JPS59193953A - Polyester composition - Google Patents

Abstract

PURPOSE:A composition, obtained by incorporating an organic polymer having metallic salts of carboxyl groups in the side chain thereof with two or more polyesters in mixing them, capable of suppressing the ester interchange reaction without giving off gases nor odors by heating, and having stable physical propperties. CONSTITUTION:A polyester composition obtained by incorporating 0.01-25wt%, based on the total composition, organic polymer having metallic salts of carboxyl groups in the side chain thereof with two or more polyesters in mixing them. As the polyesters, one of the two or more polyesters used is an aromatic polyester, e.g. a polyalkylene terephthalate, and another or the other one used is an aliphatic polyester, e.g. containing adipic acid or sebacic acid as an acid component and 1,2-propylene glycol as a glycol component. The above-mentioned organic polymer is a (co)polymer of (meth)acrylic acid, maleic acid and fumaric acid and is obtained by neutralizing part or all of the carboxyl groups with a metal of Group I , II or III in the periodic table for use. EFFECT:No bleedout is caused in molded articles.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to J-lyester compositions. More specifically, the present invention relates to a novel polyester composition containing a compound that suppresses or substantially stops the transesterification reaction when a mixture of two or more polyesters is heated.

Aromatic polyesters, typified by polyethylene terephthalate and polybutylene terephthalate, are used in many products as molding materials in the fields of fibers, films, and plastics.

In particular, polyethylene terephthalate is a material with excellent mechanical properties, chemical resistance, and heat resistance, but it has a slow crystallization rate, so it is well known that it is used by adding modifiers to speed up the crystallization rate. ing.

For example, JP-A-53-65354 discloses a method of blending polybutylene adipate with a molecular weight of 2000 or less as a modifier, while JP-A-55-116751 describes a method of blending poly[propylene adipate/inphthalate (3) as a modifier. /1
)] and the like are disclosed as modifiers. However, Japanese Patent Publication No. 44-21112 discloses that when a non-sterically hindered polyester, such as polyethylene hepta-ζ-cate, is melt-blended with polyethylene terephthalate, the transesterification reaction proceeds rapidly and the melting point decreases. Although blending aliphatic polyester with polyethylene terephthalate improves many problems, such as increasing the crystallization rate and improving fluidity and slipperiness, there are several drawbacks associated with the progress of the transesterification reaction. 1 and was not currently used. These drawbacks include, for example, when blending aliphatic polyester with polyalkylene terephthalate, blending 1. When the transesterification reaction proceeds between the polyesters, a block copolymer is first obtained, and as the reaction proceeds further, a random copolymer is obtained, which lowers the melting point of the blended composition and reduces the heat resistance of the resulting molded product. Its properties are inferior to that of the original polyalkylene terephthalate. First, random copolymerization reduces the crystallinity of the composition, making it impossible to use it in fields that require crystallinity. Furthermore, these physical properties such as melting point and crystallinity vary greatly when mixing conditions during blending or processing conditions when melt processing a composition obtained by mixing change. A composition with stable physical properties,
For example, the tolerance range for manufacturing and processing conditions for obtaining molded products is extremely narrow. As a method for suppressing such transesterification reactions,
No. 500 discloses blending organic and inorganic phosphorus-containing compounds. However, these phosphorus-containing compounds have the disadvantage of decomposing or volatilizing during melt compounding, foaming the polymer and generating odor, or they may bleed out onto the surface of the molded product, causing damage to the molded product. It has defects that impair quality.

As a result of our intensive search for compounds that have the effect of suppressing or substantially stopping the transesterification reaction without these drawbacks, we found that organic polymers having a metal salt of carxyl group in the side chain were found to be remarkable. The present invention was completed based on the discovery that it has the effect of suppressing or substantially stopping the transesterification reaction.

That is, the present invention is characterized in that when two or more types of polyesters are blended, an organic polymer having a metal salt of a carzexyl group in the side chain is blended in an amount of 0.01 to 25% by weight based on the total composition. in polyester compositions.

Since the substance that suppresses the transesterification reaction used in the present invention is an organic polymer, it does not bleed out when blended with polyester, does not decompose even at a melt-kneading temperature of 300°C, and does not generate gas. There is no polymer foaming or odor generation.
All existing problems can be resolved at once.

The polyester used in the present invention is a linear thermoplastic saturated polyester composed of a dibasic acid and a glycol, and is composed of a dibasic acid and a glycol. These include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, henananosic acid, dodecanoic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene. Examples include dical I phosphoric acid and 4,4'-biphenyldicardic acid. As for glycol,
Ethylene glycol, trimethylene glycol, 1.2
7' lono ξ diol, 1,3f mouth/ξ7 diol,
1,4 butanediol, 1.3 butanediol, 213
Butanediol, 1,2butanediol 1,5'tanediol, neopentyl glycol, 1,6hexanediol, n-octanediol, 2-ethylhexane 1.6)ol, 1-10 decane diol, polyethylene glycol, Examples include polytetramethylene glycol and polypropylene glycol. These polyesters can be produced using conventional methods, such as direct esterification with a dibasic acid and a diol followed by polycondensation, or transesterification with a dimethyl or diethyl ester of a dibasic acid and a diol, followed by polycondensation. It can be produced by a method such as condensation.

Specific examples of polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene azide, polybutylene adipate, poly1,2-
Examples include propylene hexanate, polyethylene sepacate, polyethylene sepacate, polyethylene phthalate, and polybutylene phthalate. These polyesters are disclosed in Japanese Patent Publication No. 55-4853 and Japanese Patent Publication No. 55-4853.
It may also be a polyester modified by the method described in No. 6-44166.

The organic polymer having a metal salt of a carboxyl group in the side chain is a polymer or copolymer consisting of one or more components selected from acrylic acid, methacrylic acid, maleic acid, and fumaric acid, Examples include organic polymers obtained by neutralizing some or all of the carboxyl groups with metals. Alternatively, a polymer polymer or copolymer consisting of one or more components selected from acrylic esters, methacrylic esters, and maleic anhydrides may be hydrolyzed (a portion may remain as an ester). Examples include organic polymers obtained by neutralizing some or all of the carboxyl groups generated by hydrolysis with metals. Examples of monomers for making copolymers include ethylene, propylene, styrene, acrylonitrile, butadiene, etc. Metals used for neutralization include lithium, potassium, sodium, magnesium, and calcium. Examples include one or more metals selected from Group 1, Group B, and Group M of the periodic table, such as barium, zinc, and aluminum.

The blending amount of these organic polymers is preferably 0.01 to 251 to 25% by weight based on the total weight of the composition.
It is 0.2 to 15% by weight. The blending amount of these is 0.01
If the weight is too low, the effect of suppressing the transesterification reaction will be poor. When the weight exceeds 25% by weight, not only the effect of suppressing the transesterification reaction reaches saturation, but also poor dispersion occurs, which is not desirable.

These organic polymers include Surlyn (manufactured by Dupon')
, No Imiran (manufactured by Mitsui Polychemicals) and Kobore/
(manufactured by Asahi Dow) and are easily available.

The polyester composition of the present invention may contain reinforcing materials such as glass fibers, carbon fibers, asbestos, wollastonite, talc, mica, and lunum carbonate within a range that does not impair its practicality. These reinforcing materials can impart shape stability to molded products when the composition is used for plastics applications, and can also exhibit the effect of improving mechanical properties. A particularly preferred example of these reinforcing materials is glass fiber. The amount of these reinforcing materials added is 5 to 60 parts by weight based on the total weight of the composition, preferably 1 to 60 parts by weight.
5-555-55% by weight In addition, other thermoplastic or thermosetting resins as modifiers and extenders, such as polyethylene, polystyrene, polyamide, polycarbonate,
It is also possible to blend polyurethane, phenol resin, etc.

Furthermore, the composition of the present invention may contain various additives that are commonly used in the past depending on the purpose of use, such as formulation stabilizers, ultraviolet absorbers, lubricants, mold release agents, antistatic agents, colorants, A crystal nucleating agent, a crystallization accelerator or a flame retardant can be added.

The polyester composition of the present invention can be compounded by any commonly used method. The blending method is to knead the entire composition in an extruder at once, or to melt-mix the T-J1 type of polyester and an organic polymer having a metal salt of a carboxyl group in the side chain, and then melt-mix the other polyesters. I don't like the way it's done.

The polyester composition of the present invention obtained in this manner does not undergo transesterification reaction even when it is melted and heated when two or more polyesters are blended together, and even when it remains at high temperatures for a long time during processing. , the same composition can be stably obtained without changing the originally designed physical properties.

In this way, the ability to suppress or virtually stop the transesterification reaction of polyester mixtures, which was previously impossible, is coupled with the inherent physical properties such as mechanical properties, heat resistance, and chemical resistance of polyester. This is of great significance as it expands the field of application.

The composition of the invention is used in the fields of fibers, films, molding materials and thermoplastic adhesives.

The present invention will be explained below with reference to Examples. However, the technical scope of the present invention is not limited to these examples. In addition, "1 part" in Reference Examples, Examples, and Comparative Examples indicates "part by weight" unless otherwise specified.

The melting point was measured using a differential scanning calorimeter (Model DSO-20, manufactured by Nosokin Elmer) at a heating rate of 20°C/min. The NMR spectrum was measured using nuclear magnetic resonance (NMR 400 MHz manufactured by JEOL Ltd.) at 25° C. by dissolving the sample in deuterated trifluoroacetic acid at a concentration of 3% by weight and using tetramethylsilane as a reference substance.

Reference Example 1 100 parts of methyl terephthalate, 71 parts of ethyl non-glycol, 0.05 part of manganese acetate tetrahydrate, and 0.05 part of antimony trioxide were charged into a reactor, and 18
Transesterification reaction was carried out at 0 to 200°C for 3 hours. After most of the methanol was distilled off, 0.03 part of trimethyl phosphate was added, and then the temperature was raised to 260"C, the pressure was reduced, and a polycondensation reaction was carried out at 280"C under a vacuum of 0.5mHg for 3 hours. Polyethylene terestalate having a melting point of 260° C. (DSC method) and an intrinsic viscosity of 0.5 was obtained. (Hereinafter, this polymer will be referred to as PET.) Reference Example 2 100 parts of methyl terephthalate, 120 parts of 1,4-butanediol, and 0.05 part of tetranepropyl titanate were charged into a reactor and heated at 180 to 220°C under a N2 stream. The transesterification reaction was carried out for 3 hours. After most of the methanol was distilled off, 0.03 part of trimethyl phosphate was added,
Next, the temperature was raised to 240°C, the pressure was reduced, and a polycondensation reaction was carried out at 260°C for 3 hours under a vacuum of 0.351 WHg to obtain white polybutylene terephthalate with a melting point of 227°C and an intrinsic viscosity of (1.80). (Hereinafter, this polymer will be referred to as PBT.

] Reference Example 3 7) Charge 100 parts of Pier e and 142 parts of 1,4-butanediol into a reactor, and heat at 180 to 210"C in a N2 stream for 2
A time esterification reaction was carried out. After most of the water was distilled off, 0.03 part of trimethinophosphate and part of antimony trioxide O,OS were added, and then the temperature was raised to 220"C, the pressure was reduced, and the temperature was reduced to 240"C under a vacuum of 0.5mHg. The polycondensation reaction was carried out for 6 hours at
Polybutylene adipate No. 2 was obtained. (Hereinafter referred to as PBA) Reference Example 4 100 parts of dimethyl henananosinate, 86 parts of 1,2-furopylene gellicol, 0.05 part of manganese acetate tetrahydrate, and parts of antimony trioxide O and OS were charged into a reactor. The transesterification reaction was carried out for 4 hours at 180 to 220"C in a N2 stream. After most of the methanol was distilled off, 0.03 parts of trimethyl phosphate and 0.05 parts of antimony trioxide were added, and then 240" After increasing the temperature to "C" and reducing the pressure to 0.51 parts 1
m) Perform polycondensation reaction under vacuum at 260'C for 4 hours to obtain a 75% xylene solution with a viscosity of 40,000 PS and a colorless and transparent polyethylene cellulose.

(hereinafter referred to as pps) Example 1 94 parts of the PET obtained in Reference Example 1 was dried in a tumbler-type vacuum dryer to a moisture content of 30 PPM (manufactured by Kyoto Denshi, MK-A
After drying with a shaker, the PBA obtained in Reference Example 2
5 parts and 1 part of Surlyn 1601, an organic polymer having a metal salt of carxyl group in the side chain, were added and blended, and the cylinder temperature was 250 to 270°C using a twin-screw extruder (POM-30 manufactured by Ikegai Iron Works). A pellet was obtained by melt mixing. Dry this pellet to a moisture content of 50 PPM.
A sheet with a thickness of 0.5 ttrtx was molded at a cylinder temperature of 2900 G using an injection molding machine (KO-20 manufactured by Yoro Iron Works). The melting point (hereinafter referred to as To) of the obtained sheet as a sample was measured by DSC and found to be 259°C.
Met. Similarly, a sheet of 0,5rIr1n obtained by melting and residence in the cylinder of an injection molding machine for 30 minutes and then molding was measured by DSO and the melting point (hereinafter this melting point will be referred to as T2O) was 257°C. Ta. NMR of a sheet formed by melting and residence in a cylinder for 30 minutes
As a result of measuring the spectrum, 1,4- contained in the sample
The bond involving butanediol is adipic acid-1°4
-butanediol-adipic acid bond (hereinafter referred to as A
-B-A bond) is 95%, adipic acid-1,4
-butanediol-terephthalic acid bond (hereinafter this bond is referred to as A-B-T bond) is 5%, terephthalic acid-1,
The content of 4-butanediol-terental acid bond (hereinafter referred to as T-B-T bond) was 0%.

Comparative Example 1 95 parts of PET obtained in Reference Example 1 and 5 parts of PBA obtained in Reference Example 3 were blended and molded according to Example 1, and DS
As a result of measuring O, NMR, To: 259°C, T0n
'243°C, ABA bond was 52%, A-B-T bond was 40%, and T-B-T bond was 8%.

In Example 1, in which one part of Surlyn 1601 was blended, the decrease in T0n was 14°C smaller than in Comparative Example 1, and the A-B-T bond newly generated by the Nisder exchange reaction, T-B
It can be seen that the transesterification reaction has not substantially progressed since the number of -T bonds is extremely small.

The NM spectrum of Comparative Example 1 and its absorption assignment are shown in FIG. The attributions shown in Figure 1 are as follows.

■ Beak of the methylene proton at the center of 1,4-butanediol that has an A-B-A bond ■ Beak of the methylene zolotone at the center of 1,4-butanediol that has an A-B-T bond ■ 1,4- with T-B-T bond
The peak of the central methylene proton of butanediol does not exist in Examples 2-7. Comparative Examples 2 and 3 With the composition shown in Table 1, PET, PBA, and an organic polymer were blended and molded according to Example 1, and DSO was prepared.

NMR was measured. The results are shown in Table 1.

In Table 1, the prototype is a polymer obtained by heating a copolymer of ethylene and acrylic acid (containing about 8 moles of acrylic acid) with water and aluminum hydroxide, and about 25% of the acrylic acid is aluminum. It has been neutralized.

Examples 8 and 9. Comparative Example 4 PBT obtained in Reference Example 2 and PBA obtained in Reference Example 3
(The BJ acid component organic polymer had the composition shown in Table 1 as shown in Example 1 except that the cylinder temperature of the twin-screw extruder was changed to 230 to 250°C and the cylinder temperature of the injection molding machine was changed to 270°C. A sample was prepared by compounding and molding according to the method, and the DSO was measured.The results are shown in Table 1.

Examples 10-12. Comparative Example 5.6 PET obtained in Reference Example 1 and pps obtained in Reference Example 4
and an organic polymer according to Example 1 with the composition shown in Table 2,
It was molded and the DSO was measured. The results are shown in Table 2.

Example 13.14 PBT obtained in Reference Example 2 and PPS obtained in Reference Example 4
and an organic polymer according to Example 8 with the composition shown in Table 2,
It was molded and the DSO was measured. The results are shown in Table 2.

Example 15 Example 1 was prepared using 90 parts of PET obtained in Reference Example 1, 9 parts of PBT obtained in Reference Example 2, and 1 part of Kaylin 16 Old.
As a result of compounding and molding according to the following, and measuring the NSC, To
: 259°C, T3o゛256°C.

Comparative Example 7 Using 90 parts of PI)T obtained in Reference Example 1 and 10 parts of PBT obtained in Reference Example 2, blending was carried out according to Example 1.
As a result of molding and measuring DSO, 'rO: 259°C,
T3°: 247°C.

(Hereafter, extra colors)

[Brief explanation of drawings]

FIG. 1 shows the NMR spectrum of Comparative Example 1 and its absorption assignment. Patent applicant: Asahi Kasei Industries, Ltd.

Claims (5)

[Claims] (1) When blending two or more types of 2 +) esters, an organic polymer having a metal salt of a carboxyl group in the side chain is blended in an amount of 0.01 to 25% by weight based on the total composition. polyester composition (2) An organic polymer having a metal salt of a carboxyl group in its side chain has some or all of the carboxyl groups removed using a metal selected from Groups Ⅰ, Ⅲ, and Ⅲ of the periodic table. The polyester composition according to claim 1, which is an organic polymer obtained by neutralization. (3) The polyester composition according to claim 1, wherein at least one of the two or more tE' IJ esters is an aromatic polyester. (4) The polyester composition according to claim 1, wherein one of the two or more polyesters is an aromatic polyester and the other polyester is an aliphatic polyester. (5) The aromatic polyester is polyalkylene terephthalate, the acid component constituting the aliphatic polyester is adipic acid and/or cenic acid, and the glycol component is 1,2-propylene glycol and/or 1,4 - butanediol, the polyester composition according to claim 4.