JPS612733A - Polyester derivative and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain the titled derivative capable of giving polymers with high wear and heat resistance through reaction with polyisocyanate, by the reaction, in the presence of an aliphatic alcohol, between a specific polyoxyalkylene polyol and amino-benzoic acid. CONSTITUTION:The objective derivative of formula [A is n-valent polyoxy- alkylene polyol residue produced by elimination of hydroxyl group from polyoxyalkylene polyol; n is 2-8; 0<=x (mean value) <n-1; 0.05<=y (mean value) <1] can be obtained by the reaction between (A) n-valent polyoxyalkylene polyol with a molecular weight 400-10,000 (n is 2-8) and (B) aminobenzoic acid in a molar ratio of the component (A) to the component (B): 1 to 0.125n-2n (pref. 0.5n-2n) in the presence of (C) 0.125n-30n equivalents of an aliphatic alcohol (e.g. methanol, ethanol).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyether derivative having at least one terminal amine 7 group represented by the general formula [11] and a method for producing the same.

Patent application No. 57-199384, which is the applicant's earlier application;
Then, by reducing the method for producing the polymer and τ obtained by the reaction of the polyether bosiol derivative represented by the general formula and polyisocyanate, the resulting product is attributable to its structure. It is stated that it has excellent heat resistance and mechanical strength.

Furthermore, Japanese Patent Application No. 57-185447, which was filed by the present applicant, discloses a method for producing a polyether polyol derivative having 7 amino groups at the end.

The present invention is based on Japanese Patent Application No. 57-19938, which is the applicant's earlier application.
4, 57-165447, by further developing the technology.

In the reaction between polyisocyanate and the polyol derivative of the present invention, which has 7 amino groups at the terminal and a hydroxyl group as necessary, and an aromatic amide group by PAJ & at the terminal aminophenyl group, the aromatic amide Poly(urethane)ureamide polymers containing groups are obtained, which have many significant advantages compared to polyurethanes obtained from corresponding polyols and polyisocyanates.

In particular, the poly(urethane) produced by the polyaddition reaction of the polyol-induced stripe having an aromatic amide group adjacent to the terminal amide-7 phenyl group and the polyisocyanate of the present invention ) Urea amide polymers have a structure 'two-phase optical' compared to polyurethane, higher heat resistance and stronger mechanical strength.

U.S. Pat. No. 4,328,322 discloses that a polyol is reacted with para-nitrobenzoic acid chloride, and then all terminal hydroxyl groups of the polyol are converted to amide-7 groups by reacting the polyol with para-nitrobenzoic acid chloride. Polymers obtained by polyaddition reactions of isocyanates are disclosed. In addition, polyincyanate and para-amino-7 benzoic acid amide of polyamine are prepared by reacting the polyamine with para-nitrobenzoic acid chloride or para-nitrobenzoic acid and then reducing the nitro group to convert all the terminal amine groups of the polyamine into different types of amine-7 groups. Polymers obtained by polyaddition reactions are disclosed.

The present invention relates to a polyether derivative having a polyether polyol terminal having 7 amine groups bonded with an aromatic ester, an aromatic or a niamide group, and a poly(urethane/ ) Urea amide 1 conjugate is U.S. Patent No. 4.328
The chemical structure is completely different from that of the polymer of No. 322.

An object of the present invention is to provide a polyether derivative zJ having an amide 7 group and, if necessary, a hydroxyl group at the terminal, and a simple method for producing the same.

The present invention is to remove the hydroxyl group from the 11-valent polyoxyalkylene polyol of the general formula [11 [A: molecular weight 400-] 0000 (residue W of the monovalent polyoxy 7' alkylene polyol obtained by r) 8 integer This relates to ether derivatives and the manufacturing method of No. 7.

The polyether derivative of the general formula [1'I used in the present invention partially connects the terminal end of the polyether polyol to
Alternatively, all aromatic amide groups are converted into adjacent aromatic amide groups, and the production is completed by substantially 1 r'i reaction, and the yield is high and no purification is required.

The polyether derivative used in the present invention is obtained by reacting a di- to octavalent polyoxyalkylene polyol with a molecular weight of 400-10 (100) and 7-minobenzoic acid in the presence of an aliphatic alcohol.

Suitable polyoxyalkylene polyols used in the present invention include one or more alkylene oxides such as ethylene oxide, propylene oxide, and tetrahydro-7rane in the presence of a suitable initiator such as water, a low molecular weight polyol, and a low molecular weight amine. Polyether polyols having a valence of 2 to 8 molecules @400 to +0000 can be mentioned, which are obtained by addition polymerization of 2- to 8-valent molecules in any order, and these can be obtained by one known method.

Examples of low molecular weight polyols suitable as the above-mentioned initiators include ethylene glyfur, propylene glyfur,
1.4-butanediol, 1.6-hexaneol,
Examples include glycerin, I-trimethylolpropane, pentaerythritol, sorbitol, sucrose, hydroquinone, 2,2-bis(4-hydroxyphenyl)propane, and examples of paper-based amines include methylamine, butalamine, and ethylenediamine. , aniline, tolylene diamine, etc., and flukanolamines such as ethanolamine, jetanolamine, and triethanolamine can also be used.

Among the above-mentioned polyoxyalkylene polyols, the polyether of the present invention obtained therefrom has a terminal 7-amino group and optionally a hydroxyl group, and an aromatic amide group adjacent to a part of the terminal 7-minophenyl group. When polyol derivatives are used as raw materials for elastomer synthesis, molecules 111
Divalent to trivalent polyoxytetramethylene glycol of 000 to 4000, polyoxypropylene polyol, polyoxybrobylene polyoxyethylene polyol, and the like are suitable. Further, when used as a synthetic raw material for plastics, trivalent to octavalent polyoxypropylene polyols having a molecular weight of 400 to 1,500 are suitable.

The amino-7 benzoic acid used in the present invention may be any of ortho, meta, or para-ami7 benzoic acid, but when the polyether N conductor of the present invention is used as a synthetic raw material for elastomers and plastics, para-ami7 benzoic acid is particularly preferred. It is.

Various types of aliphatic alcohols can be used in the present invention, and preferred examples include methanol, ethanol, propyl, butyl, hexanol, octatool, cyclobutanol, and cyclopentyl. chain or cyclic monoalcohols having 1 to 8 carbon atoms such as cyclohebutamele, cyclohebutamele, ethylene glyfur,
Examples include alcohols having 2.-8 carbon atoms, such as propanediol, butanediol, hexaneol, and hexaneol. Also suitable are cellosolves such as 2-butoxyshetanol and 2-nitoxyethanol.

In the present invention, 0.125n of amide-7 benzoic acid per 1 mole of the above-mentioned 11-valent polyoxyalkylene polyol.
-2nmol, preferably 0.5n-2nmol, 0,1
It is preferred to carry out the reaction in the presence of 25n to 3011 equivalents of aliphatic alcohol.

The aromatic amide group in the polyether derivative having an aromatic or near amide group in contact with the terminal aminophenyl group is N
It can be quantitatively confirmed by MR analysis and nitrogen elemental analysis.

Although the reaction of aromatic amide radicals has not yet been fully elucidated, it can be inferred as follows.

ROI+ +' +1. , N%COO1l →
It OCObeφΣold1□Roco()Nu2+ o
2-)coon→ ROCO-@)-N HCO((Σ
and old 12 The polyether derivative obtained by the method of the present invention is an esterified product in which all the terminal hydroxyl groups are converted to amide 7 groups, or a partially esterified product in which some unreacted hydroxyl groups remain, and the terminal 7 Contains an aromatic amide group adjacent to the minophenyl group. The degree of esterification, that is, the degree of amine conversion and amidation, can vary over a wide range depending on the application, and it is necessary that on average at least one hydroxyl group of the polyether polyol is esterified. , preferably the esterification rate, that is, the amine conversion rate is about 50 to 100%, and WA is added to the aminophenyl group.
The strained amino group is 10-50% of the terminal amino group 7J&
is preferred. When the 7-mido group is in this range, the polyether derivative has an appropriate viscosity and good moldability.

The polyether derivative of the present invention can be dehydrated and dealcoholized by heating to usually 150 to 250°C while passing an inert gas such as nitrogen gas or +8 gas into F without a catalyst or in the presence of a known esterification catalyst. This is achieved by When using a catalyst, a weakly acidic or weakly basic catalyst that does not produce ether or olefin by dehydration of the polyol is preferable, such as metal oxides such as antimony trioxide, -lead oxide, tetraisopropyl titanate, and tetrabutyl. Examples include organic titanium compounds such as titanates, alkaline earth metal salts of weak acids such as calcium acetate, and 1) titanium compounds are preferred. The catalyst amount is usually 1000 or more or less than 1111. Further, in the reaction, an active solvent, a coloring inhibitor such as 1-rifenyl phosphate, etc. can also be used. The reaction is first carried out until the water is distilled off, but in the first step, water and excess aliphatic alcohol may be distilled off at the same time without being separated, or water and aliphatic alcohol may be separated and only water removed. Alternatively, a method may be used in which the aliphatic alcohol is distilled off and the aliphatic alcohol is returned to the reaction system. The reaction is then continued until the aliphatic alcohol has been distilled off, and the system is further reduced in pressure to completely distill off the alcohol and excess amiobenzoic acid, if present. No particular purification is required.

In the polymer obtained by the reaction of the polyether derivative and polyisocyanate of the present invention, the effect of containing an aromatic amide group is noticeable in terms of wear resistance and heat resistance.

The present invention will be specifically described below with reference to Examples and Reference Examples.

Example 1 Polyoxytetramethylene glycol [Mitsubishi Chemical Corporation (
Co., Ltd., PTM (:1500, MM]49]3000
g (4,01eq), para-aminobenzoic acid (Gyudon Chemicals, 1632H (4,6IC+1) as a reagent, 520g (3
, 99eq), Te1 Butyl Titanium) 0,6. was heated in a Yotsuro 7 Laser while blowing dry nitrogen gas, and when the temperature was raised to 215°C, 2-ethyl-1-hexanol refluxed, and when the temperature was further raised to 219°C, it settled in the F section of the cooler. A: Water droplets began to drip into the liquid separation tube. Continue heating to 215-23 +1'C
If fi Il, '7 questions are held in the range of ζ
73.5H of water was distilled out.

Then, at a temperature of 200-210°C, 17-110 ro! l
1II (ε), ethyl-1-hexanol was distilled off, and the temperature was further raised to 220-240°C,
1+l I+l Under a reduced pressure of 88, 2-ethyl-1-hex/-l was added to 11'1) I5.The viscosity at 27°C was 950.
A reddish brown liquid of 0 cps was obtained.

The yield was 210:i. This liquid was analyzed using Gel Permeation Chromatograph 7, and it was found that almost no free para-amino-7-benzoic acid and para-amino-7-benzoic acid octyl ester were detected.

Furthermore, the production of a polyether derivative having 7 terminal amine groups was confirmed using the following analysis method for this liquid.

That is, according to titration with perchloric acid in glacial acetic acid (Divided Chemistry Handbook, revised 3rd edition, page 261), the amine value is], 082
The hydroxyl value measurement method (1557 in llS) that can measure the total of 6-fold, hydroxyl groups and 7-amino groups, which was the ring eq/ε, J:
If so, it was 1.1691Oeq/&te. When this product was analyzed by del permeation chromatography, free para-7m-7benzoic acid and octyl para-7-benzoate were not detected, and the molecular weight distribution of the single peak was almost the same as that of the raw material PTMG 1500. there were. Therefore, the terminal hydroxyl group of 1500 in P1'H is 92.6% amino7
This means that it has been converted to the base.

Furthermore, the presence of an amide group was confirmed in the lcoC-NMR fraction 41i of this product. The amide group contained was present at 11.5% based on the terminal amino group. In addition, nitrogen 'LA
9 ar Iil'l HaI, 7 d196 te;
J) −, r r knee. - Method 7 Mi7 fffli Nitrogen content based on Ami 7 group calculated from total 9 is 1.51
%. Based on the nitrogen element 'Jf, the fractionation value is 1) After subtracting the amount of nitrogen content (%) determined from the amine value as the nitrogen based on amide JJ-, the amount of amide groups contained is determined, based on the 7 terminal amide groups. Therefore, it is present at 12.4%. ”C-
There are differences in the analytical methods between the amount of amide groups contained as determined from the NHf < 0 ratio and the amount of amide groups contained as determined from the elemental analysis values, and no matching values were obtained, but in both cases, 10% or more of amide groups It shows that it exists.

Real JAiPIJ2 Molecule 'i+ 021 polyoxytetramethylene cryfur [3W+&<MatchHJ[, P1'NG+(1001
15 (I (2,94 pq), para-amino-7 benzoic acid 48
The reaction was carried out in the same manner as in Example 1 using 0.69 g of 48 (: (, 53 t・q), 2-ethyl-1-hexyl 7-7 (i6H (5,88 rq), tetrabutyl rapeseed). Row ivy, Q, i; t, l 9 i! + I;
A pale yellow liquid with a viscosity of 5980 cps at 27°C was obtained.

The amine value was 1.453 meq/g, and the total number of amine 7 groups and hydroxyl groups was 1, (i08 meq/g), which means that 90.4% of the terminal hydroxyl groups of the polyol were converted to amine 7 groups.

In addition, the amide content determined in the same manner as in Reference Example 1 was “'C
-13.2% from NMR analysis, 1 from nitrogen elemental analysis
It was 4.3%.

Reference Example 1 200g (32g) of the polyether derivative obtained in Example 2
Heat 2 meq) to 50°C and melt 4.4 at 50°C.
'-Cyphenylmethane diisocyanate) (MDI) 4
Add 2.3B (938iaeq), mix, defoamer,
It was poured into an iron mold at 0°C. Pot life was 7 minutes. After 1 hour, the mold was removed and placed in an oven at 110°C.
After heating 6RIi11 and curing at room temperature for 7 days, physical properties were measured. The results are shown in Table 1.

Example 3 Polyoxytetranotylene glycol with molecule @+986: l-
[manufactured by Mitsubishi Kasei Corporation, P'rHG20001150]
08(], 51eq), para-aminobenzoic acid 249bi(
1,81eq), 2-ethyl-1-hex/-l: 19
38 (3,02+・(ri,tetrabutyl rapeseed)0.
The reaction was carried out in the same manner as in Example 1 using 548. Yield F7+ [199H Viscosity at 127℃ 9800cps
A pale yellow liquid was obtained.

The amine value was 0.795 meq/g, and the total of the amine 7 groups and hydroxyl groups was 0.927 meq/g, which means that 85.8% of the terminal hydroxyl groups of the polyol were converted to amine 7 groups.

In addition, the amide content determined in the same manner as in Example 1 was “C-
NHR analysis: 1) 14.9%, nitrogen elemental analysis: 1
It was 5.2%.

Reference Example 2 Polyether derivative 11.2008 obtained in Example 3 (
18511+t・Ll) to 50°C,
24.3H (1911aeQ) of molten Mi)l at 60'C was added, mixed, defoamed and poured into a steel mold at 60'C. Pot life was 12 minutes. The following operations were performed in the same manner as in Reference Example 1. The results are shown in Table 1.

Example 4 Polyoledipropylene glycol (Mitsuiguchiso Urethane, ED56) 150011 (1,52PC+) was capped with ethylene oxide having a molecular weight of 1980.
, para-amino-7 benzoic acid 272g (L98eq), 2-ethyl-1-hexanol 258B (+, 98eq
) and tetrabutyl nathanate (1.02%) in the same manner as in Example 1. Yield 1735g, 27
A yellow liquid was obtained with a viscosity of 2350 cps at °C.

The amine value was 0.787I11eq/g, and the total of amide 7 groups and hydroxyl groups was 0.935 + aeq/g, which means that 84.2% of the terminal hydroxyl 7,1 of the polyol was converted to amide 7 groups. The amide content was determined from elemental analysis of nitrogen and was 10.1%.

Reference Example 3 200g (18g) of the polyether derivative obtained in Example 4
71 oeq) to 50°C and molten Ml at 50°C.
)l of 24.5g (196IIleq) and mix;
The mixture was degassed and poured into a 50'C iron mold. The pot life was 1 min. After 1 hour, it was demolded and placed in an oven at 110°C for 13 hours.
1k, which was born 1/i, was measured. The results are shown in Table 1.

Claims (2)

[Claims] (1) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] [A: n-valent polyoxyalkylene polyol obtained by removing hydroxyl groups from n-valent polyoxyalkylene polyol with a molecular weight of 400 to 10,000 Oxyalkylene polyol residue n: an integer from 2 to 8 x: an average value, and a number of 0≦x<(n-1) y: an average value, and a number of 0.05≦y<1] Polyether derivatives represented. (2) 0.1 aminobenzoic acid per mol of n-valent polyoxyalkylene polyol with a molecular weight of 400 to 10,000
A method for producing a polyether derivative of general formula [I], which comprises reacting 25n to 2n moles in the presence of 0.125n to 30n equivalent of aliphatic alcohol.