JPS61126124A - Polymer and its production - Google Patents

Abstract

PURPOSE:To obtain an amorphous polymer having excellent mechanical strength and compatibility and moderate reactivity, by reacting a specified polyester polyol derivative with a polyisocyanate. CONSTITUTION:1mol of an n-hydric condensed or lactone-type polyester polyol and 0.25n-10nmol of an alkyl aminobenzoate (e.g., ethyl p-aminobenzoate) are subjected to alcohol elimination reaction at 150-250 deg.C in the presence (absence) of an esterification catalyst to obtain a polyester polyol derivative of formula I (wherein A is an n-hydric polyester polyol residue containing a group of formula II in the main chain, 2<=n<=4, 0<=x<=n-1 and the -NH- group in the group of formula II is bonded with the =CO group of aminobenzoic acid and/or polyester polyol polybasic acid to form an amide group and the -CO- group forms an ester group or an amide group). A polymer obtained by reacting this polyester polyol derivative with a polyisocyanate is incorporated to obtain a poly(urethane)urea amide polymer.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to poly(
(urethane) ureamide polymer.

(Prior art) Patent application No. 57-199384, which is the applicant's earlier application. Same 5
7-165447. 58-75182. 59-66
599. No. 59-124019 discloses a polyether polyol transparent conductor having an amino group at the end of the molecule, a method for producing the same, a polymer obtained by reacting the polyether polyol derivative with a polyisocyanate, and a method for producing the same 9I. The polyols used as starting materials in these inventions are all polyether polyols and do not contain polyester polyols.

In the reaction of a polyester polyol derivative having a 7-mino group and optionally a hydroxyl group at the molecular end and an aromatic amide group in the main chain with a diisocyanate, a urea group,
Poly(urethane)ureamide polymers containing aromatic amide groups are obtained and have a number of significant advantages compared to the corresponding polyurethanes obtained from polyester polyols and polyisocyanates.

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

U.S. Patent No. fjS4,328.322 discloses a polyisocyanate and para-aminobenzoic acid ester of a polyol in which all the terminal hydroxyl groups of the polyol are converted to amino groups by reacting the polyol with para-nitrobenzoic acid chloride and then reducing the nitro groups. Polymers obtained by polyaddition reactions are disclosed. In addition, polyamine p-aminobenzoic acid amide and polyisocyanate are prepared by reacting polyamine with varanitrobenzoic acid a-ride or p-nitrobenzoic acid, and then reducing the nitro groups to convert all the terminal amino groups of the polyamine into different types of amino groups. Polymers obtained by polyaddition reactions are disclosed.

The present invention produces poly(urethane)ureamide polymers by a polyaddition reaction between polyester polyol derivatives in which part or all of the terminals of polyester polyols are substituted with aromatic amino groups and have aromatic 7-mido groups in the main chain, and polyisocyanates. It is something that obtains union. Therefore, the polymer of the present invention has a completely different chemical structure from the polymer of US Pat. No. 4,328,322.

(Problems to be Solved by the Invention) The object of the present invention is to provide a polyester polyol derivative having an amino group at the end, a hydroxyl group if necessary, and an aromatic amide group in the main chain, and a polyisocyanate. It is an object of the present invention to provide a polymer including a poly(urethane)ureamide polymer produced by reaction, and a simple method for producing the same.

(Means for Solving the Problems) The present invention relates to a polyester polyol derivative of the general formula [I] [A: molecular fi 400 to 10 (n obtained by removing a terminal H atom from ruboriol in the main chain of 100).
Value of polyester polyol residue n: An integer of 2≦n≦4 A poly(urethane) urea amide polymer including a polymer obtained by reacting a polybasic acid with a polyisocyanate (an amide group is formed adjacent to the carbonyl residue of a polybasic acid, and the -Co- group forms an ester group or an amide group) and a polyisocyanate. This relates to coalescence and its manufacturing method. Furthermore, the present invention relates to polymers including those obtained by the reaction of the polyester polyol derivative of general formula [I], a chain extender, and bocincyanate, and a method for producing the same.

The polyester polyol derivative of the general formula 1"■) used in the present invention is a polyester polyol whose ends are partially or completely converted into aromatic amide groups to contain an aromatic amide group in the main chain. The production is completed in one step of reaction, the yield is high, and no purification is required.

The polyester polyol derivative used in the present invention is
It is obtained by reacting a divalent to tetravalent polyester polyol with a molecular weight of 400 to too much and a 7-minobenzoic acid furkyl 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.
Saturated or unsaturated dibasic acids such as terephthalic acid, isophthalic acid, maleic acid, and hexamaric acid, acid anhydrides such as maleic anhydride and heptallic anhydride, nofurkyl esters such as methyl terephthalate, and ethylene glycol. It is a polyester polyol obtained by a condensation reaction with glycols such as , fluoropylene glycol, butylene glycol, diethylene glycol, nopropylene glycol, neopentyl glycol, and 6-hexylene glycol. Adipate polyols consisting of one type of acid and one type of glycol such as polyol, polybutylene 7-nopate polyol, polyhexylene acbate polyol, polyethylene butylene 7-nopate polyol, polyethylene butylene 7-nopate polyol, polyhexylene neo Adipate polyols consisting of one type of acid and multiple types of glycol such as benthlene anovate polyol, polyethylene adipate tere-7 tallate polyol consisting of multiple types of acids and one type of glycol, and polyethylene adipate iso-7 tallate polyol. Aromatic polyols such as ol are used in seasoning.

Lactone-based polyester polyols are obtained by ring-opening polymerization of tictones such as C-cablockone and γ-butyrolactone, and polyols with various compositions can be obtained depending on the type of initiator. As an rR initiator, glycols such as ethylene glycol and butylene glycol, polyether polyols such as polyoxypropylene glycol (PPG) and polyoxytetramethylene glycol (PTMG), and polyester polyols of condensed threads such as 77 base) All of them are suitable for use in the present invention.

Further, polyols having two or more functional groups such as condensed polyester polyols and lactone polyester polyols are also suitable for the present invention. For example, condensed polyester polyols include polyester polyols that use glycerin or trimethylolpropane as part of the glycol component, polyester polyols that use polybasic acids such as trimellitic acid as part of the dibasic acid, and lactone polyester polyols. As an initiator for ring-opening polymerization, glycerin,
Polyester polyols obtained using trimethylolpropane, pentaerythritol, etc. are also suitable for use in the present invention.

Among the above polyester polyols, when the polyester polyol derivatives obtained therefrom are used as raw materials for elastomer synthesis, molecular weights of 2 to 4000
Trivalent polyester polyols are preferred.

In addition, when used as a synthetic raw material for plastics, the molecular weight is 4.
00-1500 tri- to tetravalent polyester polyol,
For example, lactone-based polyester polyols obtained by using pentaerythritol as an initiator are 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 raw material for synthesis of elastomers and plastics, para-aminobenzoic acid alkyl ester is particularly suitable.

Various types of alkyl groups can be exemplified as the alkyl group of the aminobenzoic acid alkyl ester, and preferred examples include chains having 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, octyl, cyclobutyl, cyclopentyl, and cycloheptyl. or cyclic alkyl.

Also suitable are 2-butoxyethyl, 2-ethoxyethyl and the like.

Further, bis(aminobenzoic acid)furkyl 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 hexylene glycol are preferred.

In the present invention, the amount of aminobenzoic acid furkyl ester is 0.2 to 1 mole of the monovalent polyester polyol.
It is preferred to react 5n-10 nmol, preferably 0.5n-2 nmol.

The polyester polyol derivative of the present invention can be obtained by dealcoholization without a catalyst or in the presence of a known esterification catalyst, usually by heating to 250 to 250° C. while passing through an inert gas such as a nitrogen bath. When using a catalyst, it is preferable to use a weakly acidic or weakly basic catalyst that has little effect on the ester bonds in the polyester polyol and is less likely to cause side reactions such as hydrophilic reactions of hydroxyl groups, such as antimony dioxide, -lead oxide, etc. Examples include metal oxides such as, organic titanium compounds such as tetraisoprobyl titanate and tetrabutyl titanate, alkaline earth metal salts of weak acids such as calcium acetate, and organic titanium compounds are particularly preferred. The amount of catalyst is usually 1000 pp or less, and an inert solvent or a coloring inhibitor such as phenyl phosphate can also be used in the reaction. The reaction may be continued until the aliphatic alcohol is distilled off, and the system is further reduced in pressure to completely distill off the alcohol and, if present, excess 7-minobenzoic acid furkyl ester. No particular purification is required.

In addition, it should be noted that in the reaction between polyester polyol and 7-minobenzoic acid alkyl ester, g represents the ester bond in the molecular chain of polyester polyol and the terminal OH
NH2g of radical or aminobenzoic acid alkyl ester
This means that the transesterification reaction or amide production reaction proceeds simultaneously.

These two reactions can be carried out by adjusting the reaction temperature, the molar ratio of polyester polyol and 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 7-minobenzoic acid alkyl ester has a molecular weight different from the calculated molecular weight determined from the charged polyester polyol and the charged amount of the aminobenzoic acid alkyl ester. Since a compound with a certain molecular weight is obtained, the amount of raw materials charged should also be taken into consideration in order to obtain a polyester polyol derivative with a desired molecular weight. The content of amide groups is an important factor for achieving the purpose of the present invention, which is to produce a polymer with higher heat resistance and stronger mechanical strength.

Although the reaction for producing aromatic amide groups has not yet been fully elucidated, it can be inferred as follows.

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

The aromatic 7-mido group in the above polyester polyol derivative can be quantitatively confirmed by NMR analysis and nitrogen elemental analysis.

As a result of I''C-NMR analysis, the number of 7-mido groups in the polyester polyol derivative of the present invention when an aliphatic polyester polyol was used as a starting material was found to be greater in the main chain than in the adjacent terminal.From this result, the following Since the difference in the number of the two types 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, it is natural that the probability of reaction occurring is higher in the main chain. This is considered to be the reason why the reaction to generate amide groups in the polyester main chain became predominant.

The polyester polyol derivative obtained by the method of the present invention is an esterified product in which all terminal hydroxyl groups have been converted to amino groups, or a partially esterified product in which some unreacted hydroxyl groups remain, and has an aromatic amide group in the main chain. Contains. The degree of amination (i.e., the esterification rate of terminal hydroxyl groups) and the degree of esterification can vary over a wide range depending on the application, and on average at least one hydroxyl group of the polyester polyol is not esterified. Preferably, the amination rate is about 50 to 100%, and the 7-mido group is about 5 to 2000 mol% of 1@ with respect to the terminal amino group.
Although it can vary over a range, it is preferably about 5 to 100 mol%. Within this range, the polyester polyol derivative has a suitable viscosity and excellent moldability.

In the present invention, an example of the polyester polyol derivative of general formula (I) when ethylene 7novate is used as the raw material polyester is given by the following formula.

However, in the formula, each segment does not indicate the order of bonding but the ratio, and the -NHC,84CO- groups in the main chain are bonded randomly rather than in blocks, and when bonding to the terminal ami/benzoyl group, It may not be combined.

R: CH2CH2 Rz: CH2CH2CH2CH2
Number q of 0≦p≦-: This is an average value indicating the number of structural units contained in one molecule, and is not the number of 0.05≦q≦10 or the number of repeats.

蒲：Positive loss determined by molecular weight, p + r = e
a Also, C-turnip a? An example of the polyester polyol derivative of general formula [1] when a diol obtained by ring-opening polymerization of chthons is used as a raw material is similarly given by the following formula.

R3: CH, CH2CH2CH2CH2R4: CH
2CH2 or a furkyl group such as CH2CH, CH2CH2, etc. Number of solenoids t: An average value indicating the number of structural units contained in one molecule, a number of 0.05≦t≦10, not a repeating number.

+l A positive number determined from the bimolecular view, s + u + v = 蹶 The above two examples are examples of when a bifunctional polyester polyol is used, and do not limit the structure of the polyester polyol derivative of the present invention. s.

The polyisocyanate used in the present invention may be any polyisocyanate known in polyurethane chemistry, for example hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-cyclohexylmethane diisocyanate, 2,4- ) lylene diisocyanate (2,4-T DI ), 2.
6-) lylene diisocyanate (2t8-TD
I), 4,4°-diphenylmethane diisocyanate (MDI), carposiimide-modified MDI, polymethylene polyphenyl polyisocyanate (PAPI), orthotoluidine diisocyanate (TODI), sodium 7-ethylene quisocyanate (NDr), xylylene diisocyanate (XDr) and the like, and one type or two or more types can be used.

In the present invention, the production of a poly(urethane)ureamide polymer by the polyaddition reaction of 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 with a polyisocyanate is as follows:
This means that it may be carried out in any manner known in polyurethane chemistry, ie in the presence of active hydrogen-containing compounds capable of reacting with the incyane. Also all additives known in polyurethane chemistry, such as catalysts,
Flame retardants, plasticizers, fillers, blowing agents, anti-aging agents, pigments,
Inactive 8! This means that a solvent or the like may be added.

In the present invention, for example, when producing an elastomer, it is preferable to carry out the production in the presence of a suitable chain extender. Examples of the chain extender include di- to tetrafunctional polyols with a molecular weight of 400 or less and diamines having a primary or secondary terminal amino group with a molecular weight of 400 or less. Suitable chain extenders include, for example, (a) ethylene glycol, diethylene glycol, propylene glycol, nopropylene glycol, butaneol, hexanediol, glycerin, trimethylolpropane, bentaerythritol, sorbitol, 1,4-cyclohexane; (b) Hydrazine, ethyleneimine, tetramethylene diamine, hexamethylene diamine, 1,4-cyclohexanoamine, phenylene diamine, xylylene diamine, 2 .4-) lylenediamine, 4.4°-noaminonophenylmethane, 3.3'-dichloro-4,4'-diaminodiphenylmethane, 1,4-fuchloro-3,5-
Diamines (C) such as diaminobenzene and 1,3-propanediol di-paraaminobenzoate; 77 Lecanolamines (cl) such as ethanolamine, jetanolamine, and triethanolamine;
Molecular weight 400 obtained by adding propylene oxide and/or ethylene oxide to hydroquinone, pyrol, 4,4'-isopropylidene diphenol, aniline, and the above polyols, cyamines, and flukanolamines in any order. Examples include the following polyols, among which diamines are preferred in order to enhance the effects of the present invention.

In the present invention, active hydrogen-containing compounds such as known long-chain polyols, polyamines, and aminopolyols that can react with incyanate can be used in combination. A suitable long chain polyol is a compound having a molecular weight of 1,400 to 10,000.2 to 8,000,000.
Polyoxyfulkylene polyols such as polyoxyethylene polyol, polyoxypropylene polyol, polyoxyethylene oxypropylene polyol, and polyoxytetramethylene polyol, and so-called polymer polyols in which styrene or acrylonitrile is grafted to these polyols, the so-called polymer polyols of the present invention All polyester polyols that can be used as raw materials for the synthesis of polyester polyol derivatives are mentioned. In addition, epoxy groups are ring-opened with polycarbonate polyols such as polyhexamethylene carbonate polyol, polyolefin polyols such as polybutadiene polyol containing terminal hydroxyl groups, terminal epoxy oligomers containing hydroxyl groups in the side chains, and their furkanolamines. The resulting polyols are also suitable.

Suitable long chain polyamines are compounds having a molecular weight greater than 400 and having at least one heptadmin group. Examples include polyether polyamines obtained by reacting the terminal hydroxyl group of polyoxyfulkylene polyol with ammonia or the like, and polyether polyamines obtained by reacting a known polyol with ethyleneimine or the like.

Long-chain 7-minoboliol is a compound with a molecular weight of over 400 that contains both an amino group and a hydroxyl group in the molecule. For example, Amitsubo-11ol, which has a part of the hydroxyl group of a polyol replaced with an amino group by the method described above, is a compound with a molecular weight of over 400. Can be mentioned. Also preferably used are polyether polyol derivatives having at least one aminobenzoic acid ester group at the end, which are disclosed in JP-A No. 59-53533.

In the present invention, the polyaddition reaction between a polyester polyol derivative having at least one terminal amino group and a polyisocyanate usually has an incyanate index of 95.
It is preferable to carry out in the range of 120 to 120. The same holds true even in the coexistence 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 using a polyisocyanate that is liquid at room temperature, the reaction system can be at room temperature. When reacting in the presence of a known long-chain active hydrogen-containing compound, chain extender, or blowing agent, it is preferable to mix and dissolve these components in the polyester polyol derivative in advance. Another effective method is a prepolymer method in which part or all of the polyisocyanate is reacted in advance with excess polyisocyanate to form an incyanate-terminated prepolymer, which is then reacted with the remaining polyester polyol derivative and/or chain extender. Alternatively, part or all of a known long-chain polyol may be reacted in advance with an excess of polyisocyanate to form an isocyanate-terminated prepolymer, and the prepolymer may be reacted with the polyester polyol derivative and the chain extender. These prepolymers are heated at 60-80°C to reduce viscosity and improve processability.
It is preferable to use it by heating it above or by dissolving it in an inert solvent.

In addition, when the polymer of the present invention is made into an elastomer by casting, it is preferable that the mold temperature is usually heated to 50 to 100°C.6 When the polymer of the present invention is made into a foam, water or The reaction may be carried out in the presence of a blowing agent such as a low boiling point compound such as monochlorotriple olomethane.

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

Compared to the corresponding polyester urethane, 1.1
f11 Excellent mechanical strength. This is especially noticeable at high temperatures.

2. Moderate reactivity.

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

3. Excellent compatibility.

When using an amine chain extender, the apparent reaction becomes extremely fast in the case of ordinary polyester polyols. This is because the chain extender component that reacted first precipitates from the reaction solution due to the low compatibility of the reaction system and the large difference in reaction rate between the polyol and chain extender. In the present invention, since the compatibility is excellent and the reaction rate is well balanced, an appropriate reaction rate can be obtained.

4. It is immoral.

The polymer obtained by the present invention is of good quality and does not change over time in hardness or the like due to crystallization, unlike polymers obtained from ordinary polyester polyols.

(Examples) The present invention will be specifically explained below with reference to reference examples, working examples, and comparative examples.

Reference Example 1 (Synthesis of polyester polyol derivative) Lactone-based polyester polyol [Plaxel-21
0, manufactured by Daicel Corporation, MW 990, OH value 2.02
meq/g] 2442 g (4,935 eq) was placed in a 4-tubular flask equipped with a stirring bar, a cooling tube, a thermometer, and a nitrogen gas introduction tube, and dehydrated under reduced pressure at 100° C. for 1 hour under a nitrogen gas flow. Next, 570.5 g of para-7-ethyl 7-benzoate [manufactured by Gyudon Kagaku Yakuhin Kogyo Co., Ltd., first grade reagent]
3.48 mole) and raise the temperature to 88°C.

Next, 1,025 g (340
When the mixture was stirred and heated, the reaction system became a homogeneous solution at 110° C., and the wall of the four-tube flask began to be wetted with the produced ethanol. Continue to raise the temperature to 225
The reaction was carried out for 2 hours and 30 minutes in the temperature range of ~230°C, and the tar 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 flow. The system was heated to 200°C, and unreacted ethyl para-aminobenzoate was distilled off for 3 hours to obtain a reddish brown liquid with a viscosity of 11,000 cps at 30°C. Yield was 2854g.

When this liquid was analyzed by del permeation chromatography, no free ethyl para-aminobenzoate was detected. In addition, this liquid was analyzed using the following analysis method.
The production of a polyester polyol derivative having a terminal amino group was confirmed.

That is, the amine value was 0.998 according to titration with persalt folic acid in glacial acetic acid (Analytical Chemistry Handbook, Revised Third Edition, page 261).
meq/g. In addition, the hydroxyl value measurement method (JIS K
1557), it was 1.2 fumeq/g.

These measured values are based on the calculated amine value of 1,213 meq/g and active hydrogen value of 1,728 m calculated from the charged amounts of polyester polyol and ethyl para-aminobenzoate.
It did not match eq/g. Actual active hydrogen value 1.2
77@eq/g, the molecular weight of the polyester polyol derivative having a terminal amino group is 1566, and analysis of this product by del permeation chromatography reveals that compared to the raw material polyester polyol,
It was confirmed that the molecular weight distribution was shifted toward the polymer side. Further, +SC-NMR analysis of this product confirmed the presence of a 7-mido group, and the amide group was present in an amount of 20 mol % based on the terminal amino group.

Also, according to elemental analysis, nitrogen is 1.68%, which is calculated from the amide! (total nitrogen - amine). From these results, the product polyester polyol derivative has 78.2% of the terminal hydroxyl groups converted to amino groups and contains 20 mol% of aromatic amide groups in the molecular chain based on the terminal amino groups. It was a compound. The average structure of the product is estimated to be as follows.

Mw 1566 a + b + c = 11.2 Example 1 (Polyaddition polymer of polyester polyol derivative and MDI) Polyester polyol derivative 10 obtained in Reference Example 1
Weigh out 0g into a 30011+1 polypropylene cup and heat to 50°C. 16.76 g of 4,4゛-diphenylmethane diisocyanate [pure MDI, manufactured by Japan Polyurethane Industry Co., Ltd. [Millionate MTJ] melted at 50°C
was added and mixed for 30 seconds using a propeller type stirrer. Then, the mixture was foamed in a vacuum desiccator and poured into an iron mold preheated to 100°C. Heat this mold to 110℃
I put it in the open and let it harden.

The tack free time was 11 minutes. After 2 hours, remove the cured product from the mold and continue! Bost cured at 110°C for 16 hours. The 2+ue thick sheet thus obtained was a transparent, soft but strong elastomer. 7 at room temperature
After curing for one day, physical properties were measured according to JIS K6301 (hereinafter the same), and the results are shown in Table 1.

Comparative Example 1 For comparison with the polymer of Example 1, a corresponding polymer of polyester polyol and MDI was synthesized. In order to match the molecular weight with the polyester polyol derivative used in Example 1, two types of polycaprolactone polyols (PCL) with a molecular weight of about 200 G and about 1000 were blended and used with an average molecular weight of 1566. That is, PCL
2000 (“Plaxel 220” manufactured by Gwisel Chemical Industry)
, molecular weight 1959) 74.5g and P CL 1000
(“Plaxel 210” manufactured by Daicel Chemical Industries, molecular weight 9
(16,
78g), a polymer was synthesized in the same manner as in Example 1. This reaction product was slow to cure and remained tacky even after 1 hour.

After 2 hours, an attempt was made to remove the mold, but it was too soft to remove.The mold was then cured at 110° C. for 16 hours, and the mold was cooled before being removed. The sheet thus obtained was a transparent and soft elastomer. However, this sample became opaque after 3 to 4 days at room temperature.
After 7 days, the hardness reached 86 (JISA). When this sample was heated at 50-60°C for 20 minutes, it became transparent and soft again.

When the hardness was measured after 1 hour at room temperature, it had decreased to 56. This phenomenon is thought to be caused by crystallization of the polyester component in the elastomer.

In the elastomer of Example 1, no change in hardness due to such crystallization was observed. The physical properties of the sample of Comparative Example 1 were measured after crystal removal. The results are shown in Table 1.

mi table Example 2 (Polyaddition polymer of polyester polyol derivative and TDI) 100 g of the polyester polyol derivative of Reference Example 1 heated to 50°C and 2,4'-)lylentin cyanate (2,4-) heated to 25°C TD11 Nippon Polyurethane Kogyo *-) T-100J) 11.67g
A polymer was synthesized in the same manner as in Example 1 using

Tack 717- was approximately 1 hour. After 4 hours, the mold was demolded and subsequently post-cured at 110°C for 16 hours.

A transparent, soft but strong elastomer was thus obtained. The results are shown in Table 2.

Comparative Example 2 For comparison with the polymer of Example 2, a corresponding polymer of polyester polyol and TDI was synthesized. The polyol used was the same as the mixed polyol used in Comparative Example 1. 100g of this mixed polyol (50℃) and 2.4-
Example 1 using T DI (25°C) 11.67.
A polymer was synthesized in the same manner. This reactant cures extremely slowly and is difficult to remove from the mold.
Curing was continued for 20 hours, and the mold was cooled and demolded. The sample thus obtained showed significant crystallization. That is, this sample was transparent and very soft immediately after demolding, but turned white and hardened after one day at room temperature. The hardness reached 94 (JIS A) after 78. When this sample was heated at 50° C. for 20 minutes, it became transparent again and the hardness decreased to 15 (JISA). This is considered to be due to crystallization of the polyester component in the elastomer.

No such change in hardness was observed in the sample of Example 2. The physical properties of the sample of Comparative Example 2 were measured after crystal removal. The results are shown in Table 2.

Table 2 (Note) Measurement was not possible due to softening and deformation. Example 3 (Polyaddition polymer of polyester polyol derivative, chain extender, and MDI) 3 to 100 g of the polyester polyol derivative of Reference Example 1.
, 3'-fuchloro-4,4'-diaminonophenylmethane (Ihara Chemical Industry "Curemin MTJ") 8.5g
108.5 g of a mixed solution of which was dissolved and the liquid temperature was adjusted to 50°C.
and using molten M Dr (25,1 g) at 50 °C,
A polymer was synthesized in the same manner as in Example 1. However, the mixing time was 20 seconds, the defoaming was performed for 1 minute, and the 0
The tack of the reactant was 717-4 minutes.

The mold was removed in 30 minutes and subsequently post-cured at 110°C for 16 hours. In this way, a translucent and tough sheet-like elastomer was obtained. The physical properties are shown in Table 3.

Comparative Example 3 A polymer was synthesized using the corresponding polyester polyol for comparison with the polymer of Example 3.

That is, to 100 g of the mixed polyol used in Comparative Example 1, 3.
Mixture 108 in which 8.5 g of 3'-fuchloro-4,4'-diaminodiphenylmethane was dissolved and the liquid temperature was adjusted to 50°C.
．． 5 g and 50° C. molten M D I (25, Ig) was used. When the same operation as in Example 3 was carried out, the reaction was too fast and the reaction solution became white and thickened at 1 minute and 10 seconds during the defoaming process, making it impossible to cast. It is now possible to cast the mold by shortening the time to completion to 45 seconds.

As expected, the reaction solution turned white in 1 minute and 10 seconds, and became tack-free in 2 minutes and 15 seconds. Even though the assimilation reaction is fast, demolding is difficult due to the brittleness of the cured product in 30 minutes;
It took 0 minutes. Subsequently, it was post cured at 110°C for 16 hours. In this way, a cloudy white hard elastomer was obtained.

This sample showed a change in hardness due to crystallization. That is, the hardness of the sample reached 96 (JISA) after 7 days, but after heating at 60°C for 20 minutes, the hardness decreased to 77.
It declined to . No such change in hardness was observed in the sample of Example 3. Physical properties were measured after crystal removal. The results are shown in Table WS3.

Table 3 I couldn't measure it because it was destroyed.

Example 4 (Polyaddition polymer of polyester polyol derivative, chain extender, and TDI) 3 to 100 g of the polyester polyol derivative of Reference Example 1
, 3'-dichloro-4,4'-diamino:) A mixed solution of 117. 2.4-T DI (2
A polymer was synthesized in the same manner as in Example 3 using 3.3g). The tack-free time of the reaction product was 9 minutes. The mold was demolded in 30 minutes and subsequently post-cured at 110°C for 16 hours. In this way, a transparent and tough sheet-like elastomer was obtained. The physical properties are shown in Table 4.

Comparative Example 4 For comparison with the polymer of Example 4, a polymer was synthesized using the corresponding polyester polyol.

That is, to 100 g of the mixed polyol used in Comparative Example 1, 3.
3'-fuchloro-4,4'-noamifudiphenylmethane17. Mixture 11 in which Og was dissolved and the liquid temperature was set to 50°C
2.4-T D I (23,3
g) was used. When the same procedure as in Example 3 was carried out, the reaction was extremely rapid, and the reaction solution turned white in about 40 seconds during the defoaming process, making it impossible to cast. Therefore, the liquid temperature of the above mixed liquid was
The temperature was lowered to 4°C, the mixing time was shortened to 15 seconds, and the mixture was immediately cast without defoaming. The reaction solution turned white and solidified in about 40 seconds. Despite the rapid solidification reaction, demolding was difficult in 40 minutes because the cured product was brittle, and when curing was continued, cracks appeared in about 2 hours, so demolding was performed. It is thought that the cracks occurred because the strength was insufficient to withstand curing shrinkage. 1 at 110℃
Post cured for 6 hours. A cloudy white hard I-1 sheet elastomer was thus obtained - this sample showed a change in hardness due to crystallization. That is, the hardness of the sample was 97 (JISA) after 7 days, but the hardness decreased to ±82 when heated at 60° C. for 20 minutes. No such change in hardness was observed in the sample of Example 4. The physical properties of the sample of the comparative example were measured after crystal removal. The results are shown in Table tjS4.Table 4 Because it was destroyed, it could not be measured.

Example 5 (Addition polymer foam of polyester polyol derivative, chain extender, and MDI) To 100 g of the polyester polyol derivative of Reference Example 1,
5.8 g of 1,4-butadiol (1st class reagent), 0.3 g of pure water o, ag, ) lyethylenenoamine (manufactured by Toyo Soda Kogyo, TEDA) were added and dissolved, and the liquid temperature was raised to 47°C.
And so. Melt M D I (36
, 2g) was added, mixed vigorously for 10 seconds, and immediately poured into an iron mold with a thickness of 4III and 7 taps preheated to 60°C, and foamed. The foam surface becomes tack 7 in about 40 seconds.
! It became 7-. It was demolded in 10 minutes. In this way, a soft sheet-like foam with a density of 0.60 was obtained. Physical properties were measured after 7 days. The results are shown in Table 5.

Comparative Example 5 In order to compare with the foam of Example 5, a foam was synthesized in exactly the same manner as in Example 5, using the mixed polyol of Comparative Example 1 instead of the polyester polyol derivative of Example 5. The height of this foam was 1 minute and 20 seconds. Since the reaction was rather slow, demolding required 20 minutes. In this way, a soft sheet-like foam with a density of 0.60 was obtained.

This sample showed hardness changes due to crystallization.

That is, the hardness of the sample after 7 days was 46 (JTS A), but the hardness decreased to 36 after heating at 60° C. for 20 minutes. Note that such a change in hardness was not observed in the foam of Example 5. The physical properties of the sample of Comparative Example 5 were measured after crystal removal. The results are shown in Table 5.

(that's all)

Claims (6)

[Claims] (1) Polyester polyol derivative with general formula [I]▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [A: There are ▲numerical formulas, chemical formulas, tables, etc.▼ groups in the main chain with a molecular weight of 400 to 10,000. n-valent polyester polyol residue obtained by removing a terminal H atom from an n-valent polyester polyol n: an integer of 2≦n≦4 x: average value, 0≦x≦(n-1) There are mathematical formulas, chemical formulas, tables, etc. in the main chain of -NH- group of ▼ group has an amide group adjacent to the carbonyl residue of aminobenzoic acid and/or the carbonyl residue of polybasic acid of polyester polyol. and the -CO- group forms an ester group or an amide group] and a polyisocyanate. (2) In the reaction with polyisocyanate, the molecular weight is 4.
The polymer according to claim 1, which is obtained by reacting in the coexistence of a chain extender of 0.00 or less. (3) In the reaction with polyisocyanate, the molecular weight is 4.
The polymer according to claim 1, which is obtained by reacting in the coexistence of a long-chain polyol, a long-chain polyamine, and/or a long-chain amino polyol exceeding 0.00. (4) Reacting polyisocyanate with a polyester polyol derivative of general formula [I] obtained by reacting 0.25 n to 10 n mole of aminobenzoic acid alkyl ester with 1 mole of n-valent polyester polyol having a molecular weight of 400 to 10,000. A method for producing a polymer according to claim 1, which comprises: (5) In the reaction with polyisocyanate, the molecular weight is 4.
4. The method according to claim 4, wherein the reaction is carried out in the presence of a chain extender of 0.00 or less. (6) In the reaction with polyisocyanate, the molecular weight is 4.
The method according to claim 4, wherein the reaction is carried out in the coexistence of a long-chain polyol, a long-chain polyamine, and/or a long-chain amino polyol exceeding 0.00.