JPS61126132A - Polyester polyol derivative and its production - Google Patents

Abstract

PURPOSE:To obtain the titled derivative which can give a polymer terminated with an amino group and being excellent in heat resistance and mechanical strength, by reacting a specified polyester glycol with an alkyl aminobenzoate. CONSTITUTION:1mol of an n-hydric (n is 2-4) polyester polyol (a) of a MW of 400-10,000 is reacted with 0.25n-10nmol of alkyl aminobenzoate (b) at 150-250 deg.C in an inert gas in the presence of, if necessary, 1,000ppm or below esterification catalyst, an inert solvent, a color stabilizer, etc., to obtain the titled derivative of formula I [wherein A is an n-hydric polyester polyol residue obtained by removing the terminal H atoms from component (a) having a group of formula II in the main chain, x is an average in the range of 0<=x<=n-1, in the group (formula II) in the main chain, the group of formula III is bonded with the carbonyl group of aminobenzoic acid and/or a polyester polyol polybasic acid to form an amide group and the group of formula IV forms an ester group or an amide group].

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a polyester polyol derivative having at least one terminal amine 7 group represented by the general formula (1).

(Prior art) Patent application No. 57-199384, which is the applicant's earlier application. Same 5
7-165447. 58-75182. 59-66
No. 599, No. 59-124019 discloses polyether polyol derivatives having an amino group at the end of the molecule, a method for producing the same, a polymer obtained by reacting these polyether polyol derivatives with a polyisocyanate, and a method for producing the same. 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 an amide group and optionally a hydroxyl group at the molecular end and an aromatic amide group in the main chain with a polyisocyanate, a flare group,
Poly(urethane)urea 7mide polymers containing aromatic amide groups are obtained and have a number of distinct advantages compared to the corresponding polyurethanes obtained from polyester polyols and polyisocyanates.

In particular, the poly(urethane) ureaamide polymer obtained by the polyaddition reaction of a polyester polyol derivative having an amide 7 group and optionally a hydroxyl group at the terminal end and an aromatic 7 amide group in the main chain and a polyisocyanate. The union is
It has higher heat resistance and stronger mechanical strength compared to structurally equivalent polyurethanes.

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, polyamine para-ami7 benzoic acid amide and polyamine were obtained by reacting the polyamine with para-nitrobenzoic acid chloride or para-nitrobenzoic acid, and then reducing the nitro group, thereby converting all the terminal 7 amide groups of the polyamine into 7 different types of amide groups. Polymers obtained by polyaddition reactions of isocyanates are disclosed.

The present invention produces a poly(urethane) urea amide polymer by a polyaddition reaction between a polyester polyol derivative having an aromatic amide group in the main chain and a polyisocyanate, in which a part or all of the terminals of a polyester polyol are substituted with 7 aromatic amide groups. This is what you get. 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 amide 7 groups at the end, a hydroxyl group if necessary, and an aromatic amide group in the main chain, and a simple method for producing the same. It is about providing.

(Means for Solving the Problems) The present invention provides a polyester polyol derivative of the general formula [1] [A: 11 obtained by removing terminal Hw and a child from ruboriol in the main chain with a molecular weight of 4.00 to 10,000.
Value of polyester polyol residue 1: Integer of 2≦n≦4×: Average value, number of 0≦X≦(n-1) 7 Carbonyl residue of minobenzoic acid and/or polybasic of polyester polyol An amide group is formed adjacent to the carbonyl residue of an acid, and the -C- group forms an ester group or an amide group] and a method for producing the same.

The polyester polyol N conductor of the general formula CI) of the present invention is a polyester polyol whose ends are partially or completely aromatically aminated to contain an aromatic amide group in the main chain, and substantially the reaction of 15F is carried out. The production is completed, the yield is high, and no purification is required.

The polyester polyol derivative of the present invention is obtained by reacting a di- to tetravalent polyester polyol with a molecular weight of 400 to too much and a 7-minobenzoic 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 7 nobic acid, sebacic acid,
Saturated or unsaturated dibasic acids such as terephthalic acid, isophthalic acid, maleic acid, and 7-malic acid; acid anhydrides such as maleic anhydride and 7-thalic anhydride; nofurkyl esters such as dimethyl terephthalate; and ethylene glycol. It is a polyester polyol obtained by a condensation reaction with glycols such as propylene glycol, butylene glycol, queethylene glycol, noprobylene glycol, neopentyl glycol, and 1,6-hexylene glycol. Specific examples include polyethylene adipate polyol. , polybutylene azobate polyol, polyhexylene adipate polyol, etc., anovate polyols consisting of one type of acid and one type of glycol, polyethylene butylene adipate polyol, polyethylene diethylene anovate polyol-7, polyhexylene neoventrene. Adipate polyols made of 01 types of acids and many types of glycols such as 7novate polyol-71, polyenalene 7novatetere 7 tallate polyols made of many types of acids and one type of glycol, polyethylene adipate in 7 tallate polyols, etc. Examples include aromatic polyols.

Lactone-based polyester polyols are obtained by ring-opening polymerization of lactone necks such as ε-caprolactone and γ-butyrolactone, and polyols with various compositions can be obtained depending on the type of initiator. Glycols such as ethylene glycol and butylene glycol as initiators,
Polyether polyols such as polyoxybu-a-pyrene glycol (PPG) and polyoxytetramethylene glycol (PTMG), condensed polyester polyols such as 7 Nove) 31%, etc. are selected, but any of them can be used in the present invention. It is suitable.

Further, polyols having two or more functionalities such as condensed polyester polyols and lactone polyester polyols are also suitable for use in 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 derivative of the present invention obtained therefrom is used as a raw material for elastomer synthesis, the molecular fi 1000 to 4
000 di- to trivalent polyester polyol is suitable.

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 using pentaerythritol as an initiator are suitable.

The ami-7 benzoic acid alkyl ester used in the present invention is ortho, meta or para-ami7 benzoic acid fi! Although any fullkyl ester may be used, when the polyester polyol derivative of the present invention is used as a synthetic raw material for elastomers or plastics, a varaminobenzoic acid alkyl ester is particularly suitable.

Various types of alkyl groups can be exemplified as the alkyl group of the ami7benzoic acid alkyl ester, and preferred examples include 11M1-8 linear or Cyclic full kills can be mentioned.

In addition, 2-butoxyethyl, 2-ethoxyethyl, etc. are also suitable6.Also, bis(ami7benzoic acid) alkyl esters can also be used. Bis(ami7benzoic acid) esters such as glycols having 2 to 8 carbon atoms such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and pebtylene glycol are preferred.

In the present invention, the amount of the amicyl-7benzoic acid alkyl ester is 0.00% per mole of the above-mentioned zero-valent polyester polyol.
It is preferred to react 25n-10nmol, preferably 0.5n-2nmol.

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 150 to 250° C. while passing through an inert gas such as a nitrogen bath. When using a catalyst (soil, 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 dehydration of hydroxyl groups, such as antimony dioxide, -lead oxide, etc.) is preferable. metal oxides, organic titanium compounds such as tetraisopropyl titanate and tetrabutyl titanate, alkaline earth metal salts of weak acids such as calcium acetate, and organic titanium compounds are particularly preferred.The catalyst amount is usually 10001) 9T.
Il or less is good. In addition, an inert solvent and a coloring inhibitor such as triphenyl phosphate can also be used in the reaction.

The reaction may be continued until the distillation of the aliphatic alcohol is completed, and the system is further reduced in pressure to completely distill off the alcohol and, if present, the excess aminobenzoic acid alkyl ester. No particular purification is required.

Note that in the reaction between polyester polyol and 7-7benzoic acid alkyl ester, it is important to note that the ester bond in the molecular chain of polyester polyol and the terminal 1108
group or alkyl 7benzoic acid ester of N H2
A transesterification reaction or an amide formation reaction with the group 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. In order to obtain a polyester polyol derivative with a desired molecular weight, attention should also be paid to the amount of raw materials charged. The content of 7-mido groups is an important factor in 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 the aromatic 7-mido group has not yet been fully elucidated, it can be inferred as follows.

Formula (1) is the reaction of terminal amide Z conversion, and formula (2) is the reaction of terminal 7
This reaction produces an aromatic amide group adjacent to a phenyl group. Formula (3) is a reaction in which an aromatic amide group is inserted into the polyester main chain.6 Formula (4) is a reaction in which an aromatic amide group is further inserted into the polyester main chain having an aromatic 7-mido group. The aromatic amide group in the polyester polyol derivative described above can be quantitatively confirmed by NMR analysis and nitrogen elemental analysis.

As a result of 13C-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 found to be greater in the main chain than in the adjacent end. From this result, the following estimation can be made.

Since there is a large difference in the number of two types of ester groups, that is, the difference in the number of terminal ami-7benzoic acid ester groups and the number of ester groups in the main chain,
Naturally, the probability of reaction occurring is greater in the main chain. It is considered that for this reason, the reaction of forming amide groups in the polyester became predominant.

The polyester polyol derivative obtained by the method of the present invention is an esterified product in which all the terminal hydroxyl groups are converted to 7 amide groups, or a partially esterified product in which some unreacted hydroxyl groups remain, and the aromatic amine in the main chain. Contains an r group. 7
The degree of esterification (that is, the esterification rate of terminal hydroxyl groups) and the amidation rate can vary over a wide range depending on the application, and on average at least one hydroxyl group of the polyester polyol is esterified. It is necessary that the amide conversion ratio is preferably about 50 to 100%, and the 7-mid group can be varied over a range of about 5 to 2000 mol % with respect to the terminal 7 amide group, but it is about 5 to 100 mol %. Mol% is preferred. When the 7-mido group is this [12ff], the viscosity of the polyester polyol derivative is appropriate and the moldability is excellent.

In the present invention, an example of the polyester polyol derivative of general formula [I] when ethylene anobate 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, H, CO- groups in the main chain are bonded randomly rather than in blocks, and when bonded to the terminal aminobenzoyl group. and may not bond. 6R,: CH2CH2 R2: CH2CH2CH2CH2 0
≦I) Number q of vr≦m: It is an average value indicating the number of structural orders contained in one molecule, and is not a number of 0.05≦q≦10 or a repetition number.

A positive number determined from ffl bimolecular expression, p + r = m. Similarly, an example of the polyester polyol derivative of general formula [1) when nool obtained by ring-opening polymerization of ε-cabrofuctone is used as a raw material is as follows. It is given by Eq.

R,: CH2CH2CH2CH2CH2R4: CH
2CH2 or an alkyl group such as CH2Cl, CH2CH2, etc. Number of scales E: Average number of structural units contained in one molecule (1't
'a'), o, os≦t≦tonumber+11'l is not the return number.

m: a positive number determined from the molecular weight, s + u + v = kasu The above two examples are examples of the use of bifunctional polyester polyols, and do not limit the structure of the polyester polyol derivative of the present invention. (Effect) The polyester polyol derivative of the present invention reacts with a polyinsyanate to polycondense a poly(urethane) urea 7 amide polymer with a polycarboxylic acid to provide a poly(ester) amide polymer.

The polyester polyol derivative of the present invention is also useful as a curing agent for epoxy resins.

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

Example 1 (Synthesis of polyester polyol derivative) 2-chthonic polyester polyol [Plaxel-21
0, manufactured by Daicel Corporation, MW 990.08, valence 2.02
neq/g) 2442g (4,935eq) was added to a 4-meter tube equipped with a stirring bar, cooling tube, thermometer, and nitrogen gas introduction tube.
The mixture was placed in a Tulo flask and dehydrated under reduced pressure at 100° C. for 1 hour under a popular flow of nitrogen. Next, ethyl para-7-benzene [
Manufactured by Gyudon Kagaku Yakuhin Kogyo Co., Ltd., first grade reagent] 570.5g
(3.46 mole) and raise the temperature to 88°C.

Next, 1.025 g (340
ppm) and stir and raise the temperature, i io'
At c, the reaction system became a homogeneous solution, and the wall of the four-tube flask began to get wet with the produced ethanol. The temperature was further increased, and the reaction was carried out for 2 hours and 30 minutes in the temperature range of 225 to 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 tnmHg* under a nitrogen bath. The temperature of the system was raised to 200°C, and unreacted ethyl para-7-benzoate was distilled off for 3 hours to obtain a reddish brown liquid with a viscosity of 11,000 cps at 30°C. The yield is 2854. Met.

When this liquid was analyzed by del permeation chromatography, free ethyl para-amino-7 benzoate was not 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 perchloric acid in glacial acetic acid (Analytical Chemistry Handbook, Revised 3rd Edition, page 261).
It was n+eq/g. In addition, the total of hydroxyl groups and 7 amino groups (
Hydroxyl value measurement method (JIS
According to K1557), it is 1.277 meq/g. These measured values are based on the calculated amine value of 1.0% calculated from the charged amounts of polyester polyol and ethyl para-aminobenzoate. Z13meq/g, active hydrogen value 1,728
It did not match with meq/g. Actual active hydrogen value 1.
From 277 meq/g, the molecular weight of the polyester polyol conductor having 7 terminal amino groups is 1566, and according to del permeation chromatography 7 (GPC),
Analysis of this product confirmed that the molecular weight distribution was shifted toward higher molecular weight compared to the raw material polyester polyol. Moreover, 13C-N M R of this product
The analysis confirmed the presence of an amide group, and the amide group was present in an amount of 20 mol % based on the 7 terminal amide groups. 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 7-mino groups, and 20 mol% of the aromatic 7-mido groups in the molecular chain relative to the 7-terminal amide groups.
It was a compound containing The average structure of the product is estimated to be as follows.

w1566 a + b + c = 11.2 Example 2 Lactone-based polyester polyol [Plaxel-22
0, manufactured by Daicel Corporation, MW 2000.08 valence 1.0
[27 eq/g]699 g (0,718 eq) was placed in a 4-tube flask and dehydrated under reduced pressure at 100° C. for 1 hour under a nitrogen gas stream. Then, in a 4 flask, add 86. Add Og (0,521 mole) and raise the temperature to 200''C.

next,? ) 5 FultiP *-) 0.195g
(248 ppm) was added and the temperature was raised to 240°C, and ethanol distillation started. Thereafter, ethanol was distilled off in a temperature range of 235 to 240°C for 8 hours.

Next, the reaction system was cooled to 200°C, and then the pressure was reduced to 511IIIHg under a nitrogen gas stream. 220 system
The temperature was raised to ℃, and the unreacted ethyl para-aminobenzoate was
After evaporation for an hour, a reddish-brown liquid with a viscosity of 7000 cps at 60° C. was obtained. Yield was 601g.

The amine value measured by the same method as Example 1 was 0.363.
meq/g, and the active hydrogen value is 0,599 meq/g.
It was g. According to elemental analysis, the nitrogen content was 0.94%6. Therefore, in the polyester polyol derivative of the product, 61% of the terminal hydroxyl groups were converted to amide 7 groups, and the aromatic amide group was added to the terminal amide group in the molecular chain. It was a compound containing 85% of 7 groups.

Example 3 Tuboran N-4040 in Ethylene Atsuba) M polyester polyol, manufactured by Nippon Polyurethane Industries, MW 2
014, OHHO2993meq/g) 645g (0
, 640 eq) was placed in a 4 tube 7 Tesco and dehydrated under reduced pressure at 100°C for 1 hour under a stream of nitrogen gas. Next, add 106 g (0.640 ole) of ethyl para-aminobenzoate and raise the temperature to 100°C. Next, 0.36 g (500 ppm) of tetrabutyl titanate was added and the temperature was raised with stirring, and ethanol began to distill out at about 165°C. The temperature was further increased and the reaction was continued at 200-215°C for 10 hours. The reaction system was then lowered to 200°C and heated to 5 mmH under a popular flow of nitrogen.
The pressure was reduced to 1.3 g, and unreacted ethyl para-aminobenzoate was distilled off for 6 hours. A yellow solid with a yield of 660 g and a melting point of 50° C. was obtained.

The amine value measured in the same manner as in Example I was 0.259.
meq/g't', active hydrogen value is 0. 461m
eq/g. The molecular weight calculated from the active hydrogen group value is 4330. Molecular weight was confirmed by GPC analysis. Further, unreacted ethyl beraami-7benzoate was not detected. According to elemental analysis, nitrogen content was 1.02%. Therefore, the product polyester polyol derivative was a compound in which 56% of the terminal hydroxyl groups were softened to amino groups, and the molecular chain contained 182 mol% of aromatic amide groups based on the 7 terminal amide groups.

Reference Example 1 (Polyester polyol derivative and Ml)r
polyester polyol derivative 10 obtained in Example 1
Weigh out 0 g into a 300 x 1 polypropylene cup and add 5
Heat to 0°C. 16.76 g of 4,4'-di7-functional diisocyanate [pure MDI, "Millione" MTJ manufactured by Nippon Polyurethane Industries] molten at 50°C was added and mixed for 30 seconds using a propeller-type stirrer.Then, the mixture was mixed in vacuum. The mixture was defoamed in a desiccator, poured into an iron mold preheated to 100°C, and the mold was placed in an open air at 110°C to harden.

Tack 717- was 11 minutes. After 2 hours, remove the cured product from the mold and continue! Bost cured at 110°C for 16 hours. The sheet thus obtained, 9.2 cm thick, 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.

Reference Example 2 For comparison with the polymer of Reference 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 Reference Example 1, two types of polycaprolactone polyols (P CL ) with molecular weights of about 2,000 and about 1,000 were blended and used as an average molecular weight of 11,566. That is, PCL
2000 (“Plaxel 220” manufactured by Daicel Chemical Industries)
, molecular weight 1959) 74.5g and P CL 1000
(“Plaxel 210” manufactured by Gwisel Chemical Industry, molecular weight 9
88) 25.5. Blend 100g of mixed polyol with a liquid temperature of 50℃ and molten MDI (16,
76g), a polymer was synthesized in the same manner as in Reference Example 1. This reaction product was slow to cure and remained tacky even after 1 hour.

21i? I tried to remove the mold after dark, but it was too soft to remove, so I continued curing it at 110°C for 16 hours while it was still in the mold, and then removed it after cooling the mold. The sheet thus obtained was a transparent and soft elastomer. However, this sample became opaque after 3 to 4 days at room temperature, and reached a hardness of 86 (JISA) after 7 days. 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 Reference Example 1, no change in hardness due to such crystallization was observed. The physical properties of the sample of Reference Example 2 were measured after crystal removal. The results are shown in Table 1.

Table 1

Claims (2)

[Claims] (1) Polyester polyol derivative of general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [A: In the main chain with a molecular weight of 400 to 10,000 ▲There are mathematical formulas, chemical formulas, tables, etc.▼Removal of the terminal H atom from an n-valent polyester polyol containing groups n-valent polyester polyol residue obtained by n: An integer of 2≦n≦4 x: Average value, number of 0≦x≦(n-1) ▲Mathematical formula, chemical formula, table in the main chain etc. The -NH- group of the ▼ group forms an amide group adjacent to the carbonyl residue of aminobenzoic acid and/or the carbonyl residue of the polybasic acid of the polyester polyol, and the -CO- group forms an amide group. form a group] (2) A method for producing a polyester polyol derivative of the general formula [I], which comprises reacting 0.25 n to 10 n mol of an aminobenzoic acid alkyl ester with 1 mol of an n-valent polyester polyol having a molecular weight of 400 to 10,000.