JPH0684418B2 - Poly (urethane) ureaamide polymer foam - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a poly (obtained by a polyaddition reaction of a polyester polyol derivative having at least one terminal amino group represented by the general formula [I] with a polyisocyanate. Urethane) Urea amide polymer foam.

(Prior Art) Japanese Patent Application Nos. 57-199384 and 57-165447, which are the prior applications of the present applicant.
58-75182, 59-66599, and 59-124019 describe polyether polyol derivatives having an amino group at the molecular end and a method for producing the same, a polymer produced by reacting the polyether polyol derivative with a polyisocyanate, and a method for producing the same. Is shown. The polyols used as starting materials in these inventions are all polyether polyols, and do not include polyester polyols.

In the reaction of a polyester polyol derivative having an amino group and a hydroxyl group as required at the molecular end and an aromatic amide group in the main chain with a polyisocyanate, a urea group,
Poly (urethane) ureaamide polymers containing aromatic amide groups are obtained and have many significant advantages compared to polyurethanes obtained from the corresponding polyester polyols and polyisocyanates.

In particular, the poly (urethane) ureaamide polymer obtained by the polyaddition reaction of the polyester polyol derivative having an amino group and optionally a hydroxyl group at the terminal of the present invention and having an aromatic amide group in the main chain with a polyisocyanate is ,
It has higher heat resistance and stronger mechanical strength compared to the structurally equivalent polyurethane.

U.S. Pat.No. 4,328,322 discloses a polyaddition reaction between a para-aminobenzoic acid ester of a polyol and a polyisocyanate obtained by reacting a polyol with para-nitrobenzoic acid chloride and then reducing the nitro group to convert all the terminal hydroxyl groups of the polyol into amino groups. The resulting polymer is disclosed. Also, polyamine was reacted with para-nitrobenzoic acid chloride or para-nitrobenzoic acid, and then the nitro group was reduced to convert all the terminal amino groups of the polyamine into amino groups of different species. Polyaddition of para-aminobenzoic acid amide with polyisocyanate Polymers obtained by the reaction are disclosed.

The present invention provides a poly (urethane) urea amide polymer by polyaddition reaction of a polyester polyol derivative in which a part or all of the terminals of the polyester polyol is substituted with an aromatic amino group, and the main chain has an aromatic amide group and a polyisocyanate. I will get it. Therefore, the polymers of the present invention are quite different in chemical structure from the polymers of US Pat. No. 4,328,322.

(Problems to be Solved by the Invention) An object of the present invention is to carry out polyaddition of a polyester polyol derivative having an amino group at a terminal and optionally a hydroxyl group and an aromatic amide group in the main chain with a polyisocyanate. It is intended to provide a polymer foam made of a poly (urethane) ureaamide polymer by a reaction.

(Means for Solving Problems) The present invention provides a general formula (A: In the main chain with a molecular weight of 400 to 10,000 N-valent polyester polyol residue obtained by removing the terminal H atom from the n-valent polyester polyol containing: n: an integer of 2 ≦ n ≦ 4: an average value, and 0 ≦ x ≦ (n− 1) number in the main chain -NH- group of is adjacent to the carbonyl residue of aminobenzoic acid and / or the carbonyl residue of polybasic acid of polyester polyol to form an amide group, and the -CO- group forms an ester group or an amide group. : Residue obtained by removing -NCO group from polyisocyanate] having a molecular weight of about 10,000 to 50
It relates to a foam of a poly (urethane) ureaamide polymer composed of various polymers. Further, the present invention relates to a polymer foam comprising a polyester polyol derivative of the general formula [I], a chain extender and a polymer obtained by the reaction of a polyisocyanate.

The polyester polyol derivative of the general formula [I] used in the present invention is a polyester polyol in which the terminal is partially or completely aromatically aminated and an aromatic amide group is contained in the main chain, and substantially 1 The reaction of the stage completes its preparation and yields high and does not require purification.

The polyester polyol derivative used in the present invention is
It is obtained by reacting a divalent to tetravalent polyester polyol having a molecular weight of 400 to 10,000 with an aminobenzoic acid alkyl ester.

The polyester polyol used in the present invention may be either a condensed polyester polyol or a lactone polyester polyol obtained by a known method. Condensed polyester polyols include adipic acid, sebacic acid,
Saturated or unsaturated dibasic acids such as terephthalic acid, isophthalic acid, maleic acid and fumaric acid, maleic anhydride, acid anhydrides such as phthalic anhydride, dialkyl esters such as dimethyl terephthalate and ethylene glycol, propylene glycol, A polyester polyol obtained by a condensation reaction with a glycol such as butylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,6-hexylene glycol, and specific examples include polyethylene adipate polyol and polybutylene adipate polyol. , Polyhexylene adipate polyol, etc., one kind of acid and one kind of glycol, adipate type polyol, polyethylene butylene adipate polyol, polyethylene diethylene adipate polyol , Polyhexylene neopentylene adipate polyol, etc. adipate-based polyol consisting of one kind of acid and many kinds of glycol, polyethylene adipate terephthalate polyol consisting of many kinds of acid and one kind of glycol, polyethylene adipate isophthalate polyol And other aromatic polyols.

Lactone-based polyester polyols are obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-butyrolactone, but they have various compositions depending on the type of initiator. As the initiator, glycols such as ethylene glycol and butylene glycol, polyether polyols such as polyoxypropylene glycol (PPG) and polyoxytetramethylene glycol (PTMG), and condensation type polyol polyols such as adipate are selected. However, both are suitable for use in the present invention.

Bifunctional or higher functional polyols such as condensed polyester polyols and lactone polyester polyols are also suitable for use in the present invention. For example, in a condensed polyester polyol, a polyester polyol using glycerin or trimethylolpropane as a part of a glycol component, or a polyester polyol using a polybasic acid such as trimellitic acid as a part of a dibasic acid, or a lactone polyester polyol. Then, a polyester polyol obtained by using glycerin, trimethylolpropane, pentaerythritol or the like as an initiator of ring-opening polymerization is also suitable for use in the present invention.

When the polyester polyol derivative obtained from the above polyester polyols is used as a raw material for synthesizing an elastomer, a divalent or trivalent polyester polyol having a molecular weight of 1000 to 4000 is preferable.

When used as a synthetic raw material for plastics, the molecular weight is 40
A trivalent to tetravalent polyester polyol of 0 to 1500, for example, a lactone type polyester polyol obtained by using pentaerythritol as an initiator is suitable.

The aminobenzoic acid alkyl ester used in the present invention may be any of ortho, meta or para-aminobenzoic acid alkyl ester, but when the polyester polyol derivative of the present invention is used as a synthetic raw material for an elastomer or a plastic, a para-aminobenzoic acid alkyl ester is used. It is particularly suitable.

As the alkyl group of aminobenzoic acid alkyl ester, various ones can be exemplified, and preferable examples thereof include a chain having 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, octyl, cyclobutyl, cyclopentyl, cycloheptyl and the like. Alternatively, cyclic alkyl can be mentioned. Further, 2-butoxyethyl, 2-ethoxyethyl and the like are also suitable.

Further, bis (aminobenzoic acid) alkyl esters can also be used. Bis (aminobenzoic acid) esters such as glycols having 2 to 8 carbon atoms such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and heptine glycol are preferable.

In the present invention, the amino benzoic acid alkyl ester is 0.25 n based on 1 mol of the n-valent polyester polyol.
Suitably, -10 nmoles, preferably 0.5-2 nmoles are reacted.

The polyester polyol derivative of the present invention can be obtained by carrying out dealcoholization by usually heating to 150 to 250 ° C. in the presence of a catalyst or a known esterification catalyst while passing an inert gas such as nitrogen gas. When a catalyst is used, it is preferable to use a weakly acidic or weakly basic catalyst that has little influence on the ester bond in the polyester polyol and is less likely to cause side reactions such as dehydration reaction of hydroxyl groups, for example, antimony trioxide, lead monoxide, etc. Examples thereof include organic oxides, organic titanium compounds such as tetraisopropyl titanate and tetrabutyl titanate, and weak acid alkaline earth metal salts such as calcium acetate. Organic titanium compounds are particularly preferable. The catalyst amount is usually 1000 ppm or less. Further, for the reaction, an inert solvent or a color preventing agent such as triphenyl phosphate can be used. The reaction is continued until the distillation of the aliphatic alcohol is completed, and the system is further depressurized to completely distill off the alcohol and excess aminobenzoic acid alkyl ester, if present. No purification is necessary.

Incidentally, points to be noted in the reaction between the polyester polyol and the aminobenzoic acid alkyl ester, the ester bond in the molecular chain of the polyester polyol and the terminal OH group or the NH ₂ group of the aminobenzoic acid alkyl ester,
That is, the transesterification reaction or the amide formation reaction proceeds at the same time.

These two reactions are carried out by adjusting the reaction temperature, the molar ratio of the polyester polyol and the aminobenzoic acid alkyl ester, and the time required for dealcoholization.
It is possible to control.

Therefore, the polyester polyol derivative obtained by the reaction of the polyester polyol of the present invention with the aminobenzoic acid alkyl ester is different from the molecular weight of the charged polyester polyol and the calculated molecular weight obtained from the charged amount of the aminobenzoic acid alkyl ester. Since a compound having a molecular weight is obtained, in order to obtain a polyester polyol derivative having a desired molecular weight, it is necessary to pay attention to the charged amount of raw materials. The content of amide groups is an important factor for achieving the object of the present invention to produce a polymer having higher heat resistance and higher mechanical strength.

The reaction for forming an aromatic amide group has not been fully clarified yet, but it can be inferred as follows.

Formula (1) is a reaction for terminal amination, and formula (2) is a reaction for forming an aromatic amide group adjacent to a terminal aminophenyl group. Formula (3) is a reaction in which an aromatic amide group is inserted into the polyester main chain. Formula (4) is a reaction in which an aromatic amide group is further inserted into the polyester main chain having an aromatic amide group.

The aromatic amide group in the above polyester polyol derivative can be quantitatively confirmed by NMR analysis and nitrogen element analysis.

As a result of ¹³ C-NMR analysis, the number of amide groups in the polyester polyol derivative of the present invention when an aliphatic polyester polyol was used as a starting material was higher in the main chain than in the adjacent ends. From this result, the following can be estimated. Since the difference in the number of two kinds of ester groups, that is, the difference in the number of terminal aminobenzoic acid ester groups and the number of ester groups in the main chain is large, the probability that a reaction can occur is naturally greater in the main chain. Therefore, it is considered that the amide group formation reaction in the polyester main chain became dominant.

The polyester polyol derivative obtained by the method of the present invention is an esterified product in which all terminal hydroxyl groups are converted to amino groups, or a partially esterified product in which some unreacted hydroxyl groups remain, and an aromatic amide group in the main chain. Contains. The amination ratio (that is, the esterification ratio of the terminal hydroxyl group) and the degree of the amidation ratio can be varied over a wide range depending on the application, and at least one hydroxyl group of the polyester polyol is esterified on average. Is required, and the amination ratio is preferably about 50 to 100%, and the amide group can be changed over a range of about 5 to 2000 mol% with respect to the terminal amino group, but about 5 to 100 mol% is preferable. . When the amide group is within this range, the viscosity of the polyester polyol derivative is appropriate and the moldability is excellent.

An example of the polyester polyol derivative of the general formula [I] when ethylene adipate is used as the raw material polyester in the present invention is given by the following formula. However, in the formula, each segment does not show the order of bonding but shows a ratio, and -NHC ₆ H ₄ CO- groups in the main chain are randomly bonded instead of blocks, and when bonded to the terminal aminobenzoyl group. And may not be combined.

R ₁ : CH ₂ CH ₂ R ₂ : CH ₂ CH ₂ CH ₂ CH ₂ x: a value showing an average valence, 0 ≦ x ≦ 1 p, r: an average value showing the number of repeating structural units And 0 ≦ p,
Number of r ≦ m q: Average value showing the number of structural units contained in one molecule,
It is a number of 0.05 ≤ q ≤ 10 and not the number of repetitions.

m is a positive number determined from the molecular weight, p + r = m. Further, one example of the polyester polyol derivative of the general formula [I] when the diol obtained by ring-opening polymerization of ε-caprolactone is used as a raw material is Given in.

R ₃ : CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ R ₄ : Alkyl group such as CH ₂ CH ₂ or CH ₂ CH ₂ CH ₂ CH ₂ x: a value showing an average valence, 0 ≦ x ≦ 1 S, u, v: average value indicating the number of repeating structural units, 0 ≦
Number of s, u, v ≤ m t: Average value showing the number of structural units contained in one molecule,
It is not a number of 0.05 ≦ t ≦ 10, it is not the number of repetitions.

m: Positive number determined from molecular weight, s + u + v = m The above two examples are examples of using a bifunctional polyester polyol, and do not limit the structure of the polyester polyol derivative of the present invention.

The polyisocyanate used in the present invention may be any polyisocyanate known in polyurethane chemistry, such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4-tolylene diisocyanate (2, 4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (MDT), carbodiimide modified MDI, polymethylene polyphenyl polyisocyanate (PAPI), orthotoluidine diisocyanate (TODI), naphthylene diisocyanate (NDI), xylylene diisocyanate (X
DI) and the like, and one kind or two or more kinds can be used.

The production of a poly (urethane) ureaamide polymer by a polyaddition reaction between a polyester polyol derivative having an amino group and optionally a hydroxyl group at the terminal and an aromatic amide group in the main chain and polyisocyanate in the present invention,
It may be carried out by any method known in polyurethane chemistry. That is, it means that the reaction can be carried out in the presence of an active hydrogen-containing compound capable of reacting with isocyanate. Also any additive known in polyurethane chemistry, such as a catalyst,
Flame retardant, plasticizer, filler, foaming agent, anti-aging agent, pigment,
This means that an inert organic solvent or the like may be added.

In the present invention, for example, the elastomer is preferably produced in the presence of a suitable chain extender. Examples of the chain extender include 2 to 4 functional polyols having a molecular weight of 400 or less and diamines having a primary or secondary terminal amino group having a molecular weight of 400 or less. Suitable chain extenders include (a) ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, pentaerythritol,
Polyols such as sorbitol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, xylylene glycol (b) hydrazine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,4-cyclohexanediamine, phenylenediamine, Xylylenediamine, 2,4-tolylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-dichlor-4,4'-diaminodiphenylmethane, 1,4-dichloro-3,5-diamino benzene,
Diamines such as 1,3-propanediol diparaaminobenzoate (c) Alkanolamines such as ethanolamine, diethanolamine and triethanolamine (d) Hydroquinone, pyrogallol, 4,4′-isopropylidenediphenol, aniline and the above Examples thereof include polyols, diamines, alkanolamines and other polyols having a molecular weight of 400 or less obtained by adding propylene oxide and / or ethylene oxide in an arbitrary order. Among them, diamines are preferable for enhancing the effect of the present invention.

In the present invention, a known long-chain polyol capable of reacting with isocyanate, a polyamine, an active hydrogen-containing compound such as an aminopolyol can be used in combination. Suitable long chain polyols are compounds having at least one hydroxyl group having a molecular weight of more than 400. Particularly suitable long-chain polyols include polyoxyalkylene polyols such as polyoxyethylene polyols having a molecular weight of 400 to 10000 and a divalent to octavalent polyol, polyoxypropylene polyols, polyoxyethyleneoxypropylene polyols, polyoxytetramethylene polyols, and Examples thereof include so-called polymer polyols obtained by grafting styrene or acrylonitrile onto these, and all polyester polyols that can be used as a raw material for synthesizing the polyester polyol derivative of the present invention. Further, polycarbonate polyols such as polyhexamethylene carbonate polyols, polyolefin polyols such as polybutadiene polyols having terminal hydroxyl groups, terminal epoxy oligomers having hydroxyl groups in the side chains, and polyols obtained by ring-opening epoxy groups with these alkanolamines and the like. Are also suitable.

Suitable long chain polyamines are compounds having at least one amino group having a molecular weight of more than 400. For example, polyether polyamines obtained by reacting the terminal hydroxyl group of polyoxyalkylene polyol with ammonia or the like, and polyether polyamines obtained by reacting a known polyol with ethyleneimine or the like can be mentioned.

The long-chain aminopolyol is a compound whose molecular weight contains both an amino group and a hydroxyl group in excess of 400 in the molecule, for example, an aminopolyol in which a part of the hydroxyl groups of the polyol is substituted with the amino group by the above method. To be or,
Polyether polyol derivatives having at least one aminobenzoic acid ester group at the end disclosed in JP-A-59-53533 are also preferably used.

In the present invention, the polyaddition reaction between the polyester polyol derivative having at least one terminal amino group and polyisocyanate is usually carried out at an isocyanate index of 95 to
It is preferably carried out in the range of 120. The same is true in the presence of other active hydrogen compounds. Usually, the polyester polyol derivative is reacted with the molten polyisocyanate at room temperature or around the melting temperature of the polyisocyanate. When a polyisocyanate which is liquid at room temperature is used, the reaction system can be brought to room temperature. Known long-chain active hydrogen-containing compounds,
When the reaction is carried out in the presence of a chain extender or a foaming agent, these components are preferably mixed and dissolved in the polyester polyol derivative in advance. A prepolymer method in which a part or all of the polyester polyol derivative is preliminarily reacted with an excess polyisocyanate to react as an isocyanate-terminated prepolymer with the rest of the polyester polyol derivative and / or the chain extender is also an effective method.
Alternatively, a part or all of the known long-chain polyol may be previously reacted with an excess of polyisocyanate to form an isocyanate-terminated prepolymer, and then the polyester polyol derivative and the chain extender may be reacted. These prepolymers are preferably heated to 60 to 80 ° C. or higher or dissolved in an inert solvent in order to reduce the viscosity and improve the processability.

When the polymer of the present invention is used as a foam, the reaction may be carried out in the presence of a foaming agent such as water or a low boiling point compound such as monochlorotrifluoromethane.

(Effect of the Invention) The polymer obtained by the present invention has many excellent characteristics.

Compared with the corresponding polyester-based urethane, 1. It has excellent mechanical strength. Especially at high temperatures.

2. Reactivity is moderate.

In the case of a system that does not use a chain extender, the reaction of the usual polyester polyol is extremely slow, whereas the reaction of the polyester polyol derivative of the present invention is moderate.

3. Excellent compatibility.

When an amine-based chain extender is used, the apparent reaction becomes extremely fast in the case of a normal polyester polyol. This is because the compatibility of the reaction system is low and the reaction rate of the polyol and the chain extender is too different, and the chain extender component that has reacted first is precipitated from the reaction solution. In the present invention, the compatibility is excellent and the reaction rates are well balanced, so that an appropriate reaction rate can be obtained.

4. Amorphous.

The polymer obtained according to the present invention is amorphous, and does not change with time such as hardness due to crystallization unlike polymers obtained from ordinary polyester polyols.

(Example) Hereinafter, the present invention will be specifically described with reference to Reference Examples, Examples and Comparative Examples.

Reference Example 1 (Synthesis of Polyester Polyol Derivative) Lactone-based polyester polyol [Placser-21
0, manufactured by Daicel Corporation, MW990, OH value 2.02 meq / g] 2442g
(4.935eq) was placed in a 4-necked flask equipped with a stirring rod, a cooling tube, a thermometer, and a nitrogen gas introducing tube, and dehydrated under reduced pressure at 100 ° C for 1 hour under a nitrogen gas stream. Next, 570.5 g (3.46 mole) of para-aminobenzoic acid ethyl [Hanai Chemical Co., Ltd., first-grade reagent] was added, and the temperature was raised to 88 ° C.

Next, 1.025 g (340 ppm) of tetrabutyl titanate was added, and the temperature was raised with stirring. At 110 ° C., the reaction system became a homogeneous solution, and the wall surface of the 4-necked flask began to be wet with ethanol. The temperature was further raised, the reaction was carried out in the temperature range of 225 to 230 ° C. for 2 hours and 30 minutes, and ethanol was distilled off.

Next, the reaction system was cooled to 138 ° C., and then the pressure was reduced to 7 mmHg under a nitrogen gas stream. The temperature of the system was raised to 200 ° C., unreacted ethyl paraaminobenzoate was distilled off for 3 hours, and a reddish brown liquid having a viscosity at 30 ° C. of 11000 cps was obtained. Yield is 2854
It was g.

When this liquid was analyzed by gel permeation chromatography, no free ethyl paraaminobenzoate was detected. In addition, using the following analysis method for this liquid,
It was confirmed that a polyester polyol derivative having a terminal amino group was produced.

That is, the amine value was 0.998 meq / g as determined by titration with perchloric acid in glacial acetic acid (Analysis Chemistry Handbook, Revised Edition, 3rd edition, p. 261). Also, the total number of hydroxyl groups and amino groups (active hydrogen group value)
According to the hydroxyl value measurement method (JIS K1557) that can measure
It was 1.277 meq / g. These measured values are calculated from the charged amounts of polyester polyol and ethyl para-aminobenzoate, which have an amine value of 1.213 meq / g and an active hydrogen group value of 1.72.
It did not match 8 meq / g. Measured active hydrogen radical number 1.277meq
/ g, the molecular weight of the polyester polyol derivative having a terminal amino group is 1566, and when this product was analyzed by gel permeation chromatography, the molecular weight distribution was higher on the polymer side than the starting polyester polyol. It was confirmed that there was a shift. The ¹³ C-NMR analysis of this product confirmed the presence of an amide group, and the amide group was present in 20 mol% with respect to the terminal amino group. or,
By elemental analysis, nitrogen was 1.68%, consistent with the amount of amide calculated from this (total nitrogen-amine). From these results, the product polyester polyol derivative is a compound in which 78.2% of the terminal hydroxyl groups are converted into amino groups and the aromatic amide group in the molecular chain is contained in 20 mol% with respect to the terminal amino groups. It was The average structure of the product is estimated to be:

Example 1 (Addition polymerization foam of polyester polyol derivative, chain extender and MDI) 100 g of the polyester polyol derivative of Reference Example 1, 1,4
-Putanediol- (reagent first grade) 5.8 g, pure water 0.3 g, and triethylenediamine (TEDA manufactured by Toyo Soda Co., Ltd., TEDA) 0.3 g were added and dissolved, and the liquid temperature was set to 47 ° C. To this mixed solution, add 50 M of contact MDI (36.2g), mix vigorously for 10 seconds, and immediately mix to 60 ℃.
An appropriate amount was cast into a preheated iron mold with a lid with a thickness of 4 mm and foamed. The foam surface became tack-free in about 40 seconds. It was demolded in 10 minutes. Thus, a soft sheet-like foam having a density of 0.60 was obtained. Physical properties were measured after 7 days. The results are shown in Table 1.

Comparative Example 1 For comparison with the foam of Example 1, in order to make the molecular weight of the polyester polyol derivative used in Example 1 instead of the polyester polyol derivative of Reference Example 1, the molecular weight of about 2000 and about 1000 was used. Various types of polycaprolactone polyol (PCL) were blended and used as an average molecular weight of 1566. That is, using PCL2000 (Daicel Chemical Industries "Plaxel 220", molecular weight 1959) 74.5g and PCL1000 (Daicel Chemical Industrial "Plaxel 210", n molecular weight 988) 25.5g, using a mixed polyol with a liquid temperature of 50 ° C. A foam was synthesized exactly as in Example 1. The tack-free property of this foam was 1 minute and 20 seconds. Since the reaction was rather slow, demolding took 20 minutes. Thus, a soft sheet-like foam having a density of 0.60 was obtained.

This sample showed a change in hardness due to crystallization. That is,
The hardness of the sample after 7 days was 46 (JIS A), but 60
The hardness decreased to 36 when heated at ℃ for 20 minutes. The foam of Example 1 did not show such a change in hardness.
The physical properties of the sample of Comparative Example 1 were measured after removing the crystal. The results are shown in Table 1.

Claims (1)

[Claims] 1. A general formula (A: In the main chain with a molecular weight of 400 to 10,000 N-valent polyester polyol residue obtained by removing terminal H atom from n-valent polyester polyol containing: n: integer of 2 ≦ n ≦ 4 x: average value, 0 ≦ x ≦ (n−1) In the main chain -NH- group of is adjacent to the carbonyl residue of aminobenzoic acid and / or the carbonyl residue of polybasic acid of polyester polyol to form an amide group, and the -CO- group forms an ester group or an amide group. : Residue obtained by removing -NCO group from polyisocyanate] having a molecular weight of about 10,000 to 50
Poly (urethane) urea amide polymer foam made from various polymers.