JPH0477526A - Polyamide-imide elastomer - Google Patents

Abstract

PURPOSE:To obtain the subject elastomer excellent in heat resistance and transparency by reacting a reaction product between a >= trivalent aromatic polycarboxylic acid, an organic diisocyanate and caprolactam with a glycol such as polyoxyalkylene glycol. CONSTITUTION:(A) A hard segment composed of a polyamide-imide residue synthesized from a tri- or tetra-valent aromatic polycarboxylic acid (anhydride), an organic diisocyanate and caprolactam, containing imide ring-containing constituting units derived from an organic diisocyanate or caprolactam and an aromatic polycarboxylic acid (anhydride) and its carboxylic group-containing terminal-constituting unit and having >=500 number-average molecular weight is made to react with (B) a glycol constituting a soft segment, e.g. a polyoxyalkylene glycol or alpha,omega-dihydroxyalkylene each having 500-4,000 number- average molecular weight to obtain the objective elastomer containing the components (A) and (B) in weight ratio of (15:85) to (70:30) and having >=1.5 relative viscosity measured in 0.5g/dl m-cresol at 30 deg.C and <=75% Haze number in 1mm section thickness.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel polyamide-imide elastomer having heat resistance and transparency, and more specifically, to molding materials that particularly require flexibility and transparency, such as hoses. A flexible and transparent polyamide-imide with high strength and excellent heat resistance, including a hard segment made of polyamide-imide suitable as a material for tubes, sheets, etc., and a soft segment made of polyoxyalkylene glycol, #-dihydroxy hydrocarbon, etc. It concerns elastomers.

Conventional technology In recent years, thermoplastic elastomers such as polyamide elastomers and polyester elastomers have been developed with water resistance, heat resistance,
Because they have excellent physical properties such as mechanical strength and low-temperature properties, and are easy to mold and can be expected to improve productivity, they are rapidly beginning to be used in applications such as industrial parts, sheets, and hoses.

Among the thermoplastic elastomers, polyether ester amide type and polyether amide type are known as polyamide elastomers, and nylons such as 12-nylon and 6-nylon are used as the polyamide component. Currently, 12-nylon-based fabrics are mainly used. On the other hand, as the polyether component, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, a mixture thereof, a block copolymer, etc. are used, but among these, water resistance, mechanical strength, low temperature Polyoxy/tetramethylene glycol is mainly used because of its properties.

As a polyamide elastomer made of polyoxytetramethylene glycol as a polyether component, for example, as a hard segment, the number of carbon atoms between the amide groups is 4.
~14 elastomer using polyamide (Special Publication No.14
-45419 Publication, Special Publication No. 58-11459)
, an elastomer using polyamide with 9 or more carbon atoms between amide groups as a hard segment (Japanese Patent Publication No. 57-2
4808), an elastomer using polycapramide derived from ε-aminocaproic acid as a node segment (Japanese Patent Application Laid-open No. 58-21095), etc. have been proposed.

By the way, compatibility between polyamide and polyoxytetramethylene glycol is low, particularly between polyamide with a high amide density, such as 6-nylon, and polyoxytetramethylene glycol.

This compatibility decreases as the molecular weight of both increases,
During polymerization, phase separation occurs, and the resulting polyamide elastomer is milky white and opaque, and has poor mechanical strength. Therefore, when 6-nylon is used as a hard segment, it is difficult to obtain a transparent and strong polyamide elastomer using the above method.

On the other hand, 12-nylon, which has a low amide density, is relatively compatible with polyoxytetramethylene glycol, and has improved transparency and arcuateness compared to when 6-nylon is used. Transparent or semi-transparent materials are also available. However, when the content of polyamide constituting the hard segment is lowered in order to create a flexible elastomer with low hardness, the cohesive force of the polyamide domain decreases rapidly, leading to a decrease in mechanical strength and heat resistance with a low melting point. It becomes something inferior to. For this reason, the 12-nylon polyamide elastomers that have been put into practical use so far have mainly been relatively hard, with a Shore' hardness of 40D to 70D, and are flexible, tough, transparent, and heat resistant. A 12-nylon polyamide elastomer with excellent properties has not yet been known.

On the other hand, in order to increase the compatibility during polymerization and improve the heat resistance of the resulting elastomer, aminocarboxylic acid, trimellitic anhydride, and polyether diamine are reacted to form an imide bond or bond between the hard segment and the soft segment. An elastomer linked by amide bonds has been proposed (Japanese Patent Application Laid-open No. 158222/1983). However, in this method, polyether diamine as a raw material is difficult to obtain, and production requires complicated steps, so it is inevitably disadvantageous in terms of cost.

In addition, compatibility was improved by simultaneously reacting caprolactam, polyoxytetramethylene glycol, and dicarboxylic acid and polymerizing while maintaining the water content in the reaction system at 0.1-1.0% by weight. Transparent and tough elastomers have also been proposed (Japanese Patent Application Laid-Open No. 61-247732).
Although this material has been improved in terms of flexibility, it cannot necessarily be said to be sufficient in terms of heat resistance.

By the way, when polyamide elastomer is used as a resin modifier, which is one of its main uses, it is required to have heat resistance, be easy to knead, and have good flowability during injection molding. For this reason, it is necessary to change the melting point or crystallization temperature of the elastomer depending on the partner resin, but such a polyamide elastomer has not been known so far.

Therefore, it is of extremely industrial value to obtain a polyamide elastomer with excellent transparency, mechanical strength, heat resistance, and resin modifiability by using caprolactam, which is industrially easily available and inexpensive, as the main polyamide component. Despite the high cost, the current situation is that it has not yet been realized.

Problems to be Solved by the Invention Under these circumstances, the present invention provides a bivalent transparent resin containing caprolactam as the main amide component, which has flexibility, mechanical strength, heat resistance, and resin modification properties. This was developed with the aim of providing a polyamide-based elastomer.

Means for Solving the Problems As a result of intensive research to develop a polyamide elastomer having such favorable properties, the present inventor has discovered that
Caprolactam, a trivalent or tetravalent aromatic carboxylic acid capable of forming at least one imide ring or its acid anhydride, and a polyamide imide residue containing an imide ring obtained from an organic diisocyanate compound and a polyoxyalkylene glycol or α , and glycol residues such as ω-dihydroxyalkylene, and having a specific relative viscosity and haze number, was found to be suitable for the above purpose, and based on this knowledge, the present invention was completed. I came to the conclusion.

That is, the present invention provides a polyamide-imide residue formed by the reaction of (A) a trivalent or tetravalent aromatic polycarboxylic acid or its anhydride, an organic diisocyanate, and caprolactam, which contains the organic diisocyanate. Alternatively, f: a hard segment derived from the caprolactam and the aromatic polycarboxylic acid or its acid anhydride and having a number average molecular weight of 500 or more and having an imide ring-containing structural unit and a carboxyl group-containing terminal structural unit, and (B) a number average molecular weight 500 to 4,000 polyoxyalkylene glycol and α,ω-dihydroxyalkylene, and comprises (A) component and (B) fc
weight ratio of 15:85 to 70:30, 0.5 g/dQ in m-cresol, relative viscosity measured at 30°C of at least 1.5, haze number at wall thickness of 1 m11 not more than 75%. The present invention provides a polyamideimide nylastomer characterized by:

The polyamide-imide elastomer of the present invention is composed of a hard segment having a polyamide-imide structure and a soft segment having a polyol structure.

This hard segment with polyamide-imide structure is
An imide derived from caprolactam, a trivalent or tetravalent aromatic polycarboxylic acid or its anhydride, and an organic diisocyanate, and formed by the reaction of the polycarboxylic acid or its anhydride, the organic diisocyanate, or caprolactam. It contains a ring-containing structural unit and a carboxyl group-containing terminal structural unit derived from an aromatic polycarboxylic acid or its anhydride or caprolactam.

Therefore, it is necessary that at least two carboxyl groups in the aromatic polycarboxylic acid to be removed be bonded to adjacent carbon atoms of the aromatic ring. The imide ring is formed not only by the reaction of this aromatic polycarboxylic acid with an organic diisocyanate but also by the reaction with caprolactam.

When forming an imide ring preferentially with caprolactam, the aromatic polycarboxylic acid and part of the caprolactam are reacted in advance, and then the remaining caprolactam is reacted with the organic diisocyanate. On the contrary, organic diisocyanate,
, i, and - to form an imide ring, the aromatic polycarboxylic acid and the organic diisocyanate compound may be reacted first and then reacted with caprolactam.

When caprolactam, an organic diisocyanate compound, and an aromatic polycarboxylic acid are reacted simultaneously, a structure is formed in which the nitrogen atoms of the imide ring coexist with those derived from caprolactam and those derived from the organic diisocyanate.

Examples of the trivalent aromatic polycarboxylic acid used to form this hard segment include 1.2.4-trimellitic acid, 1,2.5-naphthalene tricarboxylic acid, and 2.6-trimellitic acid.
．． 7-su7talenttricarboxylic acid, 3,3',4-diphenyltricarboxylic acid, benzophenone-3,3',4
-tricarboxylic acid, diphenylsulfone-3,3',4
-1-ricarponic acid, diphenyl ether-3,3',
4-) Ricarboxylic acid, etc., and examples of tetravalent aromatic polycarboxylic acids include pyromellitic acid,
diphenyl-2,2',3,3'-tetracarboxylic acid,
Benzophenone-2,2', 3.3'-tetracarboxylic acid, diphenylsulfone-2,2', 3.3'-tetracarboxylic acid, diphenyl ether-2,2', 3.3'
-tetracarboxylic acids and the like. In the present invention, these polycarboxylic acids can also be used as acid anhydrides.

The aromatic polycarboxylic acid or its anhydride is used in a proportion of at least 2 moles per mole of organic diisocyanate. If the amount is less than this, there will be a shortage of carboxyl groups necessary to react with the glycol component forming the soft segment, making it impossible to obtain the desired polyamideimide elastomer.

On the other hand, examples of organic diisocyanate compounds that react with these aromatic polycarboxylic acids or their anhydrides to form an imide ring include hexamethylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate. One type of these organic diisocyanate compounds may be used, or two or more types may be used in combination. This organic diisocyanate is
0 during hard segment. It is desirable to use it in a proportion of 1 to 1 mole of O. The hard and soft segments are chosen so that substantially l=1. Therefore, setting the organic diisocyanate to 0.01-1 mol in the hard segment means that the molar ratio of organic diisocyanate to glycol is from 1:100 to 1:1.
It will be selected so that. If the amount is more than this, it is not preferable because the coloring will be strong or the melting point will be too low, although it will vary depending on the type of the diisocyanate compound, and if it is less than this, the effect will not be fully exhibited.

Thus, organic diisocyanates, caprolactam,
When a trivalent or tetravalent aromatic carboxylic acid or its anhydride is used as a component, an imide ring is introduced into the node segment, which improves heat resistance and also adds a heterogeneous structure based on an organic diisocyanate to the polyamide structure. The cohesive strength of the polyamide portion decreases, resulting in a lower melting point.

As a result, the molding temperature can be lowered, and when used as a resin modifier, there are advantages such as a wider range of cross-wire conditions. Furthermore, since the crystallization temperature is lowered by increasing the amount of the organic diison atomite, flowability during injection molding can be improved.

The hard segment of the polyamideimide elastomer of the present invention, that is, the (A) portion, is derived from a unit represented by the formula %) derived from caprolactam and a trivalent or tetravalent aromatic polycarboxylic acid or its anhydride. (In the formula, Ar and Ar2 are residues having an aromatic nucleus. It has a structure without a branch consisting of units represented by (residues excluding groups) and has a number average molecular weight of 500 or more, preferably in the range of 500 to 3,000.

This number average molecular weight is calculated from the charging composition and the amount of caprolactam recovered during polymerization. If it is less than 500, the cohesive force of the hard domain will decrease, resulting in a decrease in mechanical strength. and transparency is compromised.

In the polyamideimide elastomer of the present invention, the hard segment residues include an average of 3 to 25 structural units derived from caprolactam, an average of 1.01 to 2 structural units derived from an aromatic polycarboxylic acid or anhydride thereof, It is preferable that the composition contains 0.01 to 1 structural unit derived from an organic diisocyanate.

On the other hand, the soft segment, that is, the (B) portion in the polyamideimide elastomer of the present invention is derived from at least one glycol selected from polyokinoalkylene glycol and σ, ω-dihydroxyalkylene having a number average molecular weight of 500 to 4000. It is a residue that

Examples of the polyoxyalkylene glycol include polyquine tetramethylene glycol, modified polyoxytetramethylene glycol, polyoxypropylene glycol, polyoxyethylene glycol, and copolymerized glyfurs thereof.

When polyoxytetramethylene glycol is used as the glycol component, its number average molecular weight is 4000.
If it exceeds , the low temperature properties will be poor.

In particular, when only polyoxythietramethylene glycol is used as the soft segment, it is preferable to use one having a number average molecular weight of 500 to 3,000 from the viewpoint of low-temperature properties. Furthermore, from the viewpoint of low-temperature properties, the molecular weight distribution Mvis/Mn (u
n is the number average molecular weight determined from the terminal hydroxyl group value;
It is preferable to use a sharp one of 6 or less.

In the present invention, modified polyoxytetramethylene glycol can also be used instead of the above-mentioned polyoxytetramethylene glycol. Examples of the modified polyoxytetramethylene glycol include ordinary polyoxytetramethylene glycol in which a part of -(cHx)a-0- is replaced with -R-0-. Here, R is an alkylene group having 2 to 10 carbon atoms, and specifically, ethylene group, 1,2-propylene group, 1,3-propylene group, 2-methyl-1,3-propylene group, 2.2 Preferred examples include -dimethyl-1,3-propylene group, pentamethylene group, and hexamethylene group. There are no particular restrictions on the modified layer, but it is usually selected within the range of 3 to 50% by weight. In addition, the amount of modification and the type of alkylene group are as follows:
It is appropriately selected depending on the required properties of the elastomer, such as low-temperature properties, heat resistance, and weather resistance.

This modified polyoxytetramethylene glycol can be produced, for example, by copolymerization of tetrahydrofuran and a diol using a heteropolyacid as a catalyst, or by copolymerization of a cyclic ether that is a diol or a condensation product of a diol and butanediol.

When imparting hydrophilicity to the elastomer of the present invention, polyoxyethylene glycol can be used, and depending on the hydrophilicity, it can be used alone or in combination with polyoxytetramethylene glycol or the like.

As the a8ω-dihydroxyalkylene, for example, polyolefin glycol or hydrogenated polybutash glycol obtained by polymerizing a hydrocarbon such as olefin or butadiene, converting the terminal to a hydroxyl group, and hydrogenating the double bond, etc. may be used. The number average molecular weight of these hydrocarbon polymers must be in the range of 500 to 4,000.

If the number average molecular weight is less than 500, the resulting elastomer may have a low melting point or may not have excellent physical properties. On the other hand, if it exceeds 4,000, the number of reaction points will decrease, resulting in a high molecular weight. elastomer becomes difficult to obtain.

The glycols used in the present invention may be used alone or in combination of two or more.

The type, molecular weight, and ratio of the glycol used are appropriately selected in consideration of various physical properties of the elastomer, such as low-temperature properties, weather resistance, and oil resistance.

Further, the glycol component needs to be used so that the soft segment content in the polyamideimide elastomer is 30 to 85% by weight, and this amount is 30 to 85% by weight.
If the amount is less than 85% by weight, the flexibility and transparency of the polyamide-imide elastomer will be impaired, and if it exceeds 85% by weight, the strength will decrease. The hardness of this polyamide-imide elastomer can be controlled mainly by the content of the polyamide-imide component. In particular, by adjusting the polyamideimide component in the elastomer to 15 to 45% by weight, a flexible and tough elastomer having a Shore hardness of 60A to 40D in the vulcanized rubber range can be obtained.

The polyamideimide elastomer of the present invention has a relative viscosity of 1.5 or more when measured at a temperature of 30°C at a concentration of 0.59/d12 in m-cresol, and a wall thickness of 1.
It is necessary that the haze number measured in mm is 75% or less.

Although polyamide imide dicarboxylic acid and polyoxyalkylene glycol or α,ω-dihydroxy hydrocarbon lack compatibility, homogeneous polymerization of both produces a transparent elastomer without turbidity.

Therefore, the above-mentioned haze number in the present invention is also an indicator of whether or not homogeneous polymerization is being carried out.When this haze number exceeds 75%, turbidity occurs, transparency decreases, and the homogeneity of polymerization is lost. There is a tendency for the strength to decrease due to

In order to produce the polyamide-imide elastomer of the present invention, it is preferable to polymerize under conditions that allow the polyamide-imide component and the glycol component to become compatible.

For example, first, (i) caprolactam, (ii) trivalent or tetravalent aromatic polycarboxylic acid or its acid anhydride, (
i) Organic diisocyanate and (iv) polyoxyalkylene glycol and σ, m-dihydroxyalkylene.
1i) The amount of the component and the total amount of the component (ii) and the component (iv) are mixed so that they are substantially equimolar, and the water content in the polymer is maintained at 0.1-1% by weight. While, 180~
After the reaction is carried out by heating at a temperature of about 300°C, unreacted caprolactam is removed from the reaction mixture, and if necessary, post-polymerization is further carried out at a temperature of about 200 to 300°C. In this reaction, if the reaction temperature is less than 180°C, the polymerization rate is too slow and is not practical, and if it exceeds 300°C, thermal deterioration will occur, which is not preferable.

, by simultaneously causing esterification reaction and caprolactam polymerization, and by controlling the respective reaction rates.
In order to obtain a transparent and homogeneous elastomer, the produced water is removed from the system to reduce the water content of the reaction system to 0.
．． It is necessary to maintain the amount within the range of 1-1% by weight during polymerization. When this water content exceeds 1% by weight, polymerization of caprolactam takes priority and coarse phase separation occurs, whereas when the water content is less than 0.1% by weight, esterification takes priority and caprolactam does not react, resulting in an elastomer of the desired composition. I can't get it.

Further, the water content is appropriately selected within the above range depending on the physical properties desired for the elastomer.

In the method of the present invention, a method may be adopted in which the water content in the reaction system is reduced as the reaction progresses, if desired. This moisture content can be controlled by, for example, reaction conditions such as reaction temperature, flow rate of inert gas introduced, degree of pressure reduction, or reactor structure.

In addition, as another manufacturing method, (i) component caprolactam, (...) component aromatic polycarboxylic acid, and (ii)
The component organic diisocyanate is reacted to form a polyamide imide dicarboxylic acid oligomer, and (iv)
The component glycol is condensed. At this time, it is important to make both components compatibilized; if the reaction occurs without compatibilization, homogeneous polymerization will not be possible, and the resulting polymer will be opaque and have low strength.

Component (i), caprolactam, has an affinity for both the polyamide-imide oligomer and the glycol component, so it is advantageous for commercialization. Uniform polymerization can be achieved by coexisting caprolactam with both. Since caprolactam partially reacts under such conditions, it is necessary to determine the composition of the polyamideimide dicarboxylic acid from components (i), (1i), and (ii)ff in consideration of this reaction rate.

Furthermore, as another method, components (ii) and (ij) are reacted to form imidodicarboxylic acid, which is then reacted with (
A method of reacting component i) and component (iv) can also be used.

According to these methods, the degree of polymerization of the polyamideimide elastomer can be arbitrarily changed as necessary;
In the present invention, in m-cresol, 0.5 g/dQ
At a concentration of , the relative viscosity measured at a temperature of 30°C is 1
．． It is necessary to polymerize to a molecular weight of 5 or more, preferably 1.6 or more. If the relative viscosity of the two is less than 1.5,
The polyamideimide elastomer has poor mechanical properties.

In addition, in this reaction method, an esterification catalyst can be used as a polymerization promoter, and examples of the catalyst include phosphoric acid, tetraalkyl orthotitanate such as tetrabutyl orthotitanate, tetrabutyl orthotitanate such as tetrabutyl orthotitanate, and tetrabutyl orthotitanate. Soot-based catalysts such as alkoxyzirconium, dibutyltin oxide, and dibutyltin laurate;
Manganese-based catalysts such as manganese acetate and lead-based catalysts such as lead acetate are preferably used. The catalyst may be added at the beginning of the polymerization or at the middle of the polymerization. In addition, in order to increase the thermal stability of the obtained polyamide-imide elastomer, stabilizers such as various heat-resistant anti-aging agents and antioxidants can be used. It may be added or may be added after polymerization. Examples of heat-resistant stabilizers include N,N'-hexamethylene-bis(3,5-tert-butyl-4-hydroxycinnamic acid amide), 4i4'-his(2,6-di-tert-butylphenol), 2. Various hindered phenols such as 2'-methylene his (4-ethyl-6-tert-butylphenol), N, N'-his (β-naphthyl)-p-fuylene diamine, N, N'-syl , phenyl p-phenylenediamine, aromatic amines such as holy(2,2,4-trimethyl-1,2-dihydroquinoline), copper salts such as copper chloride and copper iodide, dilaurylthiodipropionate, etc. Examples include sulfur compounds and phosphorus compounds. moreover,
The polyamideimide elastomer obtained in the present invention can optionally contain an ultraviolet absorber, an antistatic agent, a coloring agent, a filler, a hydrolysis resistance improver, and the like.

Effects of the Invention The polyamide-imide elastomer of the present invention differs from conventional ones in that it has excellent flexibility, transparency, and mechanical strength, as well as good heat resistance and resin modification properties, and has excellent transparency. It is suitably used in required applications, such as materials for hoses, tubes, sheets, etc., plastic modifiers, and 7 Otoresist base polymers.

Examples Next, the present invention will be explained in more detail with reference to examples.
The present invention is not limited in any way by these examples.

In addition, each physical property of the elastomer was determined as follows.

(1) Shore hardness was measured using a durometer in accordance with ASTM D-2240.

(2) Tensile strength at break The elastomer was formed into a sheet with a wall thickness of 1 wrm using a hot press, and dumbbell-shaped specimens were punched out in accordance with JIS K 6301, and the strength was measured using a tensile strength tester (Instron).

(3) Relative viscosity Measured in metacresol at 30°C and 0.5% by weight/volume.

(4) Thermal decomposition temperature The weight loss temperature was measured using a differential thermal balance at a heating rate of 10° C./n″c.

(5) Melting point and crystallization temperature Using a differential thermal balance, the melting point was measured at a heating rate of 10° C./min, and the crystallization temperature was determined by decreasing the temperature at a rate of 5° C./min.

(6) Haze number using a 1mm thick sheet, ASTM D 1003-6
It was measured using a haze meter according to the method based on 1.

Example 1 500 equipped with a stirrer, nitrogen inlet and distillation tube
+ii 93g of caprolactam in 2 separable flasks,
82.5 g of polyoxytetramethylene glycol (Mvis/Mn = 1.45) with a number average molecular weight of 1980,
8.8 g of trimellitic anhydride, 1.049 g of diphenylmethane diisocyanate (Millionate MT, manufactured by Nippon Polyurethane Industries, Ltd.) (diisocyanate/glycol molar ratio -0.1), N,N'-hexamethylene-bis(3, 5-di-tert-butyl-4-hydroxycinnamic acid amide) (trade name: Ilkanox 1098J antioxidant) was charged with 0.309, and nitrogen was added at 50 mQ/mi.
After melting at 150°C while flowing at
Polymerization was carried out at 'C for 4 hours. The water content in the reaction solution 1 hour, 2 hours, and 4 hours after reaching 260°C was 0.7, 0.5.043% by weight, respectively.

Next, after 0.3 h of tetrabutyl orthotitanate was added, the pressure was gradually reduced to 1 Torr to distill off 32.5 g of unreacted caprolactam from the system.

Furthermore, when polymerization was carried out for 3N at the same temperature and under a pressure of 1 Torr or less, a transparent elastomer (haze number 35%) was obtained. This elastomer has a polyoxytetramethylene glycol segment content of 54% by weight, a relative viscosity of 2.0, a melting point of 205°C, a tensile strength and elongation of 370ky/cm and 2.900%, respectively, and a Shore hardness of A and D, respectively. It was 92.34. Further, the thermal decomposition start temperature was 317°C, and the 1O% weight loss temperature was 363°C.

Example 2 90 g of polyoxyethylene glycol with a number average molecular weight of 1490, 97 g of caprolactam, and 16 g of trimellitic acid.
4g, diphenylmethane diisocyanate 4.52g (
Polymerization was carried out in the same manner as in Example 1, except that the diisocyanate/glycol molar ratio was 0.3). The water content in the polymerization system is 0.8 to 0.5% by weight.

The amount of caprolactam distilled out of the system was 24.29, and a transparent elastomer (haze number 40%) was obtained. This nilastomer has a polyoxyethylene glycol segment content of 49% by weight, a relative viscosity of 2.0,
Tensile strength and elongation are 420 to 9/cm” and 7, respectively.
50%, Shore hardness was 38. The melting point and thermal decomposition onset temperature are shown in the table.

Example 3.4 Same as Example 2 except that the molar ratio of diphenylmethane diisocyanate/polyoxyethylene glycol was changed to 0.5 (Example 3) and 0.05 (Example 4). Polymerization was carried out to obtain an elastomer having a polyoxyethylene glycol segment content of 49% by weight. Further, the haze numbers were 45% and 38%, respectively. The melting points and thermal decomposition onset temperatures of these elastomers are shown in the table.

Example 5 Anhydrous Trimerit 1119 was added to the same reactor as Example 1.
．． 6 g of diphenylmethane diisocyanate 2,2 were charged, the atmosphere was replaced with nitrogen, and the mixture was reacted at 260°C for 1 hour. A mixture of a yellow solid that did not melt at 260°C and trimellitic anhydride was obtained. The yellow solid has an IR spectrum of 1
The imide group shows absorption at 776 cm-', and the N of the amide group
Absorption of -H and isocyanate groups was not shown. Therefore, it can be seen that substantially all of the nitrogen atoms of the diisocyanate form an imide ring.

In addition, caprolactam 1469 and polyoxyethylene glycol 1 having a number average molecular weight of 1500 were added to the reaction mixture.
33.2 g and pentaerythrityl-tetrakis [3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propiosulfate] (Antioxidant Irganox 1010
) and reacted at 260°C for 4 hours while flowing nitrogen at 50 mQ/min. Next, unreacted caprolactam was distilled off under reduced pressure, and then 0.59% of tetrabutoxyzirconium was added, and the mixture was heated at 260°C.
Polymerization was carried out at 1 torr for 2 hours to obtain a pale yellow transparent polymer (haze number 36%) with a relative viscosity of 1.98. This polymer contains 54% by weight of polyoxyethylene glycol segments and has a strength of 360 kl? /cm'', elongation of 730%, and thermal decomposition onset temperature of 335°C.

Example 6 1O! equipped with a stirrer, nitrogen inlet and distillation tube! 2s
In a US reactor, 2.97J2g of caprolactam aqueous solution (caprolactam content 80% by weight) and polyethylene glycol with a number average molecular weight of 1494 were added. ookg, anhydrous trimellit rll12709, diphenylmethane diisocyanate) 17g and "Irganox" 098J
8 g were charged together, and the temperature was raised to 250°C while nitrogen was flowing at a rate of 1/min. After 1 hour and 2 hours, a small amount of the reaction solution was sampled and the water content was measured, and it was found to be 0.6% by weight. , 0.5% by weight. After polymerization for 2 hours, the pressure was gradually reduced to 1 torr to distill off 0.53 g of unreacted caprolactam from the system. Next, 8 g of tetra-n-butyl orthotitanate was added to this. Add 260
Polymerization was carried out for 5 hours at a temperature below 1 Torr. The resulting elastomer was transparent (haze number 45%), had a polyethylene glycol segment content of 48% by weight, a relative viscosity of 1.9, a melting point of 201°C, a tensile strength and an elongation of 390 to 9/cm”, respectively. 750%, and Shore hardness A and D were each 98.41.Furthermore, the thermal decomposition start temperature was 330°C.

Example 7 In the same reactor as Example 6, 2.23 kg of caprolactam,
Polyethylene glycol 2.2 with a number average molecular weight of 1980
0 kg, 224 g of trimellitic anhydride, 13.99 g of diphenylmethane diisocyanate and "Irganox 1"
1098J8 was added together and heated to 150°C to melt. Next, the temperature was raised to 250° C. under a reduced pressure of 300 Torr, and polymerization was carried out for 4 hours. After that, the pressure was gradually reduced to 1 Torr to distill off 0.64 kg of unreacted caprolactam from the system, and then tetra-n-butoxyzirconium 69 was added thereto, and the mixture was heated at 260°C for 2 hours under reduced pressure of 1 Torr or less. Polymerized. The obtained elastomer was transparent (haze number 38%), had a polyethylene glycol segment content of 55% by weight, a relative viscosity of 1.9, a melting point of 209°C, a thermal decomposition onset temperature of 327°C, and a tensile strength and elongation of 350ky
/cys 2.850%, and shear degrees A and D were 9] and 35, respectively.

Example 8: h7'o lactam 1.2OA! 9. Polymerization was carried out in the same manner as in Example 7, except that 2.804 g of polyethylene glycol (number average molecular weight 1980), 11285 g of anhydrous trimellit, and 17.79 g of diphenylmethane diincyanate were used.

The amount of unreacted caprolactam distilled off was 0.30g. The obtained elastomer had a haze number of 30%, a polyethylene glycol segment content of 70% by weight, a relative viscosity of 2.1, a melting point of 193°C, a thermal decomposition initiation temperature of 325°C, and a tensile strength and elongation of 310J11, respectively. ?
/<1:11'', 1000%, Shore hardness A and D were each 78.24.

Example 9 In Example 1, 10.0% of pyromellitic anhydride was used instead of trimellitic anhydride. b, hexamethylene diisocyanate L4y instead of diphenylmethane diisocyanate
Polymerization was carried out in the same manner as in Example 1, except that .

During this period, the water content in the polymerization system was 0.3 to 0.6% by weight,
A transparent (haze number 50%) elastomer was obtained.

This nilastomer contains 55% by weight of polyoxytetramethylene glycol segments, has a melting point of 206°C, a thermal decomposition onset temperature of 323°C, a tensile strength of 350ky/cta",
The elongation was 920% and the Shore hardness was D37.

Example IO In place of the polyoxytetramethylene glycol of Example 1, a saturated polyolefin glycol with a number average molecular weight of 2200 (manufactured by Mitsubishi Kasei Corporation, trade name Polytail HA) was used.
Containing 57% by weight of polyolefin glycol segments in the same manner as in Example 1 except that 91.7g was used.
Melting point 205°C1 Pyrolysis start temperature 32piC1 Tensile strength 2
A transparent elastomer (Heiss number 37%) having a hardness of D35 and an elongation of 830% was obtained.

Example 11 500m equipped with a stirrer, nitrogen inlet, and distillation pipe
12 In a separable flask, 23.1 g of trimellitic acid
, 2.5 g of diphenylmethane diisonate, 9 g of caprolactam 104, [Irganox IOIO
Prepared with 3g of JO0, replaced with nitrogen, and heated at 260°C for 4 hours.
After a period of reaction, a polyamideimide oligomer was obtained.

In a similar apparatus, 44 g of the oligomer and 3 caprolactam were added.
2.7 g and 50.09 of polyoxyethylene glycol with a number average molecular weight of 1490 were charged, and nitrogen was introduced at 50 mQ/m.
After reacting at 260° C. for 2 hours while flowing in the mixture, 27.8 g of unreacted caprolactam was distilled off under reduced pressure. Next, 2 g of tetrabutyl orthotitanate was added and polymerized at 260° C. and 1 Torr for 2 hours until the relative viscosity was 1.
A pale yellow transparent polymer (haze number 43%) was obtained. This polymer shows imide absorption in the IR spectrum and has 50% by weight polyoxy/ethylene glycol segments.
It was a polyamideimide elastomer containing 370 hg/cm2 in strength and 750% in elongation. From IR spectrum and NMR measurements, this was found to be a polyamideimide elastomer similar to the polymer of Example 2.

Example 12 500m equipped with a stirrer, nitrogen inlet, and distillation tube
In a C separable flask, add 78% polyoxyethylene glycol having a number average molecular weight of 1490. h and 11.1 g of trimellitic anhydride, "Irganox I098JO13
After melting at 150°C while flowing nitrogen at 50 rn (1/min), melt at 260°C for 1
Time reacted. A colorless and transparent viscous liquid oligomer was obtained, and it was confirmed from the IR spectrum that the acid anhydride group had disappeared and ester bonds had been formed.

Next, caprolactam 9 was added to this oligomer at 100°C.
L79 and 1.3 g of diphenylmethane diisocyanate were added, the temperature was raised to 260°C, and the mixture was reacted at 260°C for 4 hours. Next, after removing unreacted caprolactam under reduced pressure, 0.3 g of tetrabutyl orthotitanate was added and polymerized at 260°C and 1 Torr, resulting in a rapid increase in viscosity, reaching a relative viscosity of 2.1 in 45 minutes. of polymer was obtained. This polymer was pale yellow and transparent with a haze number of 46%, and was found to be a polyamideimide elastomer similar to Example 2 from IR spectrum and NMR measurements. Also,
This polymer had a polyoxyethylene glycol segment content of 56% by weight, a strength of 30,072 g/C, and an elongation of 950%.

Tokken Applicant: Asahi Kasei Kogyo Co., Ltd. Dai, Rijin-a shape Akira (2 others)

Claims (1)

[Scope of Claims] 1 (A) A polyamideimide residue formed by the reaction of a trivalent or tetravalent aromatic polycarboxylic acid or its anhydride, an organic diisocyanate, and caprolactam,
A hard segment having a number average molecular weight of 500 or more and having an imide ring-containing structural unit and a carboxyl group-containing terminal unit derived from the organic diisocyanate or the caprolactam and the aromatic polycarboxylic acid or its acid anhydride; B) is composed of a soft segment consisting of a residue of a glycol selected from polyoxyalkylene glycol and α,ω-dihydroxyalkylene with a number average molecular weight of 500 to 4000, and is composed of components (A) and (B). weight ratio of 15:85 to 70:30, 0.5 g/dl in m-cresol, relative viscosity measured at 30°C of at least 1.5, haze number at 1 mm wall thickness of 75%
A polyamideimide elastomer characterized by: 2. The hard segment is formed by the reaction of at least 2 moles of the aromatic polycarboxylic acid or its anhydride per mole of the organic diisocyanate, and 3 to 25 moles of caprolactam per mole of the aromatic polycarboxylic acid or its anhydride. The polyamideimide elastomer according to claim 1. 3. The polyamide-imide elastomer according to claim 1 or 2, wherein the molar ratio of the organic diisocyanate forming the hard segment to the glycol forming the soft segment is 1:1 to 1:100.