JPH0433921A - Polyester composition having terminal amino group, its production and production of resin obtained from the polyester composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a polyester composition having an amino group at the end which is useful as a curing agent for polyurea resins and epoxy resins, a method for producing the same, and a method for producing a resin obtained from the polyester composition. More specifically, the polyester composition having an amino group at the end useful as a curing agent for polyurea resins and epoxy resins, the method for producing the same, and the mechanical strength and elasticity obtained by reacting the polyester composition with an organic polyisocyanate. A method for producing a polyurea resin that is useful as parts for automobiles and machines, etc., and an epoxy resin that is useful as electrical parts that have excellent impact resistance and flexibility by reacting the polyester composition with an epoxy resin. The present invention relates to a manufacturing method.

[Prior art]

Polyester polyols used in conventional polyurethane resins have hydroxyl groups at the terminals obtained by reacting a compound having two or more hydroxyl groups in the molecule with a compound having two or more carboxyl groups in the molecule in a state where the hydroxyl groups are in excess. It has the following. A urethane bond obtained by a reaction between a hydroxyl group and an isocyanate group has a weaker intermolecular cohesive force than a urea bond obtained by a reaction between an amino group and an isocyanate group. Therefore, resins incorporating urea bonds are superior to urethane bonds in terms of mechanical strength and the like. Methods for introducing urea bonds into resins include a method involving a reaction between an isocyanate group and water and a method involving a reaction between an isocyanate group and an amino group. In the case of a method based on a reaction between an isocyanate group and water, there is a problem in that carbon dioxide is generated during the reaction and bubbles are formed in the resin. therefore,
It cannot be used in molded products where air bubbles would have an adverse effect. On the other hand, in the method of introducing a urea bond through the reaction of an isocyanate group and an amino group, partial gelation occurs because the reaction of the hydroxyl group of the polyol used together with the amino group is slower than the reaction of the amino group, or only the amino group is reacted during the reaction process. There is a problem in that it takes a long time for the resin to reach its final strength because the reaction of the hydroxyl groups is delayed. Polyether polyamino, in which the terminal hydroxyl group of polyether polyol is converted into an amino group, has also been proposed, but the range of use is limited because the type of amino group, reactivity, etc. cannot be controlled. Also, epoxy resins are generally hard and inflexible. This is because the resin structure is highly crosslinked due to the reaction between a relatively low molecular weight epoxy resin and a relatively low molecular weight curing agent. Although various proposals have been made regarding flexible epoxy, the mechanical strength of epoxy resins is often extremely reduced by making them flexible (and, at present, they have not been put into practical use.

[Problem to be solved by the invention] The present invention not only aims to obtain a resin that can freely control the reaction rate in the reaction with isocyanate, which could not be solved by conventional techniques, and has excellent mechanical strength, etc. The purpose of this reaction is to obtain an epoxy resin with excellent flexibility and flexibility. [Means to solve the problem]

The present inventors have conducted extensive research to solve the above problems, and have now provided the present invention. That is,
A polyester composition consisting of a polyester having an amino group at the terminal and a compound having two or more amino groups in the molecule, in the production of the polyester composition, a compound having 2 to 3 hydroxyl groups in the molecule and a carboxyl group in the molecule. A compound having 2 to 3 groups is reacted with an excess of carboxyl groups to obtain a polyester with terminal carboxyl groups, and then a compound having two or more amino groups in the molecule is reacted with an excess of amino groups. A method for producing a polyester composition having an amino group at the end thereof, characterized in that it is obtained by reacting the polyester composition with a backing polyisocyanate having two or more isocyanate groups in the molecule. A method for producing a polyurea resin, and a method for producing an epoxy resin characterized in that it is obtained by reacting the polyester composition with an epoxy resin having two or more epoxy groups in the molecule. The polyester composition having an amino group at the end of the present invention consists of a polyester having an amino group at the end and a compound having two or more amino groups in the molecule, and is produced by the following method. As the first step, a compound having 2 to 3 hydroxyl groups in the molecule and a compound having 2 to 3 carboxyl groups in the molecule are reacted with an excess of carboxyl groups to produce a polyester having carboxyl groups at the terminals. Synthesize. Second
As a step, a compound having two or more amino groups in the molecule and the polyester having terminal carboxyl groups obtained in the first step are reacted in a state in which the amino groups are in excess to obtain a polyester having amino groups at the ends. At this time, since the compound having two or more amino groups in the molecule is in an excess state, the excess amino compound remains and becomes a mixture with the obtained polyester having an amino group at the end. Examples of compounds having 2 to 3 hydroxyl groups in the molecule include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butanediol, bentanediol, hexanediol, 2-methylbentanediol, hydroquinone, bisphenol A,
Compounds with two hydroxyl groups in the molecule, such as bisphenol F, and compounds with three hydroxyl groups in the molecule, such as trimethylolpropane, trimethylolethane, and glycerin, either singly or in combination of two or more. Can be used. Furthermore, relatively low molecular weight polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutadiene polyol, etc. can also be used. Compounds having 2 to 3 carboxyl groups in the molecule include adipic acid, maleic acid, maleic anhydride, azelaic acid, sebacic acid, phthalic acid, phthalic anhydride, terephthalic acid, trimellidic acid, etc. alone or in combination of two or more. Can be used in combination. Regarding the ratio of hydroxyl groups to carboxyl groups, the carboxyl groups are in excess, and the molecular weight of the polyester obtained is determined by the excess ratio. In the present invention, the ratio of carboxyl groups to 1 hydroxyl group is 1.02 to 2. Use so that the ratio is 0. The first step, the reaction of polyesterifying hydroxyl groups and carboxyl groups, is carried out in the presence or absence of a catalyst.
The reaction is carried out at 260°C under reduced pressure or in a nitrogen stream if necessary. As catalysts for esterification, sulfuric acid, tri-toluenesulfonic acid, titanates such as tetrabutyl titanate and tetrapropyl titanate, metal acetates such as manganese acetate and zinc acetate, and tin compounds such as monobutyltin oxide and dibutyltin oxide are used as necessary. Can be used. After the first stage reaction yields a polyester with terminal carboxyl groups, the second stage reaction is carried out. Second
In this step, the terminal carboxyl group of the polyester is reacted with the amino group of a compound having two or more amino groups in the molecule (hereinafter referred to as polyamino) in a state where the amino groups are in excess. The resulting carboxylic acid forms an amide bond, and the terminal end of the polyester becomes an amino group. The amount of amino groups per 1 carboxyl group is 2 or more. The second stage reaction follows the first stage reaction from 140 to
The reaction is carried out at 260°C under reduced pressure or in a nitrogen stream if necessary. Examples of polyamino include aliphatic polyaminos such as ethylene diamino, diethylene triamino, propylene diamino, and hexamethylene diamino, alicyclic polyaminos such as infron diamino and cyclohexyl diamino, phenylene diamino, tolylene diamino, diaminodiphenylmethane, and diethyl tolylene diamino. , t-butyltolylene diamino, methylenebisorthochloroaniline (MOC
Aromatic polyaminos such as A) can be used. When the polyester composition of the present invention is reacted with an organic polyisocyanate to obtain a polyurea resin, it is preferable to use aromatic polyamino. When reacting with an epoxy resin to obtain an epoxy resin, it is preferable to use an aliphatic or alicyclic polyamino. However, it can be used depending on the purpose, and which polyamino is used is arbitrary. In the polyester composition of the present invention, the amount of carboxyl groups present at the end (acid value) of the reactant in the first stage is
For the final reactant, the amount of amino groups present at the terminal (
The number average molecular weight can be calculated by measuring the amino acid value (amino value). Furthermore, the presence of excess polyamino can be confirmed by gel permeation chromatography (GPC). The preferred number average molecular weight range of the polyester having an amino group at the terminal of the present invention is 200 to 10,000, and the excess polyamino content is 0.5 to 10,000 with respect to the polyester composition.
~50% by weight is preferred. Next, the polyurea resin is obtained by the following manufacturing method. A polyurea resin is produced by reacting a polyester composition having an amino group at the end with an organic polyisocyanate having two or more isocyanate groups in the molecule at a ratio of NCO/NH, = 0.5 to 2.0. can be manufactured. The organic polyisocyanate that reacts with the polyester composition includes aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, liquid modified diphenylmethane diisocyanate, polyphenylene polymethylene polyisocyanate, 1,5-naphthalene diisocyanate, and toridine diisocyanate;
Examples include aromatic aliphatic polyisocyanates such as xylylene diisocyanate and tetramethylxylylene diisocyanate, and aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, influorone diisocyanate, and dicyclohexylmethane diisocyanate. Furthermore, prepolymers containing terminal isocyanate groups obtained by reacting polyols such as polyoxyalkylene polyols, polytetramethylene glycols, polyester polyols, and polybutadiene polyols with the organic polyisocyanate can also be used. Further, the epoxy resin of the present invention can be obtained by the following method. A polyester composition having an amino group at the end,
The epoxy resin can be produced by reacting an epoxy resin having two or more epoxy groups in the molecule at an equivalent ratio of epoxy groups to amino groups of 1.0 to 3.0. Epoxy resins that react with the polyester composition include generally commercially available amino cured resins with epoxy groups, such as bisphenol type obtained by condensation of bisphenol A and epichlorohydrin, and novolak type obtained by reaction of novolak and epichlorohydrin. Mold epoxy resin can be used. Specifically, as a bisphenol type, Epicote 828.815.82
These are commercially available as 5.827 (manufactured by Yuka Shell Epoxy ■), Adeka Resin EP-4100, EP-4300, EP-4200 (manufactured by Asahi Denka ■), and the like. The novolac type is commercially available as Epicoat 152.154 (manufactured by Yuka Shell Epoxy ■). Since the polyester composition of the present invention has an amino group at the end, it can be used as a curing agent for producing the polyurea resin or epoxy resin of the present invention, and the method for obtaining the cured resin is to mix the two components and then A method of obtaining a desired resin molded product by pouring it into a mold or injecting it and reaction-curing it can be applied. It is also possible to apply the method to a method in which mixing and injection molding are performed almost simultaneously using equipment such as reaction injection molding (RIM). In the case of coating, a method can be used in which the mixture is mixed and then applied to the surface to be coated to form the desired resin after reaction and curing. In the present invention, any method can be used to obtain the desired resin. Moreover, when carrying out the curing reaction, pressure and temperature can be applied to accelerate the reaction if necessary.

[Effect]

The resin using the polyester composition having an amino group at the terminal of the present invention has better tensile strength, elongation, abrasion resistance, etc. when reacted with an organic polyisocyanate than the conventional polyurethane resin. It not only has excellent mechanical strength, but also has excellent workability such as moldability and dimensional accuracy when molded by RIM molding method or the like. This is probably because urea bonds, which have higher cohesive energy than urethane bonds, are the main group. When cured with epoxy resin, impact resistance and flexibility can be imparted without impairing weaving strength. This is probably because the ester bond in the molecule provides flexibility while maintaining mechanical strength.

【Example】

Hereinafter, the present invention will be specifically explained with reference to Examples. In addition,
In Examples and Comparative Examples, "parts" and "%" are based on weight. ! 876 parts (6 moles) of uradipic acid, 450 parts (5 moles) of 1,4-butanediol, and 6.6 parts of tetrabutyl titanate (hereinafter referred to as TBT) were added to a 4-meter tube equipped with a nitrogen inlet tube, a stirrer, and a flow divider. I put it in a double flask. The mixture was heated to 200° C. over 1 hour using a mantle heater while stirring in a nitrogen stream. Water started flowing out around 160 degrees Celsius. The reaction was further carried out at 200°C for 2.5 hours. Acid value 10
5゜8 mgKOH/g (number average molecular weight 1060)
A polyester having terminal carboxyl groups was obtained. Methylenebisorthochloroa and 801 parts of phosphorus (hereinafter referred to as MOCA)
3 mol) at 200℃ for 2.5 hours.
The reaction was carried out at 20°C for 2 hours, and then at 220'C under reduced pressure for 10 hours. Amino value is 75.3mgKOH/g (
Number average molecular weight 1490), viscosity at 70°C 980
A polyester composition having an amino group at the terminal of 00cP was obtained. Furthermore, the presence of free MOCA was confirmed by GPC. Polyester 1146 with terminal carboxyl group of Example 1
534 parts of diethyltolylene diamino (hereinafter DETD)
A, 3 mol) was charged and heated at 200℃ for 2.5 hours.
The reaction was carried out under reduced pressure at 20° C. for 12 hours. Amino value is 1
20mgKOH/g (number average molecular weight 935), 7
A polyester composition having an amino group at the end and a viscosity of 6200 cP at 0"C was obtained. The presence of free DETDA was also confirmed by GPC. . 540 parts (6 mol) of 4-butanediol and 7.3 parts of TBT were placed in four Lof flasks and heated to 200°C for 1 hour. The reaction was carried out at 200°C for 1 hour, and then at 200°C under reduced pressure for 10 hours. A polyester having a terminal carboxyl group with an acid value of 37.5 mgKOH/g (number average molecular weight 2990) was obtained. 288 parts (1.08 mol) of MOCA was added and the mixture was heated at 200°C for 2.5 hours under reduced pressure at 200°C. The reaction was carried out for 11 hours.The amino value was 40 mgKOH/g (number average molecular weight 2
800), a polyester composition having amino groups at the terminals and having a viscosity of 1280OcP at 70°C was obtained. The presence of free MOCA was also confirmed by GPC. Branch 5A Polyester with terminal carboxyl group of Example 3 1253
Add 192 parts (1.08 mol) of DETDA to 2 parts.
The reaction was carried out at 0°C for 2.5 hours and then at 200°C under reduced pressure for 15 hours. Amino value is 42mgKOH/g (number average molecular weight 2670), viscosity at 70°C is 18400c
A polyester composition having an amino group at the P end was obtained. The presence of free DETDA was also confirmed by GPC. Support tm 1206 parts (8.26 mol) of adipic acid, 823 parts (7.76 mol) of diethylene glycol, 30 parts of TBT in 4
The mixture was placed in a double flask and heated to 200°C over 1.5 hours. The mixture was heated at 200° C. for 2 hours and reacted for 7.5 hours to obtain a polyester having terminal carboxyl groups and an acid value of 38 mgKOH/g (number average molecular weight 2950). Furthermore, 267 parts (1.5 mol) of DETDA was added, and the mixture was reacted at 200° C. for 1 hour and then at 210° C. under reduced pressure for 13 hours. Amino value is 53, 5 mgKOH/g
(number average molecular weight 2100), viscosity at 70°C is 5
A polyester composition having terminal amino groups of 800 cP was obtained. The presence of free DETDA was also confirmed by GPC. 1251 parts (8,566 moles) of Shigoyadama adipic acid, l. 4-butanediol 363 parts (4,033 mol), diethylene glycol 427 parts (4,033 mol), TBT
Pour 4 parts of 30.6 parts into a flask and make 2 in 1.5 hours.
It was heated to 00°C. Further at 200℃ for 2 hours, 200℃
The reaction was carried out for 10 hours under reduced pressure with "C". Acid value: 44 mgKO
A polyester having a terminal carboxyl group of H/g (molecular weight of several thousand molecules, 2550) was obtained. Add 267 parts (1.5 mol) of DETDA and heat at 200°C for 2 hours at 210°C.
The pressure was reduced and the reaction was carried out for 20 hours. Amino value 46, 5
A polyester composition having an amino group at the terminal end had mgKOH/g (number average molecular weight 2410) and a viscosity at 70°C of 8000 cP. The presence of free DETDA was also confirmed by GPC. 1. Phthalic anhydride rM 740 parts (5 moles), adipic acid 730 parts
parts (5 mol), 810 parts (9 mol) of 1,4-butanediol
mol) and 101 parts of TE were charged into a four-hole flask equipped with a nitrogen inlet tube, a stirrer, and a flow divider. 200°C with a mantle heater while stirring in a nitrogen stream
It was heated for 1 hour. The reaction was carried out at 200°C for 3 hours and then at 200°C under reduced pressure for 6 hours. Acid value 59
, 6 mgKOH/g of terminal carboxyl group polyester was obtained. Next, 306 parts of diethylenetriamino (
3 mol) was added thereto and reacted at 120° C. in a nitrogen stream for 3 hours. Amino value is 132 mgKQH/g (number average molecular weight 1700), viscosity at 70°C is 9800
A polyester composition having an amino group at the terminal of 0 cP was obtained. Also, as a result of GPC measurement, the average molecular weight was approximately 2.
It was confirmed that it was a mixture of 000 polyester and diethylenetriamino. ! Gogotama terephthalic acid 598 parts (3.6 moles), adipic acid 87
6 parts (6 moles), 223 parts (3,6 moles) of ethylene glycol
mol), 430 parts (4.8 mol) of 1,4-butanediol, and 101 parts of TE were charged into a four-loaf flask and heated to 200° C. for 1 hour. The reaction was carried out at 200°C for 2 hours and then at 210°C under reduced pressure for 8 hours. A polyester having a terminal carboxyl group and an acid value of 90 and 2 mgKDH/g was obtained. DET
427 parts (2.4 mol) of DA was added and the mixture was reacted at 220° C. under reduced pressure for 9 hours. Amino value is 72, 5 mgKO
A polyester composition having an amino group at the end and having a melting point of 112°C was obtained. A small amount of DETDA was also confirmed by GPC. ! 2190 parts (15 moles) of adipic acid, 1080 parts (12 moles) of 1,4-butanediol, 134 parts (1 mole) of trimethylolpropane, and 17 parts of TBT were placed in four flasks and heated to 200°C in 1 hour. . 200℃
The reaction was carried out for 3 hours under reduced pressure at 210"C for 5 hours. A polyester having a carboxyl group at the end and an acid value of 58.3 mg KOH/g was obtained. 713 parts (3.6 moles) of diaminodiphenylmethane were added. Reaction was carried out for 8 hours at 220°C under reduced pressure.Amino value: 66, 1 m
A polyester composition having an amino group at the end of 7 g of gKOH was obtained. Further, as a result of measurement by GPC, it was confirmed that it was a mixture of polyester with an average molecular weight of about 34oO and free diaminodiphenylmethane. 10-15 and 1-4 Table 1 from the polyester compositions having amino groups at the terminals of Examples 1.2 and 3, and MOCA and DETDA alone as comparative examples and epoxy resins (Epicote 828, manufactured by Yuka Shell Epoxy ■) Various epoxy resins were obtained according to the following methods according to the blending ratio. Each material listed in Table 1 was heated to lower its viscosity so that it could be easily handled, and then measured at a predetermined ratio into a cup and mixed. The mixture was poured into a mold coated with a mold release agent to a thickness of 2 mm, and cured for a predetermined time in an oven at the temperatures listed in Table 1. Table 1 summarizes the curing conditions and the strength of the obtained resin. As is clear from Table 1, the resins of Examples using the polyester compositions of the present invention not only have good elongation and flexibility, but also exhibit high impact strength and excellent impact strength. On the other hand, the resin of the comparative example was hard and showed a high value in tensile strength, but the elongation was extremely low and the impact strength was low. 16-23 and Examples 5-6 Prepolymer of terminal isocyanate obtained from polybutylene adipate 2,4-tolylene diisocyanate having a molecular weight of 2000 (free isocyanate = 3.5%) and the polyester composition of Examples 1-6 and Using the mixture of the polyester composition and polyamino, various polyurea resins were obtained in the following manner according to the blending ratios shown in Table 2.3. Each of the ingredients listed in Table 2.3 was heated for ease of handling, measured into a cup, and mixed rapidly. The mixture was poured into a mold coated with a mold release agent, cured for 5 minutes at 150° C. using a hot press, and then finally cured under the conditions listed in Table 2.3. Table 2.3 shows the curing conditions and the strength of the resin obtained. As a comparative example, the results are shown when a prepolymer was cured using only MOCA or DETDA. As is clear from Table 2, when the hardness is the same,
The resin of the present invention had excellent tensile strength and tear strength. Also, from Table 3, resins with lower hardness were obtained with the same tensile strength. 88.7 parts of the polyester composition of Example 3 and DETDA
The first liquid is a uniform mixture of 1.3 parts of I, and the liquid M
Using DI (Millionate MTL, manufactured by Nippon Polyurethane ■) as the second liquid, the first liquid was heated to 80°C and injection molded using a high-pressure RIM machine into a 70°C mold that had been previously coated with a mold release agent. It was possible to demold the mold 30 seconds after injection. Table 4 shows the performance of the obtained resin. Molecular weight 600 with ethylene oxide capped at the end
86 parts of polyoxypropylene triol and DETD
4 parts AI, 0.3 dibutyltin dilaurate as catalyst
A resin was obtained using the RIM machine in the same manner as in Example 19, using the same liquid MDI as used in Example 19 as the second liquid. The mold could not be demolded until 90 seconds after injection.

【Effect of the invention】

By reacting the polyester composition having an amino group at the end of the present invention with an organic polyisocyanate, it has superior mechanical strength and workability compared to conventional polyurethane or polyurethane-urea resins, and can be used for automobile, machine parts, etc. It is suitable as Furthermore, the polyester composition having amino groups at the terminals of the present invention can also be used as a curing agent for epoxy resins. Compared to conventional epoxy resins, the epoxy resin obtained from the polyester composition of the present invention has
It is clear that the material has excellent flexibility and impact resistance, and is suitable for use in electrical parts, etc. No. 5: Measurement method follows ASTM 69

Claims (4)

[Claims] (1) In producing a polyester composition, a compound having 2 to 3 hydroxyl groups in the molecule and a compound having 2 to 3 carboxyl groups in the molecule are reacted with an excess of carboxyl groups to form a polyester with terminal carboxyl groups. 1. A method for producing a polyester composition having an amino group at its terminal, which is obtained by reacting a compound having two or more amino groups in the molecule with an excess of amino groups. (2) A polyester composition comprising a polyester having an amino group at the end and a compound having two or more amino groups in the molecule. (3) The polyester composition according to claim 2 and 2 in the molecule.
1. A method for producing a polyurea resin, which is obtained by reacting an organic polyisocyanate having at least three isocyanate groups. (4) The polyester composition according to claim 2 and 2 in the molecule.
A method for producing an epoxy resin obtained by reacting with an epoxy resin having two or more epoxy groups.