JPS63235321A - Production of thermosetting resin - Google Patents

Abstract

PURPOSE:To obtain the title resin excellent in modulus, heat resistance and impact resistance, by reacting an organic polyisocyanate with a specified polyol in the presence of a trimerization catalyst. CONSTITUTION:A polyol component (b) is obtained by mixing 10-80wt.% high- molecular polyol (i) (e.g., polyether polyol) of an OH value >=70 with 20-70wt.% oxyalkylated cyclic amine or polyol (ii) of formula I (wherein Ar is a cyclic amine or polyol residue, X is O or formula II, A is a 2-4C alkylene, R is H or a 1-4C alkyl, m is 0-4, n is 1-4, and p is 2-4) and an OH value of 300-750 and 0-20wt.% low-molecular polyol (iii) of an OH value >=800. An organic polyisocyanate (a) (e.g., tolylene diisocyanate) of an NCO index of 105-1,000 is reacted with component (b) at 40-200 deg.C for 10min-5hr in the presence of a trimerization catalyst (c) and, optionally, other catalysts.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing thermosetting resins.

[Conventional technology]

Conventionally, a method for producing a thermosetting resin is known in which an organic polyisocyanate and a polymeric polyol are reacted.

[Problem that the invention seeks to solve]

However, conventional thermosetting resins do not simultaneously satisfy high elastic modulus, heat resistance, and impact resistance.

[Means for solving problems]

As a result of repeated studies by the present inventors to find a method for producing a thermosetting resin having elastic modulus, heat resistance, and WJ impact resistance,
We have arrived at the present invention.

That is, the present invention provides a method for producing a thermosetting resin by reacting a polyisocyanate and a polyol in the presence of a trimerization catalyst and, if necessary, other melting medium, (1) a polyisocyanate having a high OH value of 70 or less; Molecular polyol (A), amine or polyol (B) having an oxyalkylated cyclic group with an OH value of 300 to 750
And if necessary, use low molecular weight polyol (C) 2
) with an isocyanate index of 106 to 1000 3) 4
This is a method for producing a thermosetting resin characterized by heat treatment at a temperature of 0 to 200°C.

In the present invention, the amine or polyol (B) having an oxyalkylated cyclic group has the general formula % (1) (where Ar is a residue of an amine having a cyclic group or a polyol having a cyclic group). residue, X is -N〈(Ao)mR
or an oxygen atom, A is an alkylene group having 2 to 4 carbon atoms, R
is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m is θ to 4
n is an integer of 1 to 4, and p is an integer of 2 to 4.

) Compounds (B) having an OH value of 300 to 750 are exemplified.

In the general formula (1), the amine forming the amine residue having a cyclic group is disclosed in Japanese Patent Application Laid-open No. 61-17172.
Unsubstituted aromatic polyamine, aromatic polyamine having a nuclear substituted alkyl, nuclear substituted phosphorus, phenylene diamine, tolylene diamine (hereinafter abbreviated as TL A), crude tolylene diamine, diethyl tolylene diamine, described in Publication No. 0 , diphenylmethanediamine (hereinafter abbreviated as MDA), crude MDA, naphthalene diamine, diaminodiphenylsulfone, benzidine, 4,4'-bis(
C-toluidine).

Thiodianiline, dianisidine, methylenebis(C-chloroaniline), bis(8,4-diaminophenyl)sulfone, diaminoditolylsulfone.

2.6-Diamitsupyridine, 4-chloro-0-phenylenediamine, 4-methoxy-6-methyl-m-phenylenediamine 7.1Il-aminobenzylamine, 4,4
°-diamino-3,3°-dimethyldiphenylmethane,
These hydrogenated products and mixtures of two or more thereof are included. Preferred among these are aromatic h'A amines, especially aniline, MDA, TDA and 4,4-diamino-3,3°-dichlorodiphenylmethane.

The polyols forming the residue of a polyol having a cyclic group include, for example, diols having a cyclic group described in Japanese Patent Publication No. 1474/1982: bis(hydroxymethyl)cyclohexane, m-t3 and Kano xylylene. Glycol, bis(hydroxyethyl)benzene, 1.4-
Bis(2-hydroxyethoxy)benun, ethylene oxide and/or propylene oxide adduct of bisphenol A [4,4-his(2-hydroxyethoxy)diphenylpropane, 4,4-bis(2-hydroxypropoxy)diphenyl Examples include aromatic and cycloaliphatic polyols such as propane 1, and mixtures of two or more thereof. Preferred are aromatic polyols, especially ethylene oxide to bisphenol.
/ Hl+ f-(-1 pro s l /ゝ/+ten→
F] is a; 11nn Q'rn 7S Examples of the alkylene group having 2 to 4 carbon atoms in person A include 'ethylene, propylene, and butylene groups. Preferred are ethylene and propylene groups, including yl, ethyl, propyl and butyl groups. Preferably it is a hydrogen atom.

The OH value of the compound represented by general formula (1) is usually 300 to
750. The best price is 380-700 teal. OH value is 7
When it is greater than 50, the impact resistance decreases, and when it is less than 300, the elastic modulus decreases.

The compound represented by the general formula (1) can be obtained by adding alkylene oxide to an amine or polyol having a cyclic group by a conventional method. Examples of the alkylene oxide added to the compound include -ethylene oxide (hereinafter also referred to as EO), propylene oxide (hereinafter also referred to as PO), butylene oxide (tetrahydrofuran, etc.). The alkylene oxides may be used alone or in combination of two or more. Preferred among these alkylene oxides are tetrahydrofuran jPO and EO.

Specific examples of the compound represented by general formula (1) include aniline PO adduct (OH value 580), aniline EO adduct (
OH value 590), bisphenol A PO adduct (O
H value 850), MDA PO adduct (OH value 560)
.

Examples include MDAPO and EO adducts (OH value 662).

(B) can be used as a crosslinking agent.

The polymer polyol used in the present invention includes:
Common polyols such as polyether polyols and polyester polyols can be used.

Examples of polyether polyols include compounds having a structure in which an alkylene oxide is added to a polyfunctional compound containing an active hydrogen atom, such as a polyhydric alcohol, a polyhydric phenol, or a polycarboxylic acid. The polyhydric alcohol mentioned above is ethylene glycol.

Propylene glycol, 1,4-butanediol, 1
．． Dihydric alcohols such as 6-hexanediol, diethylene glycol, neopentyl glycol, and trivalent or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose; polyhydric phenols include pyrogallol, humanboroquinone, etc. In addition to polyhydric phenols, bisphenols such as bisphenol A; polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, maleic acid, and dimer acid, and phthalic acid.

Examples include aromatic polycarboxylic acids such as terephthalic acid and trimellitic acid. Two or more kinds of the above-mentioned active hydrogen atom-containing compounds can also be used. As the alkylene oxide added to the above active hydrogen atom-containing compound, EO
, PO, butylene oxide (tetrahydrofuran, etc.), and the like. The alkylene oxides may be used alone or in combination of two or more, and in the latter case, block addition, random addition, or a mixture of both may be used. Preferred among these alkylene oxides are tetrahydrofuran, PO and EO.

Examples of polyester polyols include condensed polyester polyols and lactones (epsilon-caprolactone, etc.) obtained by reacting low-molecular polyols (such as the dihydric alcohols, trinotyrolpropane, and glycerin) with dicarboxylic acids (such as the polycarboxylic acids). Examples include polyester polyols obtained by ring-opening polymerization.

Polycarbonate diols can also be used.

Polymeric polyols can also be used.

The OH value of the polymer polyol is 70 or less, preferably 60
It is as follows. If the OH value is greater than 70, the impact resistance will be poor.

Low-molecular polyols (C include dihydric alcohols such as ethylene glycol, propylene glycol, and butanediol, and octavalent or higher alcohols such as glycene and trimethylolpropane).

The OH number of the low molecular weight polyol (C) is usually 300 or more.

In the present invention, polymer polyols), polyols (
The amount of B) and low molecular weight polyol (d) is based on the weight of the polyol (Shu usually ranges from 10 to 80%, preferably 80%).
0 to 70%, (B) is usually 20 to 70%, preferably 8
0-60%, (C) is usually 0-20%. Preferably 0-1
It is 0%. If (M), (B) and (C) are outside this range, the elastic modulus.

Impact resistance and heat resistance cannot be satisfied at the same time.

As the organic polyisocyanate used in the present invention, those conventionally used in the production of 4t polyurethane can be used. Specific examples of these include Toku D9 1985-
Compounds described in 2822 and the like can be used. For example, aliphatic polyisocyanates (hexamethylene diisocyanate, lysine diisocyanate, etc.), alicyclic polyisocyanates (hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, etc.), aromatic polyisocyanates [tolylene diisocyanate (TDI), diphenylmethane, etc.] Examples include diisocyanates (such as naphnaphthylene diisocyanate silylene diisocyanate containing MDI) and mixtures thereof. Among these, aromatic diisocyanates are preferred, and particularly preferred are TDI and M)I. These polyisocyanates may be crude polyisocyanates, such as crude polyisocyanates, such as crude % MDI, or modified polyisocyanates, such as liquefied Iul.
DI (carposiimide modification, trihydrocarbyl phosphate modification, etc.) or excess polyisocyanate (TD
It can also be used as a free isocyanate-containing prepolymer obtained by reacting a polyol with a polyol, or they can be used in combination (for example, a modified polyisocyanate and a prepolymer are used in combination).

The polyols used in the production of the prepolymer include posiols having an equivalent weight of 80 to 200, such as glycols such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; triols such as trimethylolpropane and glycerin; and pentaerythritol and sorbitol. Highly functional polyols; and alkylene oxide (ethylene oxide and/or propylene oxide) adducts thereof.

Among these, those having 2 to 8 functional groups are preferred.

The free isocyanate group content of the modified polyisocyanate and prepolymer is usually 10 to 35%, preferably 15%.
-80%, particularly preferably 15-28%.

When the content of free isocyanate groups is less than 10%, the elastic modulus is low, and when it exceeds 85%, the impact strength is low.

As the trimerization catalyst used in the present invention, known ones can be used. Specifically, gold RiM of carboxylic acids (sodium acetate, potassium octylate, lead octylate, zinc octylate, cobalt naphthenate, etc.), alkoxides and phenoxides of alkali and alkaline earth metals (sodium methoxide, sodium phenoxide, etc.) ), tertiary amine CI, 9.5. -) lis(3-dimethylaminopropyl)hexahydro-5-triazine, dimethylaminomethyl eastphenol, pyridine], quaternary ammotyl-4-methylimidazole, etc.). Among these, preferred is a combination system of a metal salt of carboxylic acid and a tertiary amine.

The amount of trimerization catalyst used is usually 0.01 to 10 parts, preferably 0.06 to 6 parts, per 100 parts of the organic polyisocyanate.

Other catalysts that may be used as necessary in the present invention include 8th class amines, organic tin compounds, and organic lead compounds other than those mentioned above.

Examples of 8th class amines other than the above include triethylamine,
Examples include N-methylmorpholine.

Examples of the organic tin compound and organic lead compound include dibutyltin dilaurate, tin octylate, and lead octylate. Further, a blowing agent (freon, methylene dichloride, etc.) and other additives (pigment, filler, etc.) can also be used if necessary.

In the present invention, the isocyanate index is usually 105 to 1.
000, preferably 110-900. When the isocyanate index is high, heat resistance is good but impact resistance is poor.

On the other hand, when the isocyanate index is low, the performance is the opposite.

In the present invention, the heat treatment temperature is usually 40 to 200°C1
Preferably 60-180°C1, more preferably 60-1
It is 50°C. If the heat treatment temperature is less than 40°C, heat resistance will be insufficient, and if it is higher than 200°C, thermal decomposition of the resin will occur.

The heat treatment time is usually 1 to 5 hours, preferably 30 minutes to 2 hours.
It's time.

The heat treatment conditions have a great influence on the completion of the reaction and the microphase structure. This makes it possible to produce a thermosetting resin with excellent impact resistance and heat resistance.

As the molding method in the present invention, vacuum casting method and molding method are useful, but other molding methods can also be applied.

〔Example〕

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. Parts in Examples and Comparative Examples are parts by weight. The measurement method is as follows.

Heat distortion temperature ('C) (According to JISK6911. Load 18.6 kg) Flexural modulus (k/cut), IZOD impact (notched) (#g・an/ad
) (According to JIS K69111C) Example 1 OH obtained by adding PO to propylene gelylcol by a conventional method
50 parts of polyether polyol having a value of 56, P to aniline
1.3.5. to 50 parts of polyol (B) having an OH value of 530 added with O. -) Lis(3-dimethylaminopropyl)
- Add 0.1 part of hexahydro-5-triazine, 0.1 part of potassium octylate and 0.05 part of a silicone antifoaming agent, adjust the temperature to 25°C, and add polypropylene glycol with an OH value of 56 and MDI at a constant temperature. NC0 obtained by reaction by method
%20% prepolymer 179 parts (NGO index 200)
The mixture was heated to 25°C, mixed, defoamed, poured into a mold with a mold temperature of 60°C, cured at 60°C for 10 minutes, and then heat-treated at 150°C for 1 hour. A resin with excellent elastic modulus, impact resistance, and heat resistance was obtained.

Example 2 OH with PO added to propylene glycol by a conventional method
PO was added to bisphenol A in 60 parts of a polyether polyol with a value of 28 (polyol (n) with an M value of 350).
1,3,5 in 40 copies. - 0.1 part of tris(3-dimethylaminopropyl)-hexahydro-3-triazine,
0.1 part of potassium octylate and 0.0 part of silicone antifoaming agent
5 parts were added and the temperature was adjusted to 25°C. In addition, NC0%2 obtained by reacting propylene glycol and MDI by a conventional method
6% FuL/Ho'J v 90 parts (NCO index 2
00) Add the mixture to 25°C, mix, defoamer, and pour into a mold with a mold temperature of 60°C for 10 minutes at 60°C.
After curing at C, heat treatment was performed at 150''C for 1 hour. A resin with excellent elastic modulus, impact resistance, and heat resistance was obtained.

Example 3 50 parts of a polyester polyol with an OH value of 56 obtained by ring-opening polymerization of caprolactone, 40 parts of a polyol (B) with an OH value of 560 obtained by adding PO to MDA, 10 parts of ethylene glycol, and 0 parts of dibutyltin dilaurate. 05 parts were added and the temperature was adjusted to 25°C. 178 parts of the prepolymer (N index 110) used in Example 1 was added to it at 25°C, mixed and stirred, poured into a mold with a mold temperature of 60°C, cured at 60°C for 10 minutes, and then heated to 180°C. A resin with excellent elastic modulus, impact resistance, and heat resistance was obtained by heat treatment with CX for 1 hour.

Comparative Example 1 A resin was obtained in the same manner as in Example 2, except that a polyol with an OH value of 850, which was obtained by adding PO to ethylenediamine, was used in place of the polyol (B) used in Example 2.

Comparative Example 2 A shock-resistant type of polypropylene was molded using an injection molding machine.

Test Example 1 The performance of the resins obtained in Examples 1 to 8 and Comparative Example 1.2 was tested.

The results are shown in Table-1.

〔Effect of the invention〕

According to the present invention, a thermosetting resin can be obtained which has superior elastic modulus, impact resistance, and heat resistance compared to conventional thermosetting resins, and has excellent moldability.

Also, traditional thermoplastics (polypropylene).

A thermosetting resin with superior elastic modulus, impact resistance, and heat resistance compared to A% resin, etc.) can be obtained, and this resin can be used for molds (silicon molds, resin molds, etc.) that are cheaper than thermoplastic resins. It is industrially advantageous because it can be used.

Due to the above-mentioned effects, the resin obtained by the present invention can be used in various fields of application, such as automobile exteriors.

Claims (1)

[Claims] 1. In a method for producing a thermosetting resin by reacting an organic polyisocyanate and a polyol in the presence of a trimerization catalyst and, if necessary, other catalysts, (1) a polyol having a high OH value of 70 or less; Molecular polyol (A), OH value 30
Using an amine or polyol (B) having an oxyalkylated cyclic group of 0 to 750 and, if necessary, a low molecular weight polyol (C), (2) setting the isocyanate index to 105 to 1000, and (3) a temperature of 40 to 200°C. A method for producing thermosetting resin characterized by heat treatment. 2, (B) has the general formula Ar-[X-(AO)nH]p(1) (wherein, Ar is a residue of an amine having a cyclic group or a residue of a polyol having a cyclic group, and X is - N<(AO)m
R or an oxygen atom, A is an alkylene group having 2 to 4 carbon atoms,
R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m is 0 to
n is an integer of 1 to 4; p is an integer of 2 to 4; ) The manufacturing method according to claim 1, wherein the compound (B) has an OH value of 300 to 750. 3. The amounts of (A), (B), and (C) used are 10 to 80% for (A) and 20 to 20% for (B), based on the weight of the polyol.
70% and (C) is 0 to 20%.