invention is obtained by reacting a crystalline aromatic polyester with lactones. In the present invention, the 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 the main returning unit and has a hydroxyl group at the end of the molecule. It is something. Crystalline aromatic polyester is Ii
It is preferable to use a polyester having a melting point of 150° C. or higher when the r-polymer is formed. The molding material preferably has a molecular weight of 15,000 or more. Note that the Vti material and coating material may have molecules of 500 or less.

Preferred specific examples include polyethylene terephthalate, polytetramethylene terephthalate, poly-1,4-
Homopolyesters such as cyclohexylene dimethylene terephthalate and polyethylene-2,6-naphthalate,
Polyester ethers such as polyethylene oxybenzoate and poly-p-phenylenebisoxyethoxytere-7-talate, mainly consisting of tetramethylene phthalate units or ethylene 7-talate units, in addition to tetramethylene or ethylene isophthalate units, tetramethylene or ethylene adipate units , tetramethylene or ethylene bicarbonate) units, 1,4-cyclohexylene dimethylene terephthalate units, and tetramethylene or ethylene-p-oxybenzoate units.

In the case of a copolymer, it is desirable that the content of tetramethylene terephthalate or ethylene terephthalate units is 60 mol % or more.

As the lactone, 8-caprolactone is most preferred, and enantolactone, cabrylolactone, etc. can also be used. Two or more lactones can also be used simultaneously.

The copolymerization ratio of the crystalline aromatic polyester and lactone varies depending on the use. Generally, as the amount of aromatic polyester increases, the polymer becomes harder, improving mechanical properties such as strength and elongation, and as the amount of lactone increases, the polymer becomes softer, improving low-temperature properties and the like. Therefore, the ratio of heavy i+ is 97/3 for aromatic polyester/lactones.
It is preferable to appropriately select from the range of 9515 to 30/70, preferably 9515 to 30/70. For example, when obtaining a hard molded product, it is preferable to select the above ratio in the range of 9515 to 70/30, and when using it for a flexible molded product, a 422:4 agent coating agent, a sealant, etc., the above ratio is preferably selected. is 7
It is preferable to select a range of 5/25 to 30/70.

In order to obtain the polyester type block copolymer used in the present invention, when the crystalline polyester and lactones are reacted, no catalyst may be used, or a catalyst may be used.

As the catalyst, those generally used for polymerization of lactones are used, and preferred ones include lithium, sodium, potassium, rubidium, cesium, magnesium,
Calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, egg element, cerium, 61II! These include metals such as cadmium and manganese, their oxides, organometallic compounds, pentaisolates, and alkoxides. Particularly preferred are organotin, organoaluminium, and arithmetic titanium compounds, such as diacyl stannous, tetraacyl stannous,
These include diptyltin oxide, dibutyltin dilaurate, tin dioctanoate, tin tetraacetate, triisobutylaluminum, tetrabutyltitanium, germanium dioxide, antimony trioxide, and two or more yuzus may be used in combination. These polymerization catalysts may be added all at once during the polymerization of the crystalline aromatic polyester, or may be added in portions during the polymerization of the crystalline aromatic polyester and the rest during the polymerization with the lactone. You may. Alternatively, it may be added all at once during the polymerization of the crystalline aromatic polyester and lactone. The amount of these catalysts used is 0 to 0.2 weight %, preferably 0.001 to 0.1 weight %, based on the total amount of the crystalline aromatic polyester and lactone.

When the reaction is carried out in a solvent-free system, the mixture of the crystalline aromatic polyester and the lactones is melted at a temperature higher than the q-nim temperature and at a gii degree higher than the melting point of the produced block copolymerized polyester. Mix. :A: In the case of a medium system, it is generally preferable to carry out the reaction at a temperature in the range of 180 to 260°C. At temperatures below 180°C, it is difficult for the crystalline aromatic polyester to dissolve uniformly with the lactones, and at temperatures above 260°C, decomposition and other undesirable side reactions occur. α- in the solvent
Methylnaphthalene and the like are commonly used.

The oxazoline compounds used in the present invention are those having one or more oxazoline rings in the same molecule;
The ItIt structure is not particularly limited.

Specifically, 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2.5-dimethyl-2-oxazoline, 2.4-diphenyl-2-
Monooxazoline compounds such as oxazoline, 2.2'
-(1,3-phenylene)-bis(2-oxazoline)
Examples include dioxazoline compounds such as.

When melt-kneading an oxazoline compound and a polyester type block copolymer, it varies depending on the amount of end groups in the polyester type proester type block copolymer, but it is usually 0.02% by weight or more based on the polyester type block copolymer.
It is lO weight ffi%. Particularly preferably 0.05 fold ff
i%~4% by weight. If it is less than 0.02% by weight, the effect will be small, and if it exceeds 10% by weight, the surface condition of the molded product will become rough due to the presence of unreacted epoxy compounds, which is not preferable.

The mixing method is not particularly limited as long as it can be uniformly melt-mixed, such as by mixing the polyester type block copolymer nap with an oxazoline compound catalyst, etc., and then heating and melt-mixing the mixture. The melting and mixing temperature is preferably 3°C below the crystalline melting point of the elastic body to 280°C. The mixing time is about 30 seconds to 120 minutes, and is determined by the mixing method and temperature.

Further, even if pigments, stabilizers and additives of each village are added at the same time during mixing, the effects of the present invention on hydrolysis resistance and heat aging resistance do not change.

(Effects of the Invention) By adding an oxazoline compound to +1jJ of the present invention, a polyester elastic body having excellent heat aging resistance and hydrolysis resistance can be obtained.

The composition of the present invention can be applied to various molded products, such as tubes, hoses, films, sheets, backings, bottles, rolls, healds, gears, name plates, covers, hooks, switches, resin springs, fasteners, automobile exterior parts, and armor. It can be used for molded products such as decorative materials or as a coating agent.

(Example) The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto. Naomi I
In Asahi Example, the reduced specific viscosity and 5M elongation were measured according to the following procedure.

(1) Reduced specific viscosity Measured under the following conditions Solvent: Phenol, ``rcg'' Ratio 6/4 Concentration: 50
~/25 temperature: 30℃ (2) Tensile strength and elongation If the chip is made into a flat plate with a thickness of 2+IIIm using a heat press
, No.1, punch out a dumbbell-shaped No. 3 test piece, stretch it at a speed of 50 per minute, and what is the load (Ky) at which it breaks? The value divided by the 71st stage cross-sectional area Cdl> is the strength (Kg/c-
j), and the ratio of the elongation of the sample until it breaks to the original sample length is defined as the elongation (%).

Production Example Epolytetramethylene brephthalate 70, 9 and ε-caprolactone 30 F4 were placed in a reaction vessel, and after N2 purge, the melting temperature was allowed to disappear for 2 hours with stirring at 230°C, and unreacted e-caprolactone was removed under vacuum. I removed it. The obtained polyester type block copolymer has a reduced specific viscosity of 1.1.
It was 63. Tensile strength at break is 17 t+'v/crI
The tensile elongation at break was 708%.

Example 1 Polyester type block copolymer chips obtained in Production Example I 1000. fr and 2.2'-(1,3-)unisine)-bis(2-oxazoline) were placed in a LOtr-7 pump tank, brought to room temperature, stirred for 30 minutes, and the mixture was transferred to a 30G1 twin screw press. Extruded at 240℃ using
A water-cooled cutting chip was created. The reduced specific viscosity of the resulting chips was 1.2 Q8, and the tensile strength at break was -380 to 9.
/-2 tensile elongation at break was 700%.

Example 2 00rr of the polyester block copolymer chip 11) obtained in the production example and 2rr of 2-phenyl-2oxazoline were placed in a drum tumbler and pressed for 30 minutes at room temperature. The mixture was extruded at 240° C. using a 30Ω twin-screw extruder, cooled with water, and then cut into chips. The resulting chip has a reduced specific viscosity of 1.095 and a shark breaking strength of 360F4.
/crA, and the tensile elongation at break was 695%.

Comparative Example 1 Polyester-type block copolymer 1 obtained in the production example process
0 Q Ofr% Irganox toto (phenolic stabilizer, manufactured by Ciba Geigy) 3. After mixing the Orr in a drum tumbler, it was extruded at 240°C using a 30-inch twin-screw extruder, and after cooling with water, it was made into one chip of cut vinegar.

The resulting chip had a reduced specific viscosity of 1068, a tensile strength at break of 355, and a g/-1 elongation of 700%.

Example 3 After drying the chips obtained in Manufacturing Example 11 fljj, @1.2 and Comparative Example 1 under reduced pressure at 100°C, using a hot press instead, they were made into a sheet with a thickness of 211 JI, and No. 3 Dan≠Rumbel was maintained at 140°C with the gear open, and the heat aging properties were measured. The results are shown in Table 1.

Table 1 Breaking strength and elongation retention after 12 days of 140°C gear oven treatment Example 4 No. 3 dumbbells obtained in the same manner as in Example 3 were heated to 100°C.
The water resistance was measured by keeping it in hot water.

The results are shown in Table 2.

Table 2 Breaking strength and elongation retention after treatment in hot water at 100℃ for 5 days Patent applicant Toyobo Co., Ltd. Procedural amendment (voluntary) March 12, 1985 Michibe Uga, Commissioner of the Patent Office! , Indication of the case 1985 Patent Application No. 27121 (No. 3 No. 2 Name of the invention Polyester type block co-merged composition 3 Relationship with the person making the amendment 434 cases Patent applicant 2-2-8 Dojimahama, Kita-ku, Osaka City No. 1. 15 of the "Detailed Description of the Invention" of the specification to be amended δ, Contents of the amendment (1) Old copy of the specification, page 9, line 3 "61.3.13, -;- ゝ---.

Correct "epoxy compound" to "oxazoline compound".

Claims (1)

[Claims] A polyester type block copolymer composition characterized in that an oxazoline compound is mixed into a polyester type block copolymer obtained by reacting a crystalline aromatic polyester and a lactone.