JPH0328225A - Polyamide polyester polyol and polyurethane prepared therefrom - Google Patents

Abstract

PURPOSE:To prepare a polyamide polyester polyol useful for producing a polyurethane excellent in the resistance to heat, moist heat, and abrasion and mechanical strengths by reacting an alcoholic component comprising a specific polyol contg. an amide linkage with an acid component. CONSTITUTION:An alcoholic component comprising a polyol contg. an amide linkage which is obtd. by reacting an alkanolamine (e.g. monoethanolamine) and/or a diamine (e.g. ethylenediamine) with a lactone (e.g. caprolactone) is reacted with an acid component (e.g. adipic acid).

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides an alcohol component containing an amide bond-containing zool obtained by reacting an alkanolamine or/D and zoamine (&) with a lactone (b). The present invention relates to a polyester polyol as a raw material and a polyurethane elastomer composition having excellent heat and humidity resistance and heat resistance, which is characterized by using the polyester polyol.

(Prior art and its problems) Polyester polyols can be used to produce polyurethane elastomers with excellent mechanical strength, abrasion resistance, heat resistance, light resistance, etc., so they are used in synthetic leather, snowboarding, adhesives, industrial parts, and sports. It is used in a wide range of applications, including supplies and daily necessities. However, since there are problems in terms of moisture and heat resistance and heat resistance, attempts have been made to improve this and various methods have been proposed. All of the previous attempts were not fully satisfactory, as the degree of improvement was only a step up, and even if one was satisfactory, the other was significantly deteriorated.

As a polyurethane containing an amide bond, 1.4-
There are polyurethane elastomers obtained from the reaction of diisocyanates with ordinary polyester polyols such as butanediol/adipate, amide bond-containing diols obtained by the reaction of alkanolamines or diamines with lactones, etc.; was not completely satisfactory.

(Means for Solving the Problems) The present inventors have developed a polyester polyol with improved moist heat resistance and heat resistance without impairing the excellent characteristics of polyester polyols such as mechanical strength, abrasion resistance, heat resistance, and light resistance. The present invention was arrived at as a result of intensive research into highly satisfactory polyurethanes.

That is, the present invention provides a polyester polyol obtained by a reaction between an alcohol component and an acid component, in which (a
) alkanolamine or/and diami, shishichi, (
b) To provide a polyamide polyester polyol characterized in that an amide bond-containing polyol obtained by reaction with a lactone is used as an alcohol component, and a polyurethane characterized in that it has excellent heat resistance and moist heat resistance. .

The present invention will be explained in detail below.

(Constitution) Examples of the alkanolamine (.) used in the present invention include monoethanolamine, zoethanolamine,
Examples include triethanolamine, N-methyldiethanolamine, gcXhanolamine, and ingropanolamine.

Examples of the diamine (a) include alicyclic diamines such as piperazine and inphorone diamine, methylenezoamine,
Examples include aliphatic diamines such as ethylenezoamine and propylene diamine, and aromatic noamines such as phenylenesoamine and 4,4'-methylenebisorthochloroaniline.

As the lactone, lactones having K2 or more carbon atoms in the ring or mixtures thereof are used. Specific examples include δ-parerolactone, β-ethyl-δ-
Parerolactone, C-caglolactone, α-methyl-ε
-caprolactone, β-methyl-caprolactone,
r-methyl-ε-caglolactone, β. a-Somethyl-C-caglolactone, 3, 3. 5-trimethyl-caglolactone, enantolactone (7-hegutanolide)
, dodecanolactone (12-dodecanolide DL).

The reaction of the alkanolamine or/and diamine (a) with the lactone (b) is usually carried out at 0 to 150C in a room under a nitrogen atmosphere. Usually, the reaction can be carried out without using a catalyst, but it may be used. The reaction temperature is preferably carried out at a low temperature of 0 to 100 DEG C., since there is a risk of coloring at high temperatures.

Examples of this reaction catalyst include L1, Na, K, Rh,
Ca. Mg, Sr, Zn1AL%Tl%V,
Cr, Mn, Fe, Co, Nl, Cu%
Metal oxides, chlorides, hydroxides such as Zr, Pd, Sn, Sb1pb, fatty acid salts such as acetic acid, oxalic acid, octylic acid, lauric acid, nanthenic acid, sodium methylate, sodium ethylate, aluminum isoglobo oxide, isoglobil titanate, n-butyl titanate, octyl titanate, etc., heptaenolates such as sodium phenolate, kt,?
amount, organometallic compounds of metals such as Zn, Sn, Zr, Pb, /? Conventional esterification and transesterification catalysts, such as strong acids such as latoluenesulfonic acid, can be used.

The amount of this catalyst used is 0.05 to soooppm
, preferably 0.1 to 1000 ppm.

The reaction time varies depending on the type of alkanolamine or diamine used as the polymerization initiator, the type of lactone, the mixing ratio thereof, the amount of catalyst, the reaction temperature, etc., but it usually takes 1 to 24 hours to achieve a reaction time of 99.5% by weight or more. lactone conversion rates can be reached.

The ad bond-containing diol thus obtained preferably has a molecular weight of 190 to 2,000, preferably an acid value of 3 or less, and preferably an OH value of 56 to 59o. This diol can be reacted with dicarboxylic acids in combination with other polyols. Examples of the polyols include ethylene glycol, 1,4-notanediol, propylene glycol, diethylene glycol, diglobylene glycol, 1,6-hexanediol, glycerin, and trimethylolprozene. Furthermore, oligomers and resins having active hydrogen can also be used.

Specific examples include polyester polyols, polyether polyols, urethane polyols, epoxy resins, acrylic polyols, styrene allyl alcohol resins, alkyd resins, polyvinyl alcohol resins, polyvinyl butyral resins, cellulose resins, and unsaturated polyester resins. It will be done.

When using other polyols in combination, the ratio of amide bond-containing zool/boriol is 5/95 to 10
0/O (molar ratio) is preferred.

Furthermore, the zocarboxylic acids to be reacted with these amide bond-containing diols include aliphatic dicarboxylic acids such as malonic acid, glutaric acid, azopic acid, pimelic acid, azelaic acid, cepatic acid, and dodecanedicarboxylic acid, fumaric acid, and maleic anhydride. Unsaturated Il such as acids! > and unsaturated acid anhydrides,
Mention may be made of aromatic acids or aromatic acid anhydrides such as isoheptalic acid, teleheptalic acid, and phthalic anhydride.

As a method for producing a polyamide polyester polyol by reacting an amide bond-containing polyol with a dicarboxylic acid, a normal pressure method or a reduced pressure method using an inert gas, a solvent method using an aromatic hydrocarbon, etc. can be used. The reaction temperature should be lower to avoid coloration, preferably 100 to 180°C.

A catalyst may or may not be used during the production of polyamide polyester polyol, but a catalyst having a weight of 0.0001 to 2 weight, preferably 0.0003 to 1.0 weight is used.

As the catalyst, Li, Na, K, Rb.
Ca, Mg, Sr. Zn%At%TI, V,
Cr. Mn, Fe, Co. Ni, C
u, Zr, Pd, . 8n, 1Sb, Pb −
'k Any metal oxide, chloride, hydroxide, fatty acid salts such as acetic acid, oxalic acid, octylic acid, lauric acid, naphthenic acid, sodium methylate, sodium ethylate, aluminum inglopoxide, inglovir titanate,
7 such as n-butyl titanate, octyl titanate, etc.
Conventional esterification and transesterification of lucolates, 7-enolates such as sodium 7-enolate, organometallic compounds of metals such as AA, TI, Zn, Sn, Zr, Pb, strong acids such as zolatoluenesulfonic acid, etc. Catalysts can be used.

The polyamide polyester polyol thus obtained preferably has a molecular weight of 400 to 10,000 and an OH of 277
~8, acid value 3 or less.

Polycrethane is produced by reacting the polyamide polyester polyol, polyisocyanate, and optionally a b-chain extender using a catalyst.

Examples of chain extenders used in this case include ethylene glycol, diethylene glycol, 1.2-propylene glycol, 1.3-f robylene glycol, 1.3-butanediol, 2.3-7' tanediol, and 1.4-f robylene glycol.
- f tankol, 1,6-hexanezool, 3
-Methyl 1.5 - Aliphatic glycols such as hentanediol, neopentyl glycol, octaneol, nonanenool, decanodiol, cyclohexanediol, cyclohexanediol, etc. These include alicyclic diols such as dimethanol, aromatic glycols such as bishydroxyethoxybenzene, and xylene glycol. Also,
Examples of diamines include aliphatic zoamines such as ethylene diamine, delobylene zoamine, and hexamethylene diamine, alicyclic zoamines such as biperazine and inholon zoamine, xylene diamine, and 4,4'-methylenepis-orthochloroaniline. These include aromatic diamines.

Further, in order to make polyurethane into a foam, a foaming agent and an antifoaming agent are used.

As the foaming agent, water, Freon, etc. are used.

As the antifoaming agent, silicone type, funnel oil, etc. are used.

As the catalyst, those used in the production of ordinary polyurethane elastomers and polyurethane foams, such as triethylamine and dibutyl tin dilacrate, can be used.

Examples of polyisocyanates include aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate, isophorone zoisocyanate,
Alicyclic diisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated hexamethylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate,
Aromatic zincocyanates such as ethylene diisocyanate, phenylene diinocyanate, and tolidine isocyanate are used.

In the production of polyurethane, the NCO/OH molar ratio is preferably 1/0.8 to 1.2, more preferably 1/0.9 to 1.2.
1. React in step 1.

By using the thus obtained polyamide polyester polyol having an amide bond of the present invention, it is possible to achieve moisture and heat resistance without impairing the characteristics of polyester polyols such as mechanical strength, abrasion resistance, heat resistance, and light resistance. We can provide highly satisfactory polyurethane with improved heat resistance and a balance of various physical properties, so it can be used for synthetic leather, snow index, adhesives, paints, coatings, sealants, flooring materials, waterproofing materials, paving materials, and shoe soles. It can be used in a wide range of applications, including sports goods, daily necessities, industrial parts, and foams.

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto. Physical properties described in Examples,
The method for measuring heat and humidity resistance and heat resistance is shown below. In the Examples, "part" means "part by weight".

Measurement method 1. Physical properties hardness, tensile b strength, elongation, tear strength are JISK-63
The measurement was carried out under the conditions of 23° C. and relative humidity of 604 in accordance with 01.

26 Temperature and heat resistance The test pieces were exposed to conditions of a temperature of 80°C and a relative humidity of 904°C for 15 days, and after drying, the tensile strength was measured and the strength retention rate was calculated.

3. The heat resistance test piece was exposed to a Zeyer open dryer at a temperature of 120° C. for 30 days, and after cooling to room temperature, the tensile strength was measured and the strength retention rate was calculated.

Example 1 500 parts of monoethanolamine and 18 parts of cabrolactone
66 parts were charged into a flask and reacted at 100° C. for 3 hours to obtain a colorless and transparent liquid amide bond-containing diol having an acid value of 0.10 and an OH value of 388. (referred to as Diol A) 2000 parts of this Sool A, 819 parts of adivic acid, and tetrabutyl titanium} 0. 1 Prepare 4 parts, about 20
Reacted at 0°C for about 20 hours, acid value 0.21, OR value 53.
．． A polyamide polyester polyol of No. 6 was obtained. (referred to as polyester [1]) 1000 parts of this polyester (1), 107.9 parts of 1,4-butanediol, diphenimethanezoisocyanate}
440.6 parts were reacted at 100°C, and the resulting thermoplastic polyurethane was heated at 80°C for 30 minutes. After cooling, the mixture was crushed and injection molded to produce an elastomer sheet approximately 2 mm thick.

Example 2 000 parts of Zool A obtained in Example 1, 311 parts of 1.4-f tanediol, 873 parts of adipic acid, and 0.11 parts of tetrabutyl titanate were charged and heated at about 200°C for about 20 minutes.
The reaction was carried out for a period of time to obtain a polyamide polyester polyol having an acid value of 0.36 and an OH value of 57.1.

(referred to as polyester [2]) 470.5 parts of this polyester [: 211000 parts, 1 1 5.2 parts of 1,4-butanediol, zophenimethane diisocyanate] were reacted at 100°C to obtain the The thermoplastic polyurethane was cured at 180° C. for 30 minutes, then pulverized and injection molded to produce an elastomer sheet with a thickness of about 2 mm.

Example 3 600 parts of ethylenediamine and 2,280 parts of cabrolactone were charged into a flask and reacted at 100° C. for 3 hours to obtain a white wax-like amide bond-containing diol having an acid value of 0.12 and an OH value of 390. (referred to as diol B) 2000 parts of this diol B, 824 parts of adipic acid, and 0.14 parts of tetrabutyl titanate were charged and heated to about 200°C.
The acid value was 0.22 and the OH value was 56.6.
) 1000 parts of this polyester (3), 114 parts of 1,4-butanediol, zophenymethane diisocyanate}46
5.6 parts were reacted at 100°C, and the resulting thermoplastic polyurethane was reacted at 180°C for 30 minutes. After cooling, it was pulverized and injection molded to produce an elastomer sheet with a thickness of about 2 mm.

Example 4 250 parts of monoethanolamine, 30 parts of ethylenediamine
Charge 0 parts and 2073 parts of caderolactone into a flask,
Reacted at 100°C for 3 hours, acid value 0.11, OH value 39.
A diol containing 0 amide bonds was obtained. (referred to as diol C) 2000 parts of this diol 0, 824 parts of adivic acid, and 0. ．． Prepare 13 parts, approximately 200
The reaction was carried out at ℃ for about 20 hours, and the acid value was 0.25 and the OH value was 55.
A polyamide polyester polyol of No. 1 was obtained. (referred to as polyester [4]) 1000 parts of this polyester (4), 115 parts of 1,4-butanediol, 4 parts of diphenylmethane zoisocyanate
64.9 parts were reacted at 100°C, and the resulting thermoplastic polyurethane was cured at 180°C for 30 minutes, then crushed and injection molded to produce an elastomer sheet with a thickness of about 21IlII.

Comparative Example I 1,000 parts of 1,4-butanzool, 133 parts of asobic acid
Add 5 parts, 0.12 parts of tetrabutyl titanate, and 2
Reacted at 00°C for 20 hours, acid value 0.28, OH1if
A polyester polyol with a fi of 56.5 was obtained.

(referred to as polyester [5]) 1000 parts of this polyester (5), 113.79 parts of 1,4-butaneol, and 465.0 parts of di-7enymethane diisocyanate were reacted at 100°C to obtain a thermoplastic polyurethane. After curing at 180° C. for 30 minutes, the mixture was crushed and injection molded to produce an elastomer sheet with a thickness of about 2 mm.

Comparative Example 2 Thermoplastic polyurethane obtained by reacting 1000 parts of the polyester (5) obtained in Comparative Example 1, 362 parts of Zool A obtained in Example 1, and 460.2 parts of zophenymethane diisocyanate at 100°C. The mixture was aired at 180° C. for 30 minutes, pulverized, and injection molded to produce an elastomer sheet approximately 2 mm thick.

Table 1 shows the physical properties, moist heat resistance, and heat resistance of the polyurethane elastomers obtained in Examples and Comparative Examples.

(Effects) The polyamide polyester polyol of the present invention has amide bonds in the main chain, so when it is made into polyurethane, it can introduce many amide bonds into the urethane main chain, and has excellent moisture and heat resistance.
It can provide polyurethane with excellent heat resistance and various physical properties.

Claims (1)

[Claims] 1. In a polyester polyol obtained by the reaction of an alcohol component and an acid component, an amide bond-containing polyol obtained by the reaction of (a) an alkanolamine and/or diamine and (b) a lactone is used as an alcohol component. A polyamide polyester polyol characterized by: 2. A polyurethane characterized by using the polyamide polyester polyol according to claim 1.