JPS63189436A - Production of polyesteramide - Google Patents

Abstract

PURPOSE:To easily obtain a polyesteramide with wide selectivity for various constituent monomers, having desired physical properties, by reaction between a polyester and polyamide in the presence of a glycol. CONSTITUTION:The objective polyesteramide can be obtained by reaction be tween (A) 100pts.wt. of a polyester with a reduced viscosity >=0.2dl/g (e.g., saturated copolymer prepared from terephthalic acid, etc. and saturated dihydric alcohol) and (B) 10-200(pref. 20-150)pts.wt. of a polyamide with a reduced viscosity 0.5-2dl/g (e.g., nylon 6, nylon 66) in the presence of (C) 1-100pts.wt. based on 100pts.wt. of the components A plus B, of a glycol (e.g., ethylene glycol).

Description

Detailed Description of the Invention (a) Purpose of the Invention [Field of Industrial Application] The present invention relates to a method for producing polyesteramide. It can provide polyesteramides that can be used in a wide range of fields, and can be used in a wide range of fields.

[Conventional technology]

Traditionally, polyesters (typically polyethylene terephthalate, for example) have excellent stiffness and strength, and their melting points can be lowered by adjusting the composition of the tribasic acid and glycol that make up the polyester.

Because physical properties such as glass transition point and flexibility can be set as desired, it is widely used as a molding material, adhesive, coating agent, etc.

However, polyester has problems with chemical resistance and weather resistance, and when used as an adhesive, there are problems such as a decrease in strength, which is thought to be due to crystallinity, and poor chemical resistance.

In order to improve these problems, various attempts have already been made to copolymerize polyester with an amide component to produce polyester amide, and to use this for various purposes.

The following is known as a general study example for producing polyesteramide.

■ Polyester such as polyethylene terephthalate and nylon 6, nylon 6 are used for modification as fibers.
．． A method of melt-blending polyamides such as No. 6 at a high temperature above the melting point of both to form a polyester amide (J, ^
ppli, Polym, 'Sci, 17 84
9, 1973).

■ A manufacturing method for products used as molding materials, in which a low-molecular-weight polyester and a low-molecular-weight polyamide or nylon salt are synthesized in advance, and a block polyester amide is synthesized by a reduced pressure reaction in the presence of both. (Tokuko Sho 49-13640, Sho 55-464
12, Japanese Unexamined Patent Publication No. 56-103221).

(2) A method in which amino acid monomers such as 11-aminoundecanoic acid and ε-caprolactam are added during the synthesis stage of a polyester of a specific composition and reacted to synthesize a random polyether. (JP-A-51-125193, JP-A-59-
46975).

However, each of the above methods still has problems to be solved.

That is, in method (2), since the compatibility between polyester and polyamide is poor, not only is the exchange reaction insufficient, but when the reaction is allowed to proceed, the mixture of polyester and polyamide may decompose and become colored at high temperatures.

In addition, method (2) can only be used to produce a limited number of polymers or oligomers due to problems with the mutual compatibility and reactivity of each component. method, it is difficult to control the physical properties of the polyesteramide produced. .

Furthermore, in method (2), the amide component is not only limited to amino acid monomers that have good reactivity with polyesters or lactams, which are cyclic products thereof, but also basically only polyesteramides with a random structure can be obtained, so it is extremely limited. The physical properties that can be expected are limited, the scope of application is narrow, and the effectiveness is lacking. Furthermore, thermal decomposition of amino acids and distillation of monomers from the system may occur, making it difficult to obtain a polymer with a stable composition (and causing problems such as coloring).

Regarding the structure of the polyester amide obtained by each of the above manufacturing methods, for example, when diamine is used as the amide monomer component, an aliphatic tribasic acid is generally essential and the polyester amide has a block structure, while the amide monomer component When using amicic acid or a lactam as the polymer, there is a drawback that there are significant restrictions on the composition and structure of the polymer, such as randomization by transesterification being a prerequisite. Therefore, both methods have the problem of lacking in versatility.

[Problem that the invention seeks to solve]

As mentioned above, in conventional methods for producing polyesteramide, it is difficult to obtain polyesteramide with desired physical properties due to limitations in starting materials, limitations in the reaction mechanism, or difficulty in controlling. Otherwise, there were problems such as decomposition and coloration, and the inability to obtain a stable product.

The present invention solves the above-mentioned conventional problems, and is not limited by specific skeletons, such as polyester skeletons and polyamide skeletons, and can be used in any type of polymer, from block copolymers to random copolymers. The object of the present invention is to provide a method for producing polyester amide that is easy to produce and allows the molecular structure of polyester amide to be freely controlled, thereby making it possible to synthesize polyester amide having a novel molecular structure.

(B) Structure of the invention [Means for solving the problems and their effects] As a result of intensive studies aimed at obtaining a method for producing polyesteramide having the above-mentioned excellent features, the present inventors have discovered a method for producing a specific The inventors have discovered that by adopting certain conditions, a manufacturing method that satisfies the above requirements can be obtained, and the present invention has been completed. That is, in the present invention, (A) polyester, (B) polyamide, (C
) The present invention relates to a method for producing polyesteramide, which is characterized by heating and reacting in the coexistence of glycol, and the present invention has made it possible to produce polyesteramide having the above-mentioned advantages.

Furthermore, after heating and reacting the above (A), (B), and (C), the glycol is subsequently distilled off under normal pressure or reduced pressure, preferably while distilling off the glycol, particularly preferably under reduced pressure. By heating the reaction while
This is a preferable method for obtaining a high molecular weight polyester amide, since it can provide an even more excellent manufacturing method.

The configuration of the present invention will be described in further detail below.

The polyester (A) used in the present invention will be explained. Polyester is generally a polymer synthesized by polycondensation of a polybasic acid and a polyhydric alcohol, and various types are known for various uses. For example, for molding materials, polybutylene terephthalate and polyethylene terephthalate, together with phthalic acid, aliphatic tribasic acids, aliphatic glycols, and polyoxyalkylene glycols.

Polyesters copolymerized with oxyacids are known. For adhesives, there are also saturated copolymerized polyesters made by combining various constituent monomers mentioned above, or products made by copolymerizing tribasic acid and glycol with trivalent or higher acid or alcohol. Examples include alkyd polyester resins obtained by copolymerizing tribasic acids or fatty acids having unsaturated groups.

As the polyester (A) of the present invention, for example, those explained above can be arbitrarily mixed and used. In addition, the polyester (A) used may be used alone or as a multicomponent system consisting of multiple types of polyester.
Although any of them can be used, in the present invention, it is preferable to use a polyester substantially formed from a difunctional monomer as the polyester (A). Here, "substantially" refers to a monomer that has almost the same characteristics and functions as a polyester consisting only of difunctional monomers, and contains monomers other than difunctionality to the extent that the above characteristics and functions are not inhibited. It also includes polyester consisting of. It is preferable for the present invention to use a polyester formed substantially from difunctional monomers because there is no risk of problems such as gelation or coloring occurring during the reaction.

That is, in the present invention, since the raw material composition is heated and reacted at high temperatures in many cases, if a polyester consisting of an acid or alcohol with a valence exceeding 2 and a monomer having an unsaturated group in the molecule is used. , there is a risk of gelation or coloration during the reaction, and special measures may be required to prevent this.This problem becomes even more serious when attempting to increase the molecular weight through condensation polymerization. Become. Therefore, in order to prevent the above-mentioned problems associated with the reaction from occurring as much as possible, it is preferable to use a polyester formed substantially from trifunctional monomers.

Specifically, the polyester (A) preferably used in the present invention is terephthalic acid.

A tribasic acid appropriately selected from aromatic tribasic acids such as isophthalic acid and phthalic acid, and saturated aliphatic tribasic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanoic acid, and ethylene. Glycol, propylene glycol, butanediol.

It is a saturated copolymerized polyester formed from a dihydric alcohol appropriately selected from saturated dihydric alcohols such as hexanediol, neopentyl glycol, polyethylene glycol, polypropylene glycol, and polybutylene glycol. In particular, saturated copolyesters synthesized from terephthalic acid and other aromatic tribasic acids and saturated dihydric alcohols, or saturated copolymerized polyesters synthesized from terephthalic acid and other aromatic tribasic acids and saturated dihydric alcohols. Preference is given to using copolymerized polyesters.

Useful polyesters (A) used in the present invention have a reduced viscosity of 0.2 a/g or more,
0.34! / g or more and 2.0 dl/g or less is more preferable, and 0.5 a/g or more and 1.0 d1/g or less is particularly preferable. In this specification, reduced viscosity refers to a polymer concentration of 0.25 glo in a solvent with a weight ratio of phenol/tetrachloroethane = 6/4.

It is the reduced viscosity measured at 25 dl and 40°C. The reduced viscosity is 0.24! If the amount of polyester is less than /g, when heated in the coexistence of polyamide and glycol, the polyamide may not be completely melted or dissolved, or gelation and discoloration may occur due to heat deterioration of the polyamide. Particular measures may be required.2. O
Li! If the amount exceeds /g, the polyester itself may not be sufficiently melted and dissolved, which may impair reactivity.

In addition, in the present invention, when the glycol is subsequently distilled off while heating under normal pressure or reduced pressure and then polycondensed to increase the molecular weight, all or part of the alcohol forming the polyester (A) used is , is preferably an aliphatic glycol having 12 or less carbon atoms.

Next, the polyamide (B) used in the present invention will be explained.

Polyamide is generally a polymer having amide bonds, and various types of polyamide have been known. Specifically, for example,
Polyamide resins whose typical constituents are unsaturated fatty acids such as dimer acid and diamines such as ethylenediamine or alkanolamines, and nylon obtained by condensation polymerization of amino acids, ring-opening polymerization of lactams, or condensation polymerization of diamines and tribasic acids. 6, nylon 6.6, nylon 11
゜Nylon 12, Nylon 6.10, Nylon 6゜12
and synthetic linear polyamides such as copolymerized nylon obtained by copolymerizing these monomers, so-called nylon resins, all of which can be used in the present invention. Considering the possibility of gelation and coloring at high temperatures like polyester, nylon-based resins having no unsaturated groups in the molecule are preferable as the CB) polyamide. Further, from the viewpoint of ease of exchange reaction, nylon synthesized from amino acids or lactams, which are cyclic products thereof, is preferred.

The degree of polymerization of the polyamide (B) used in the present invention is not particularly limited, but preferably has a reduced viscosity of 0.5 dl/g or more and 2.0 dl/g or less, and 0.5 dl/g or more and 2.0 dl/g or less. If it is less than 5 dl/g, layer separation will easily occur during the reaction, and decomposition and coloration will occur easily, and if it exceeds 2.0 dl/g, dissolution will be prolonged and reactivity may be impaired. .

The reduced viscosity in this case is a value measured in a 90% formic acid solution at a polymer concentration of 0.25 glo, 25 dl, and 25°C.

Next, the glycol (C) used in the present invention will be explained.

The present inventors have discovered that the coexistence of glycol provides superior effects during the synthesis of polyesteramides, leading to the present invention.

Any arbitrary glycol can be used as the glycol (C) used in the present invention, such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, and bentanediol, which are the same as the monomer components constituting polyester.

These include aliphatic glycols such as hexanediol, aromatic diols such as bisphenol A, alicyclic diols such as hydrogenated bisphenol A, and polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol. Any can be used in the present invention.

Considering the reactivity (exchange reaction) during heating, the number of carbon atoms is 12.
The following aliphatic glycols are preferred. Even in the case where the reaction is carried out by heating while distilling off the glycol following heating, it is preferable to use an aliphatic glycol having 12 or less carbon atoms as described above.

Furthermore, it is desirable that the glycol (C) and the glycol constituting the polyester (A) used are of the same type as possible. That is, as the glycol (C), it is desirable to use the same glycol as the one constituting the polyester (A) used, and (
A) When the ester is composed of two or more glycols, the glycol (C) used is preferably the same as at least one of them, and more preferably the same as as many types as the glycol constituting the polyester. It is preferable to use exactly the same type of glycol, and it is particularly preferable to use glycols having the same component ratio as those constituting the polyester. (C) If the glycol is selected in this way, F
It is possible to easily manage the structural units of the polyester amide produced by it&+, and by such selection,
Almost identical structural unit polymers can be obtained without the need for subsequent heating to distill off the glycol.

The most distinctive feature of the present invention is that glycol is present during the reaction. That is, many methods for producing polyesteramide copolymers by heating and melting mixing nylon and polyester have been studied in the past, but in contrast to these, in the present invention, as mentioned above, free glycol, that is, non-esterified glycol, etc. coexists. This is an extremely important feature. According to the present invention, polyester amide is produced by the exchange reaction of ester amide at a lower reaction temperature than conventionally and in an extremely short time.

As a result, it is possible to obtain a product having excellent resin properties such as excellent regularity as a polymer and extremely little thermal deterioration due to polyamide.

In addition, in the present invention, it is possible to adopt a method of proceeding with condensation polymerization by successively heating under normal pressure or reduced pressure, preferably while attempting to distill off excess glycol, and this also allows the ester amidation exchange reaction to be controlled. This makes it possible to control the physical properties of the product very easily.

Next, the above (A) polyester in the present invention,
The composition ratio of the three components: ) polyamide and (C) glycol will be explained.

In carrying out the present invention, the composition ratio of the above three components is not particularly limited, but preferably 10 parts by weight or more of (B) polyamide to 100 parts by weight of (A) polyester.
The amount is 0 parts by weight or less, more preferably 20 parts by weight or more and 150 parts by weight or less. If the amount of polyamide is less than 10 parts by weight, the performance provided by the amide will be insufficient, and if it exceeds 200 parts by weight, the polyamide will deteriorate due to heat during the reaction. or the ester amide exchange reaction may not be carried out sufficiently.

(C) Glycol component consists of (A) polyester and (B)
It is preferably 1 part by weight or more per 100 parts by weight in total with the polyamide. The higher the proportion of this (C) glycol component, the faster the ester amidation exchange reaction will proceed, but if too much glycol is added, it may be necessary to distill off excess glycol, or while continuing to distill off glycol, the degree of condensation polymerization may be increased. In order to increase the reaction time, a long reaction time is required.Taking this point into consideration, the amount is preferably 100 parts by weight or less.

The present invention relates to a method of heating and reacting a mixture of the three components (A), (B), and (C) to obtain a polyesteramide, but the heating conditions at this time are not particularly limited. However, in consideration of the reactivity of the three components, it is preferable to heat the mixture to 150°C or higher, and particularly preferably to 200°C or higher. Note that the upper limit temperature is the reflux temperature of glycol, and when reactivity is considered, it is preferable to carry out the reaction under reflux of glycol.

Polyesteramide is obtained by the above heating reaction, but in order to obtain high molecular weight polyesteramide,
It is preferable to further heat the reaction under normal pressure or reduced pressure at a temperature of 200° C. to 300° C., preferably while distilling off the glycol.

In the above reaction, the reaction becomes more active when one or both of polyester and polyamide is melted in glycol, so it is preferable to heat the polyester and/or polyamide to a temperature higher than the melting point of the polyamide to cause the reaction. It is desirable to select a glycol taking into consideration its boiling point.

When reacting polyester and polyamide in glycol without melting, it is necessary to adjust the amount of glycol added so that the reaction is uniform, but in this case, it is possible to reduce the thermal history of polyester and polyamide. This is a preferable method because it can prevent thermal deterioration and allows for greater flexibility in the selection of reactors.

The present invention can be easily carried out by melting a pre-synthesized polyester in a reaction tank, adding polyamide and glycol, and heating to carry out the reaction. , using tribasic acid and glycol as main raw materials, oligoesterification is performed by esterification reaction in the coexistence of a catalyst mainly consisting of a metal salt, and then 200° under normal pressure or reduced pressure.
Glycol is distilled off at C to 270°C to obtain a polyester having a high molecular weight, to which polyamide and glycol are added and reacted at the boiling point temperature of the glycol under reflux, or further subsequently at 220°C to 270°C at normal pressure or preferably Examples include a method in which polycondensation is carried out under reduced pressure while distilling off glycol to increase the molecular weight. This reaction is preferably carried out under a nitrogen stream, and a polymerization catalyst used for polyester polymerization, an inorganic filler such as calcium carbonate, talc, zinc white, titanium oxide, silicon oxide, or other substances are added to the reaction system. Monomers or polymers such as polyester, polyether, caprolactone, polycaprolactone, etc. may also be present.

In the present invention, by adjusting the amount of glycol (C) in the three components (A), (B), and (C) above, and controlling the normal pressure reaction temperature and reaction time in the coexistence of the king, it is possible to easily The ester amidation exchange reaction can be controlled. In addition, if a higher degree of polymerization is to be achieved subsequently, the ester amidation exchange reaction can be suppressed.

In the present invention, since the reaction can be controlled as desired as described above, the desired product can be obtained by controlling the extent of the exchange reaction. Thus, it is possible to control the desired polyesteramide, from blocked polyesteramides to essentially randomized products.

The composition ratio of the product can be determined as follows.

That is, the product is dissolved in trifluoroacetic acid, H'-N of -C
By measuring MR, it is possible to know the monomer ratio of each constituent unit of polyester and polyamide, and the peak of H bonded to the carbon adjacent to the carbonyl group of polyamide is obtained at 6 = 2 to 3 PPM. , the exchange ratio can be estimated using the fact that the peak shifts to the higher magnetic field side due to ester-amide exchange. Generally, the composition ratio of the product can be controlled by the melting point by utilizing the fact that the melting point of the product decreases as the randomization of the copolymer progresses. At this time, the component distilled out of the reaction system is glycol, so if the glycol constituting the polyester used is the same as the glycol used, the composition ratio itself can be controlled by the melting point. It becomes possible to do so.

As described above, by the production method of the present invention, it has become possible to easily produce various polyesteramides, which have been difficult to synthesize in the past, as desired. By using the present invention, it is possible to easily obtain polyesteramide with novel physical properties that were previously difficult to obtain, and for the first time it is possible to produce polyesteramide that can be used extremely effectively in applications such as adhesives, molding materials, and coating materials. became.

〔Example〕

Examples of the present invention will be described below along with comparative examples. Note that, as a matter of course, the present invention is not limited only to the examples described below.

Example-1 70 moles (13.6 kg) of dimethyl terephthalate, 100 moles (6.2 kg) of ethylene glycol, 1°4
- Add 100 moles (9.1 kg) of butanediol and 0.1 mole of tetra-n-butoxytitanium to the reaction vessel,
The transesterification reaction was carried out at 140 to 190°C in a nitrogen stream. After the transesterification reaction was completed, 1.30 mol (4.4 kg) of adipine was added, and the esterification reaction was carried out at 190 to 210°C. After that, the temperature was increased and the pressure decreased at the same time, and 5
Polyester a was obtained by polymerization at wHg and 210°C to 280°C. The obtained polyester a has terephthalic acid residue/adipic acid residue/ethylene glycol residue/1
．． The composition ratio of 4-butanediol residue is 70/3015
0150 (molar ratio). The reduced viscosity of this polyester is 0.65 dl/g, the melting point ■ is 152°C,
The melting point (■) was 147°C, and the appearance was white and opaque.

Here, the melting point (■) is the endothermic peak temperature measured by differential scanning calorimetry (DSC) and expressed in °C.

Further, the melting point (■) is the melting end temperature of the product measured using a polarizing microscope type melting point measuring device and expressed in °C.

In FIG. 4, the measurement results of the differential scanning calorific value of this polyester a, which is the raw material used, are shown by a curve indicated by the symbol a. Fourth
As shown in the figure, an endothermic peak indicating the melting point ■ appears at 152°C.

200 g (100 parts by weight) of the polyester a obtained above was placed in an oil bath at 240°C.
0n+j! Pour into a four-loaf flask, and after melting, add nylon 1
1 (Nippon Rilsan (■)) 60 g (301°C parts) and 6 g (3 parts by weight) of ethylene glycol were added and reacted under nitrogen atmosphere under reflux for 1 hour at normal pressure. Scanning calorimetry data are already shown in FIG.

As shown in the figure, the peak indicating the melting point (■) was at 190°C, while the melting point (■) was 189°C.

After the above reaction, the produced resin was sampled, the differential scanning calorimetry was measured, and from the endothermic peak, the number of components and the melting point I
was measured. The results are shown in FIG. 1(a). Comparing this curve in Figure 1 (A) with curves a and b in Figure 4, the curve in Figure 1 (A) has a peak at 145°C, which is close to 152°C, which is the peak of polyester a, and Nylon I
It can be seen that a peak at 185°C, which is close to 190°C, which is the peak of I, appears, and it can be seen that at this stage, the peaks of polyester a and nylon 11 are still obtained. (The value of the corresponding melting point ■ is shown in brackets [ ] in the figure. It is the same in each attached figure). From FIG. 1(a), it can be seen that copolymerization did not progress much in the 1 hour reaction. Subsequently, the normal pressure reaction was carried out, and a similar measurement was carried out after 4 hours, and it was found that the resulting resin was transparent and had a melting point I of 133.
A single peak at °C was obtained (the data after 4 hours was
(See figure (d)). It can be seen here that copolymerization has proceeded. The measurement results for the 2-hour reaction and the 3-hour reaction during this period are shown in FIGS. 1(B) and 1(C), respectively. Furthermore, even after the glycol was distilled off under reduced pressure of 5 Q Hg and the reaction was carried out for 1 hour to increase the molecular weight, a resin with almost the same quality was obtained (see FIG. 1 (e)). These results are shown in Table 1. Example-2 As Example-2, the amount of ethylene glycol in Example-1 was changed from 3 parts by weight to 10iii parts, and the other changes were as in Example-2.
Polyesteramide was obtained in the same manner as in Example 1. Figure 2 (
A) shows the results of differential scanning calorimetry after reaction at normal pressure and 240° C. for 1 hour. Figure 2 (a) and the above embodiment-
A comparison with FIG. 1 (a) of Example 1 shows that in this example, a single peak has already appeared at this stage, indicating that copolymerization is progressing. Therefore, this shows that copolymerization was promoted by increasing the amount of glycol. Figure 2 (b) and (c) are shown at normal pressure and 240°C, respectively.
When the reaction was carried out for 4 hours, and subsequently in Example-1
The measurement results are shown when the reaction was carried out at 240° C. for 1 hour under the same reduced pressure.

In both cases, it was found that the copolymerization reaction was progressing, and the polymerization reaction was progressing extremely well.

Example 3 As Example 3, polyesteramide was obtained by changing the amount of ethylene glycol to 20 parts by weight.

Figure 3 (A) shows normal pressure and 240°C for 1 hour, Figure 3 (B) shows the same 4 hours, and Figure 3 (C) continues under reduced pressure for 24 hours.
The measurement results obtained when the reaction was carried out at 0°C for 1 hour are shown. The results show that copolymerization is significantly promoted by increasing the amount of glycol, and that the degree of reactivity, that is, the degree of blocking, can be controlled by changing the reaction time under normal pressure and by changing the amount of glycol.

It is also found that the physical properties can be stabilized by the reaction under reduced pressure.

Comparative Example-1 Here, the reaction was carried out without adding glycol, but in the same manner as in Example-1 (that is, when the raw materials of Example-1 except glycol were used). The peak temperatures of polyester a and nylon 11 appear at the peak temperatures of the differential scanning calorimetry curves shown in Figure 5 (a), (b), and (c), respectively, which indicates that the two do not react sufficiently. Recognize. In addition, phase separation of nylon and coloration due to thermal decomposition were observed.

Example-4 Under the same synthesis conditions as polyester a of Example-1, 45 mol of dimethyl terephthalate, 55 mol of isophthalic acid,
1. Using 200 mol of 4-butanediol as a raw material, 45 mol of terephthalic acid residue, 55 mol of isophthalic acid residue, 1
．． A polyester consisting of 100 moles of 4-butanediol residue and having a reduced viscosity of 0.5 was synthesized. To 220 parts by weight of this polyester, 92 parts by weight of nylon 11, which corresponds to 50 molar equivalents, and 1. 10 parts by weight of 4-butanediol was allowed to coexist, and the reaction was carried out at normal pressure and 240°C for 1 hour, and then the reaction was carried out for 3 hours under a reduced pressure of 5 Hg. The physical properties and adhesive performance of the resulting resin were measured. The results are shown in Table 2. As is clear from Table 2, this produced resin has no color and is heated at 200°C under nitrogen gas.
Even after aging by heating for 5 hours, it exhibited a stable melting point and excellent adhesive performance. In addition, the adhesiveness shown in Table 2 was evaluated as follows. That is, the resulting resin was heat-pressed into a 100μ thick sheet, then sandwiched into a commercially available canvas, and heat-pressed to form a sheet of 170'CX 1m1.
This adhesive piece was cut into 25u width, and the normal strength at 23℃ and 80
The hot strength at °C and the strength after one week of toluene immersion were measured and expressed in 'g'f/25 am.

At this time, the tensile speed was 200 w/n+in.

Examples 5 and 6, Comparative Examples 2 to 5 Example 5 was prepared under the same conditions as Example 4 except that the isophthalic acid in the polyester component was replaced with sepatic acid. Further, in Example 4, 1,4-butanediol was used in an amount of 30 parts by weight, and the polymerization conditions were changed to normal pressure reaction at 240° C. for 2 hours to accelerate the reaction, which was designated as Example 6. This example-6
On the other hand, Example 7 was carried out in which the isophthalic acid of the polyester component was changed to sepatic acid. The results are shown in Table 2.

In addition, in the polymerization step of the polyester used in Example 4, ω-aminoundecanoic acid, which is a monomer of nylon 11, was allowed to coexist with the polyester monomer in an amount corresponding to the added amount of nylon 11, and polymerized it. Similarly, Comparative Example 3 was obtained by polymerizing ω-aminoundecanoic acid in the coexistence of the monomer in Example 5. Also, comparative examples-2 and 3
Similarly, Comparative Examples 4 and 5 were prepared in which nylon 11 was allowed to coexist with the monomer at the polyester polymerization stage. These results are also summarized in Table 2.

As can be understood from Table 2, compared to Comparative Examples 2 and 3 synthesized from monomers, Examples 4 and 5 had a higher degree of blocking, so they had higher melting points, no coloration, and after aging at 200°C for 5 hours. The melting point was also stable and high adhesive strength was obtained.

In Examples 6 and 7, by increasing the amount of glycol and extending the normal pressure reaction time, melting points equivalent to those of Comparative Examples 2 and 3 synthesized from monomers were obtained, and the resulting resins were less colored.

At this time, as confirmed by the aforementioned H' NMR,
The resins produced in Examples 4 to 7 and Comparative Examples 2 and 3 had the same constituent units of the respective monomers calculated from the polyester component and the polyamide component.

In Comparative Examples 4 and 5, nylon 11 underwent phase separation and no polymerization product was obtained.

Examples-8 to 17 In the same manner as in Example-1, dimethyl terephthalate 10
A so-called polyethylene terephthalate, which is a polyester consisting of 100 moles of terephthalic acid residues and 100 moles of ethylene glycol residues synthesized from 0 moles of ethylene glycol and 200 moles of ethylene glycol, was produced. On the other hand, nylon 6 (Ube Industries) or nylon 6.6 (Ube Industries)
+1) or nylon 11 and ethylene glycol or polytetramethylene glycol (PTMG, several thousand equivalents MMN = 2000) were added as shown in Table 3, reacted at normal pressure, and continued at 24.0 ° C. for 2 hours. 5 mm
The reaction was carried out at 240° C. for 3 hours under reduced pressure with Hg (Examples 8-13, see Table 3). Table 3 shows the results of measuring the appearance, reduced viscosity, and melting point I.

Similarly, as a polyester component, terephthalic acid residue 10
Example 2 shows the case where a resin was obtained using so-called polyethylene terephthalate consisting of 0 mol and 100 mol of 1,4-butanediol residues, nylon 6 as the polyamide, and 1,4-butanediol as the glycol.
I went there as 14.

Furthermore, a composition consisting of polyester a used in Example-1 and nylon 6 or copolymerized nylon (Buratamide H005゜Nippon Rilsan side), or dimer acid polyamide (Persalon 1165゜Henkel Hakusui side), and ethylene glycol was used. Examples 15 to 17 are the cases in which the resulting resins were obtained.

The above results are also shown in Table 3.

As understood from Table 3, good polyesteramides with little coloring were obtained in all cases. Further, according to the present invention,
It can be seen that good polymers can be obtained even in reactions below the melting points of polyester and polyamide.

(c) Effects of the Invention As described above, according to the method for producing polyesteramide of the present invention, various constituent monomers can be selected from a wide range, unlike the conventional method. Moreover, a polymer with little coloring can be synthesized very easily. Furthermore, desired physical properties can be easily obtained by controlling the reaction, and for example, different resin physical properties can be freely selected even if the monomer composition is the same. This has made it possible to produce new polyesteramides. Therefore, the present invention provides molding materials in which polyester and polyamide have been conventionally used,
It can be effectively used in various industrial fields including adhesives and coatings, and can produce excellent effects.

[Brief explanation of the drawing]

1 to 3 are differential scanning calorimetry curves for explaining the present invention in detail, and FIGS. 4 and 5 are differential scanning calorimetry curves for explaining the raw material and comparative example, respectively. Figure 11: 1 FII 3 lines (command Ikuku Zqt beak together) Figure 2: Footwork 1 song 1 line

Claims (1)

[Claims] 1. A method for producing polyesteramide, which comprises heating and reacting polyester and polyamide in the coexistence of glycol.