JPH085943B2 - Method for producing polyamide-imide elastomer - Google Patents

Description

TECHNICAL FIELD The present invention relates to an improvement in a method for producing a polyamideimide elastomer having heat resistance and transparency.
More specifically, the present invention relates to a molding material particularly required to have flexibility and transparency, for example, a hard segment made of polyamideimide suitable as a material for hoses, tubes, sheets and the like, polyoxyalkylene glycol and α, The present invention relates to a method for efficiently producing a flexible and transparent polyamide-imide elastomer having high strength and heat resistance, which contains a soft segment composed of ω-dihydroxy hydrocarbon.

2. Description of the Related Art In recent years, thermoplastic elastomers such as polyamide elastomers and polyester elastomers have excellent physical properties such as water resistance, heat resistance, mechanical strength, and low temperature characteristics, and they are easy to mold and can be expected to improve productivity. Therefore, it is rapidly being used for industrial parts, seats, hoses and the like.

Among the thermoplastic elastomers, as the polyamide elastomer, polyether ester amide type and polyether amide type are known, and nylon such as 12-nylon or 6-nylon is used as the polyamide component. Currently, 12-nylon type is mainly on the market. On the other hand, as the polyether component, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol or a mixture thereof or a block copolymer is used, among which water resistance, mechanical strength, low temperature Polyoxytetramethylene glycol is mainly used because of its properties.

As a polyamide elastomer composed of this polyoxytetramethylene glycol as a polyether component,
For example, as a hard segment, an elastomer using polyamide having 4 to 14 carbon atoms between amide groups (Japanese Patent Publication No. 56-
45419, Japanese Patent Publication No. 58-11459), an elastomer using a polyamide having 9 or more carbon atoms between amide groups as a hard segment (Japanese Patent Publication No. 57-24808), and ε-aminocaproic acid as a hard segment. Elastomer using polycapramide derived from
-21095 gazette) etc. are proposed.

By the way, polyamide and polyoxytetramethylene glycol have low compatibility, and particularly polyamide having high amide density, for example, 6-nylon and polyoxytetramethylene glycol have low compatibility. This compatibility becomes lower as the molecular weights of the both become larger, and coarse phase separation occurs during polymerization, and the polyamide elastomer produced becomes opalescent and opaque and inferior in mechanical strength. Therefore,
When 6-nylon is used as the hard segment, it is difficult to obtain a transparent and high-strength polyamide elastomer by 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 strength as compared with the case of using 6-nylon. You will also be able to obtain translucent ones. However, when the content of the polyamide that constitutes the hard segment is reduced to make it a soft elastomer with low hardness, the cohesive force of the polyamide main is drastically reduced, resulting in a material with low mechanical strength or heat resistance with a low melting point. Will be inferior to. For this reason, the 12-nylon polyamide elastomers that have been practically used so far are mainly composed of relatively hard Shore hardness of 40D to 70D, and are flexible and excellent in all of toughness, transparency and heat resistance. 12-nylon-based polyamide elastomers are not yet known.

On the other hand, in order to increase the compatibility at the time of polymerization and improve the heat resistance of the obtained elastomer, an aminocarboxylic acid, a trimellitic anhydride and a polyetherdiamine are reacted to form an imide bond or a hard segment and a soft segment. An elastomer linked by an amide bond has been proposed (JP-A-60-158222). However, in this method, the starting material poly-ether diamine is difficult to obtain, and a complicated step is required to manufacture it, which makes industrialization difficult, and inevitably causes a cost disadvantage.

Further, by reacting caprolactam, polyoxytetramethylene glycol and dicarboxylic acid at the same time, and polymerizing while maintaining the water content in the reaction system at 0.1 to 1.0% by weight, compatibility is improved, and it is transparent and tough. Although various elastomers have been proposed (JP-A-61-247732 and JP-A-62-70422), this one is improved in flexibility but not necessarily sufficient in heat resistance. Not really.

By the way, when a polyamide elastomer is used as a resin modifier, which is one of its main uses, it is required to have heat resistance, be easily kneaded, and have good flowability during injection molding. Therefore, depending on the partner resin,
It is necessary to change the melting point or crystallization temperature of the elastomer, but hitherto no such polyamide elastomer has been known.

Therefore, it is extremely industrially valued to obtain a polyamide elastomer which is industrially easily available and inexpensive and which is excellent in transparency, mechanical strength, heat resistance and resin modification property, using caprolactam as a main polyamide component. Despite the high price, it has not been realized yet.

SUMMARY OF THE INVENTION Under the circumstances, the present invention contains caprolactam as a main amide component, and has flexibility, mechanical strength,
The purpose of the present invention is to provide a transparent polyamide elastomer having excellent heat resistance and resin modifying property.

Means for Solving the Problems As a result of intensive studies to develop a polyamide-based elastomer having such preferable properties, the present inventor has found that a trivalent trivalent group capable of forming caprolactam and at least one imide ring in a specific ratio. Alternatively, a tetravalent aromatic carboxylic acid or an acid anhydride thereof and an organic diisocyanate compound and a polyoxyalkylene glycol or α, ω-dihydroxy hydrocarbon are polymerized under specific conditions,
Polyamideimide containing an imide ring obtained from caprolactam and the aromatic polycarboxylic acid or its acid anhydride and an organic diisocyanate is used as a hard segment, and a polyamideimide elastomer having the glycol as a soft segment is obtained. They have found that they can meet the above-mentioned purposes, and have completed the present invention based on this finding.

That is, the present invention provides (A) captolactam, (B)
Trivalent or tetravalent aromatic polycarboxylic acid or acid anhydride thereof capable of forming at least one imide ring, (C) organic diisocyanate compound, and (D) number average molecular weight 500
~ 4000 polyoxyalkylene glycols and α, ω-
At least one glycol selected from dihydroxy hydrocarbons is represented by the formula as well as (However, b, c and d are the components (B),
(C) and (D) indicate the number of moles of component) are mixed in such a ratio as to satisfy the relationship, and water produced in the reaction is removed to the outside of the system so that the water content of the reaction system is 0.1 to 1% by weight.
While polycondensation is carried out at a temperature of 180 to 280 ° C., unreacted caprolactam is removed, and if necessary, post-polymerization is carried out under reduced pressure at a temperature of 200 to 300 ° C. A manufacturing method is provided.

 Hereinafter, the present invention will be described in detail.

In the method of the present invention, the amount of caprolactam used as the component (A) of the raw material is not particularly limited, but in order to obtain a transparent, excellent heat resistance and tough elastomer, based on the weight of the elastomer, Advantageously, it is used in a proportion of 10 to 65% by weight, preferably 20 to 60% by weight. The amount of caprolactam used is appropriately selected depending on the hardness and other physical properties of the intended elastomer, or the composition and molecular weight of the soft segment used.

The hard segment of the polyamide-imide elastomer in the present invention is composed of (A) component caprolactam and (B)
Derived from a polyamideimide dicarboxylic acid formed by the reaction of a trivalent or tetravalent aromatic polycarboxylic acid or its acid anhydride capable of forming at least one imide ring of the component and an organic diisocyanate compound of the component (C) It At this time, at least two of the three carboxyl groups of the trivalent aromatic polycarboxylic acid, that is, the aromatic tricarboxylic acid, are bonded to adjacent positions of the aromatic ring, and are reacted with caprolactam or an organic diisocyanate compound to give 1 Must be able to form imide rings, and the four carboxyl groups of a tetravalent aromatic polycarboxylic acid, that is, an aromatic tetracarboxylic acid,
Two of each should be bonded to adjacent positions of the aromatic ring and capable of forming two imide rings by reaction with a caprolactam or an organic diisocyanate compound.

Examples of such an aromatic tricarboxylic acid include 1,
2,4-trimellitic acid, 1,2,5-naphthalenetricarboxylic acid, 2,6,7-naphthalenetricarboxylic acid, 3,3 ′, 4-diphenyltricarboxylic acid, benzophenone-3,3 ′, 4-tricarboxylic acid , Diphenylsulfone-3,3 ', 4-tricarboxylic acid, diphenyl ether-3,3', 4-tricarboxylic acid, and the like, and as the aromatic tetracarboxylic acid, for example, pyromellitic acid, diphenyl-2,2 ′, 3,
3'-tetracarboxylic acid, benzophenone-2,2'-3,
3'-tetracarboxylic acid, diphenyl sulfone-2,2'-
3,3'-tetracarboxylic acid, diphenyl ether-2,
2'-3, 3'-tetracarboxylic acid and the like can be mentioned.
In the present invention, acid anhydrides of these polycarboxylic acids can also be used.

The organic diisocyanate compound as the component (C) reacts with a carboxyl group to form an amide or an imide.
By using such an organic diisocyanate compound, the hard segment has a structure containing a repeating unit derived from an imide ring portion and an organic diisocyanate compound in addition to the repeating unit derived from caprolactam, and the heat resistance by containing an imide ring. And the polyamide part has a different structure, the cohesive force of the polyamide part is reduced and the melting point is lowered. This brings about an advantage that the molding temperature can be lowered and that the range of kneading conditions can be widened when used as a resin modifier. Moreover, since the crystallization temperature is lowered when the amount of the organic diisocyanate compound is increased, the flowability during injection molding can be improved.

Examples of such an organic diisocyanate compound include hexamethylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate. These organic diisocyanate compounds may be used alone or in combination of two or more, and the amount used is preferably 1 time mol or less of the glycol as the component (D). This amount is 1
If the amount is more than twice the molar amount, it may vary depending on the kind of the diisocyanate compound, but the coloring becomes strong and the melting point becomes too low, which is not preferable. More preferably 0.8
The amount is not more than twice, but not more than 0.01 times because the effect may not be sufficiently exhibited.

Advantageously, the polyamideimide dicarboxylic acid has a number average molecular weight in the range of 500 to 3000. This number average molecular weight is calculated from the charge composition and the amount of recovered caprolactam at the time of polymerization, and if this is less than 500, the cohesive force of the hard domain decreases, and as a result, the mechanical strength decreases and 3000 Transparency is impaired when it exceeds.

On the other hand, the soft segment in the polyamide-imide elastomer of the present invention has a number average molecular weight of the component (D) of 50.
0 to 4000 polyoxyalkylene glycol and α, ω
-At least one selected from dihydroxy hydrocarbons
It is derived from the seed glycol. Examples of the polyoxyalkylene glycol include polyoxytetramethylene glycol, modified polyoxytetramethylene glycol, polyoxypropylene glycol, polyoxyethylene glycol and copolymer glycols thereof.

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

In particular, when only polyoxytetramethylene 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 characteristics. Furthermore, from the viewpoint of low-temperature characteristics, the molecular weight distribution of polyoxytetramethylene glycol ▲ ▼ / ▲ ▼ is the number average molecular weight obtained from the terminal hydroxyl value, and ▲ ▼ is the formula ▲ ▼ = anti log (0.493logη + 3.0646) Is a viscosity average molecular weight, and η is a melt viscosity at a temperature of 40 ° C. in poise) of 1.6 or less.

In the present invention, modified polyoxytetramethylene glycol can be used instead of the above polyoxytetramethylene glycol. As the modified polyoxytetramethylene glycol, the conventional polyoxytetramethylene glycol - a (CH _{2) 4} part of -O- -R
The thing replaced by -O- is mentioned. Here, R is an alkylene group having 2 to 10 carbon atoms, specifically, ethylene group, 1,2-propylene group, 1,3-propylene group, 2-methyl-1,3-propylene group 2,2- Preferable examples include dimethyl-1,3-propylene group, pentamethylene group, hexamethylene group and the like. The amount of modification is not particularly limited,
It is usually selected in the range of 3 to 50% by weight. The amount of modification and the type of the alkylene group are 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 by, for example, copolymerization of tetrahydrofuran and diol using a heteropolyacid as a catalyst, copolymerization of cyclic ether which is a diol or a condensation product of diol, and butanediol.

When imparting hydrophilicity to the elastomer of the present invention,
Polyoxyethylene glycol can be used, and depending on its hydrophilicity, it can be used alone or in combination with polyoxytetramethylene glycol. When polyoxyethylene glycol has a high molecular weight, it tends to crystallize even if it is incorporated in the block copolymer, and it becomes difficult to develop rubber elasticity at low temperatures.Therefore, when used alone, the number average molecular weight is 500 to 2500. It is preferable to use one of the following.

As the α, ω-dihydroxy hydrocarbon, for example, polyolefin glycol or hydrogenated polybutadiene glycol obtained by polymerizing olefin or butadiene and hydroxylating the terminal and hydrogenating the double bond can be used. These hydrocarbons have a number average molecular weight of 500 to 4
Must be in the 000 range. When the number average molecular weight is less than 500, problems such as a low melting point of the obtained elastomer and a lack of excellent physical properties occur. On the other hand, when the number average molecular weight exceeds 4000, the number of reaction points decreases, and a high molecular weight elastomer is obtained. Is difficult to obtain.

The glycol as the component (D) used in the present invention may be used alone or in combination of two or more kinds.
The type, molecular weight, and ratio of the glycol to be used are appropriately selected in consideration of various properties such as low-temperature properties, weather resistance, and oil resistance of the elastomer.

In the present invention, the component (B), the component (C) and the component (D) are represented by the formulas where the respective numbers of moles used are b, c and d. as well as It is necessary to use them in a ratio that satisfies the relationship of.
If the value of b / (c + d) deviates from the above range, the polyamide-imide elastomer does not have a high molecular weight, and the strength tends to decrease.

Further, the component (D) is preferably used so that the content of the soft segment in the polyamide-imide elastomer is 30 to 85% by weight. When the amount is less than 30% by weight, the polyamide-imide elastomer has flexibility and transparency. If the amount exceeds 85% by weight, the strength tends to 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 polyamide-imide component in the elastomer to 15 to 45% by weight, a flexible and tough elastomer having a hardness in the vulcanized rubber region with a Shore hardness of 60A to 40D is obtained.

In the present invention, (A) component caprolactam,
(B) component aromatic polycarboxylic acid or its acid anhydride,
The organic diisocyanate compound as the component (C) and the glycol as the component (D) are melt-dehydrated and condensed at a temperature in the range of 180 to 280 ° C. At this time, the reaction temperature can be raised stepwise.

At this time, some caprolactam remains unreacted, but this is distilled off under reduced pressure and removed from the reaction mixture. The reaction mixture after removing the unreacted caprolactam can be further highly polymerized, if necessary, by postpolymerization under reduced pressure at 200 to 300 ° C, more preferably 230 to 280 ° C.

If the reaction temperature in the present invention is less than 180 ° C., the polymerization rate is too slow to be practical, and if it exceeds 300 ° C., thermal deterioration occurs, which is not preferable.

Esterification reaction and polymerization of caprolactam are caused at the same time, and each reaction rate is controlled,
In order to obtain a transparent and homogeneous elastomer, the produced water is removed to the outside of the system to reduce the water content of the reaction system.
It is necessary to maintain the content in the range of 0.1 to 1% by weight for polymerization. When this water content exceeds 1% by weight, the polymerization of caprolactam preferentially causes coarse phase separation, while 0.1% by weight
When the amount is less than the above, esterification is preferentially performed and caprolactam does not react, and an elastomer having a desired composition cannot be obtained. 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, if necessary, a method of reducing the water content in the reaction system as the reaction proceeds can be employed. The control of the water content includes, for example, reaction temperature,
The reaction can be performed depending on reaction conditions such as the flow rate of the inert gas introduced, the degree of pressure reduction, or the structure of the reactor.

According to the method of the present invention, the degree of polymerization of the polyamide-imide elastomer can be arbitrarily changed as required, but the relative viscosity measured at 30 ° C. at 0.5% by weight / metacresol volume% is 1.5 or more. Preferably.
If it is lower than 1.5, there arises a defect that mechanical properties cannot be sufficiently expressed. More preferably, 1.6 or more is desirable.

Further, in this reaction method, an esterification catalyst can be used as a polymerization accelerator, and examples of the catalyst include phosphoric acid, tetraalkyl orthotitanate such as tetrabutyl orthotitanate, and tetraalkoxyzirconium such as tetrabutoxyzirconium. Tin-based catalysts such as 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 the middle of the polymerization. Further, in order to enhance the thermal stability of the obtained polyamide-imide elastomer,
Various kinds of stabilizers such as a heat resistant antioxidant and an antioxidant can be used, and these may be added at any stage of the initial, middle, and final stages of the polymerization, or after the polymerization. As the heat resistance stabilizer, for example, N, N'-hexamethylene-bis (3,5-tert-butyl-4-hydroxycinnamic acid amide), 4,4'-bis (2,6-di-tert-butylphenol) ,
Various hindered phenols such as 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), N, N '
-Bis (β-naphthyl) -p-phenylenediamine, N,
N'-diphenyl-p-phenylenediamine, poly (2,
Aromatic amines such as 2,4-trimethyl-1,2-dihydroquinoline), copper salts such as copper chloride and copper iodide, and sulfur compounds such as dilaurylthiodipropionate and phosphorus compounds. Furthermore, the polyamide-imide elastomer obtained in the present invention includes an ultraviolet absorber, an antistatic agent,
A coloring agent, a filler, a hydrolysis resistance improver and the like can be optionally contained.

EFFECTS OF THE INVENTION The polyamide-imide elastomer of the present invention, unlike conventional ones, has excellent flexibility, transparency and mechanical strength, and also has good heat resistance and resin modification properties, and requires transparency. It is preferably used for various applications such as materials for hoses, tubes and sheets, plastic modifiers and photoresist base polymers.

EXAMPLES Next, the present invention will be described 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 obtained as follows.

(1) Shore hardness It was measured according to ASTM D-2240 using a dyurometer.

(2) Tensile breaking strength Elastomer was formed into a sheet having a thickness of 1 mm by hot pressing, a dumbbell-shaped sample piece was punched out according to JIS K 6301, and the strength was measured with a tensile strength tester (Instron).

(3) Relative viscosity Measured in meta-cresol under the conditions of 30 ° C. and 0.5% by weight / volume.

(4) Pyrolysis temperature For the weight loss temperature, use a differential thermal balance and raise the temperature at 10 ° C / min.
It was measured at.

(5) Melting point and crystallization temperature Using a differential thermal balance, the melting point was measured at a temperature rising rate of 10 ° C / min, and the temperature was lowered at 5 ° C / min to obtain the crystallization temperature.

(6) Haze Number Using a 1 mm thick sheet, the haze was measured according to the method according to ASTM D 1003-61.

Example 1 500 m equipped with a stirrer, nitrogen inlet and distillation tube
l In a separable flask, 93 g of caprolactam and polyoxytetramethylene glycol with a number average molecular weight of 1980 (▲
▼ s / ▲ ▼ = 1.45) 82.5g, trimellitic anhydride 8.8
g, diphenylmethane diisocyanate [manufactured by Nippon Polyurethane Industry Co., Ltd., Millionate MT] 1.04 g (diisocyanate / glycol molar ratio = 0.1) was added to N, N'-hexamethylene-bis (3,5-di-t-butyl-4). -Hydroxycinnamic acid amide) (trade name "Irganox 1098" antioxidant) was charged with 0.30 g, and the mixture was melted at 150 ° C while flowing nitrogen at 50 ml / min, and then polymerized at 260 ° C for 4 hours. The water contents in the reaction solution 1 hour, 2 hours, and 4 hours after reaching 260 ° C. were 0.7, 0.5, and 0.3% by weight, respectively.

Next, after adding 0.30 g of tetrabutyl orthotitanate, the pressure was gradually reduced to 1 Torr and 32.5 g of unreacted caprolactam was distilled out of the system. Further, polymerization was carried out at the same temperature under a pressure of 1 Torr or less for 3 hours to obtain a transparent elastomer (haze number 35%). 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 an elongation of 370 kg / cm ² , 900%, and a Shore hardness A.
And D were 92 and 34, respectively. The thermal decomposition initiation temperature was 317 ° C, and the 10% weight loss temperature was 363 ° C.

Example 2 Polyoxyethylene glycol 90 having a number average molecular weight of 1490
Polymerization was carried out in the same manner as in Example 1 except that g, caprolactam 97 g, trimellitic acid 16.4 g, and diphenylmethane diisocyanate 4.52 g (diisocyanate / glycol molar ratio = 0.3). The water content in the polymerization system is 0.8-
It was 0.5% by weight. The amount of caprolactam distilled out of the system was 24.2 g, and a transparent elastomer was obtained.
This elastomer has a polyoxyethylene glycol segment content of 49% by weight, a relative viscosity of 2.0, a tensile strength and an elongation of 420 kg / cm ² , 750%, and a Shore hardness D.
Was 38. The melting point and the thermal decomposition start temperature are shown in the table.

Examples 3 and 4 Polymerization was performed in the same manner as in Example 2 except that the molar ratio of diphenylmethane diisocyanate / polyoxyethylene glycol was changed to 0.5 (Example 3) and 0.05 (Example 4). An elastomer having a polyoxyethylene glycol segment content of 49% by weight was obtained. The melting points and thermal decomposition initiation temperatures of these elastomers are shown in the table.

Example 5 In a 10 l SUS reactor equipped with a stirrer, a nitrogen inlet and a distillation tube, 2.97 kg of an aqueous caprolactam solution (caprolactam content 80% by weight), 2.00 kg of polyethylene glycol having a number average molecular weight of 1494, and 270 g of trimellitic anhydride , 17 g of diphenylmethane diisocyanate and 8 g of N, N′-hexamethylene-bis (3,5-di-t-butyl-4-hydroxycinnamic acid amide) were charged together, and the temperature was raised to 250 ° C. while flowing nitrogen at 1 / min. Warmed. After 1 hour and 2 hours, a small amount of the reaction solution was sampled and the water content thereof was measured to be 0.6% by weight and 0.5% by weight. After polymerization for 2 hours, the pressure was gradually reduced to 1 meter, and 0.53 g of unreacted caprolactam was distilled out of the system. Then add tetra-n
8 g of butyl orthotitanate was added, and polymerization was carried out at 260 ° C. under a pressure of 1 Torr or less for 5 hours. The obtained elastomer was transparent (haze number 45%), had a polyethylene glycol segment content of 48% by weight, had a relative viscosity of 1.9, a melting point of 201 ° C., a tensile strength and an elongation of 390 kg / cm ² , 750, respectively.
%, And Shore hardnesses A and D were 98 and 41, respectively. The thermal decomposition starting temperature was 330 ° C.

Example 6 In the same reactor as in Example 5, 2.23 kg of caprolactam, 2.20 kg of polyethylene glycol having a number average molecular weight of 1980, 224 kg of trimellitic anhydride, 13.9 g of diphenylmethane diisocyanate and N, N'-hexamethylene-bis (3,5- The-
8 g of t-butyl-4-hydroxycinnamic acid amide) was charged together, and the mixture was heated to 150 ° C. and melted. Then, the temperature was raised to 250 ° C. under reduced pressure of 300 Torr and the polymerization was carried out for 4 hours. After that, the pressure was gradually reduced to 1 Torr and 0.64 kg of unreacted caprolactam
After distilling it out of the system, 6 g of tetra-n-butoxyzirconium was added thereto, and polymerization was carried out at 260 ° C. under a reduced pressure of 1 Torr or less for 2 hours. The obtained elastomer is transparent (haze number 38%), the content of polyethylene glycol segment is 55% by weight, the relative viscosity is 1.9, the melting point is 209 ° C, the thermal decomposition initiation temperature is 327 ° C, and the tensile strength and the elongation are 350 kg / each. c
m ² , 850%, and Shore hardnesses A and D were 91 and 35, respectively.

Example 7 Caprolactam 1.20 kg, polyethylene glycol (number average molecular weight 1980) 2.80 kg, trimellitic anhydride 285 g, diphenylmethane diisocyanate 17.7 g
Polymerization was carried out in the same manner as in Example 6. The amount of unreacted caprolactam distilled off was 0.30 kg. The obtained elastomer has 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.,
Tensile strength and elongation of 310 at thermal decomposition initiation temperature of 325 ℃
kg / cm ² , 1000%, Shore hardness A and D 78 and 24 respectively
Met.

Example 8 Polymerization was carried out in the same manner as in Example 1 except that 10.9 g of pyromellitic anhydride was used instead of trimellitic anhydride and 1.4 g of hexamethylene diisocyanate was used instead of diphenylmethane diisocyanate. . During this period, the water content in the polymerization system was 0.3 to 0.6% by weight, and a transparent (haze number 50%) elastomer was obtained.

This elastomer contained 55% by weight of a polyoxytetramethylene glycol segment, had a melting point of 206 ° C., a thermal decomposition starting temperature of 323 ° C., a tensile strength of 350 kg / cm ² , an elongation of 920%, and a Shore hardness of D37.

Example 9 Instead of the polyoxytetramethylene glycol of Example 1, a saturated polyolefin glycol having a number average molecular weight of 2200 (Mitsubishi Kasei Co., Ltd., trade name Polyether HA) 9
Melting point 205, containing 57% by weight of polyolefin glycol segments as in Example 1, except 1.7 g was used.
℃, thermal decomposition start temperature 321 ℃, tensile strength 220kg / cm ² , elongation 83
A transparent elastomer having a shore hardness of D35 of 0% (a haze number of 37%) was obtained.

Comparative Example 1 In the same apparatus as in Example 1, caprolactam 82.5 g and polyoxytetramethylene glycol 150 having a number average molecular weight of 2040 were used.
g, 10.7 g of adipic acid, 0.24 g of phosphoric acid and 0.24 g of antioxidant (Irganox 1098), polymerized under the same conditions as in Example 1, containing 73% by weight of polyoxytetramethylene glycol segment, relative viscosity A transparent (haze number 32%) elastomer of 1.85 was obtained. This is the melting point
The temperature was 200 ° C, the thermal decomposition starting temperature was 281 ° C, the tensile strength was 300 kg / cm ² , and the elongation was 1000%.

Comparative Example 2 The distillation tube of the apparatus of Example 1 was replaced with a reflux condenser, 167 g of caprolactam, 33.2 g of adipic acid and 6 g of water were charged, and 260
The reaction was carried out at 0 ° C. for 6 hours to produce a terminal carboxyl group folycapamide. This product has an average molecular weight of
It was 883.

The apparatus of Example 1 was charged with 40 g of the polyamide, 97.4 g of polyoxytetramethylene glycol of Example 1, 0.3 g of an antioxidant (Irganox 1098) and 0.2 g of tetrabutyl orthotitanate, melted at 240 ° C. and then depressurized. 1 to 3 torr for 2 hours, then 1 to 3 torr, 260 ° C
After 8 hours of polymerization, coarse and coarse separation occurred during the polymerization, the melt became milky white, and milky white until the end of the polymerization, and the obtained elastomer was opaque (haze number 90% or more). The elastomer contained 70% by weight of polyoxytetramethylene glycol segment and was brittle. Also, relative viscosity 1.45, melting point 95-120
° C., the thermal decomposition temperature 308 ° C., was tensile strength 40 kg / cm ^2.

Claims (1)

[Claims] 1. A caprolactam (A), a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring or (B) an acid anhydride thereof, (C) an organic diisocyanate compound and (D). At least one glycol selected from polyoxyalkylene glycol having a number average molecular weight of 500 to 4000 and α, ω-dihydroxy hydrocarbon is represented by the formula: as well as (However, b, c and d are the components (B),
(C) and (D) indicate the number of moles of component) are mixed in such a ratio as to satisfy the relationship, and water produced in the reaction is removed to the outside of the system so that the water content of the reaction system is 0.1 to 1% by weight.
Polyamide-imide elastomer characterized by carrying out polycondensation at a temperature of 180 to 280 ° C., removing unreacted caprolactam, and further performing post-polymerization at a temperature of 200 to 300 ° C. under reduced pressure, if necessary. Manufacturing method.