JPH02255818A - Polyol composition for rigid urethane foam - Google Patents

Abstract

PURPOSE:To obtain a polyol composition which can give a rigid polyurethane foam excellent in mechanical strengths, brittleness of foam and heat resistance by mixing a polyol component with an adduct of a specified bisphenol with an alkylene oxide. CONSTITUTION:A polyol composition for rigid urethane foam is prepared from 20-50wt.%,especially 30-40wt.%, based on the polyol component, polyol (of a hydroxyl value of 50-480) comprising an adduct of resorcinol, catechol, cresol or the like with ethylene oxide and/or propylene oxide, represented by the formula (wherein R is an ethylene group or a propylene group, and the two groups containing R are meta or para to each other, m and n are each a number >=1; m+n=3-40; and R' is H or a lower alkyl) and 5-15 pts.wt., per 100 pts.wt. polyol component, crosslinking agent, desirably ethylene glycol.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyol composition that provides a rigid urethane foam with excellent mechanical strength, foam brittleness and heat resistance.

In the past, hard urethane foams have usually been produced by using low-molecular-weight or high-functionality polyols as the polyol component. Therefore, although such hard urethane foams have excellent mechanical strength, It is inferior to brittleness, and its heat resistance is naturally limited.

As a result of intensive research in order to solve the above-mentioned problems in the production of rigid urethane foam, the present inventors have found that, as a polyol component, in particular - type (wherein R is an ethylene group or Indicates a propylene group, and the two groups containing this R are in the meta or ortho position with respect to each other. m and n are numbers larger than 1, and m 10n = 3 to 40. R'
represents hydrogen or a lower alkyl group. The inventors have discovered that by using a polyol represented by the following, it is possible to improve the foam brittleness and heat resistance while maintaining excellent mechanical strength, leading to the present invention.

Therefore, an object of the present invention is to provide a polyol composition that provides a rigid urethane foam with excellent mechanical strength, foam brittleness, and heat resistance.

The polyol composition for rigid urethane foam according to the present invention has the form (wherein R represents an ethylene group or a propylene group, and two groups containing this R). The groups are in meta or ortho positions with respect to each other.

m and n are numbers larger than 1, m+n=3 to 40
It is. Ro represents hydrogen or a lower alkyl group. ) The polyol represented by 20 to 50 of the polyol component
It is characterized by containing % by weight.

In the polyol composition for rigid urethane foam according to the present invention, the above-mentioned polyol used as the polyol component can be obtained, for example, by adding a predetermined amount of ethylene 4:side and/or propylene oxide to resorcinol, catechol, cresyldin, or the like. I can do it. Therefore, in the above -format, the two groups containing R are in the meta or ortho position with respect to each other. The above polyols are usually obtained as different mixtures of m and n. In the present invention, adducts of ethylene oxide and/or propylene oxide to resorcin, catechol, cresircin, etc. can be used alone or as a mixture.

Further, in such a polyol, R" is hydrogen or a lower alkyl group, and specific examples of the lower alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, etc. However, Ro is preferable. is hydrogen.

In such polyols of the form - above, m
and n is a number larger than 1, and the number of moles of alkylene oxide added, represented by m+n, is from 3 to 40. When the number of added moles is smaller than 3, the resulting hard urethane foam has improved heat resistance, but has poor toughness and may lack practicality as various products. On the other hand, when the number of added moles exceeds 40,
The resulting hard urethane foam has poor mechanical strength, especially bending strength, and is also poor in heat resistance.

In the production of urethane foam, it is convenient to express the polyol used by its hydroxyl value. In this sense, the above adduct used in the present invention has a hydroxyl value of 50
~480.

In the polyol composition for rigid urethane foam according to the present invention, the above-mentioned adduct is 20% of the polyol composition.
It accounts for 0-50% of the double seal. When the amount is less than 20% by weight of the polyol composition, a rigid urethane foam with improved brittleness and heat resistance cannot be obtained. On the other hand, 50
When used in a large amount exceeding % by weight, the resulting urethane foam will have low hardness and will lack the practicality of hard foam and L7. Preferably, the adduct is used so as to represent 25 to 45% by weight, especially 30 to 40% by weight of the polyol composition.

Furthermore, the composition according to the invention preferably contains a crosslinking agent. Such a crosslinking agent and 1. For example, low carbon atoms having 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, etc. Molecular weight glycols, alkanolamines such as jetanolamine and triethanolamine, aliphatic polyamines such as ethyldiamine, diethylenetriamine and triethylenetetramine, methylene-0-110aniline, 4,4'-diphenylmethanediamine, Aromatic diamines such as 2.4-) lylene diamine and 2.6-) lylene diamine are used. These crosslinking agents are generally used in an amount of 5 to 15 parts by weight per 100 parts by weight of the polyol component.

In particular, the polyol composition according to the present invention uses the above-mentioned glycol having 2 = -6 carbon atoms as a crosslinking agent so that the resulting rigid urethane foam has heat resistance to withstand long-term use in a high-temperature environment. It is preferable to contain 5 to 15 parts by weight per 100 parts by weight of the polyol component.

The polyol composition for rigid urethane foam according to the present invention is combined with a polyisocyanate to produce a rigid polyurethane. Here, the polyisocyanate is not particularly limited, and for example, 2.4-tolylene diisocyanate, 2.6
-) lylene diisocyanate, mixtures of 2,4-tolylene diisocyanate and 2,6-) lylene diisocyanate in various quantitative ratios, for example 80/20 (TD
I-80) and 65/35 (TD I-65) mixture, crude tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylene polymethylene polyisocyanate known as crude MDI, dianisidine diisocyanate, toluidine diisocyanate 1. Xylylene diisocyanate 1-, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) maleate, bis(2-isocyanatoethyl) carbonate, 1,6-hexamethylene diisocyanate, 1,4-
Tetramethylene diisocyanate cyanate, cumene-2,4-diisocyanate, 4-
Methoxy-1,3-phenylene diisocyanate, 4-
Bromo-1,3-phenylene diisocyanate, 4-ethoxy-1. 3-phenylene diisocyanate, 2
．． 4'-diisocyanatodiphenyl ether, 5,6-
Cymethyl-L 3-phenylene diisocyanate, 2
, 4-dimethyl-1,3-phenylene diisocyanate, 4.4'-diisocyanatodiphenyl ether, bis-5,6-(isocyanatoethyl)bicyclo(2,2.
1) Hebr-2-ene, benzidine diisocyanate, 4,6-dimethyl-1,3-phenylene diisocyanate, 9,IO-ant-racene diisocyanate, 4.4'-=diisocyanat dibenzyl, 3,3' -dimethyl-4,4°-diisocyanatodiphenylmethane, 2,6-dimethyl-4,4'-diisocyanatodiphenyl, 2,4-diisocyanatostilbene, 3,3'
-dimethyl-4.4'-diisocyanatodiphenyl, 1
, 4-anthracene diisocyanate, 2,5-fluorene diisocyanate, 1.

8-Naphthalene diisocyanate, 2,6-diisocyanatobenzfuran, 2.4. Examples include 5-1-luentriisocyanate, carbodiimide modified products of these polyisocyanates, biuret modified products, trimers, trimers, terminal isocyanate group prepolymers of these polyisocyanates and active hydrogen compounds, etc. may be used alone or as a mixture of two or more.

As the polyisocyanate, aliphatic polyisocyanate or aromatic polyisocyanate is usually used,
In particular, aromatic polyisocyanates are preferably used from the viewpoint of the mechanical strength and hardness of the resulting rigid urethane foam.

In the polyol composition according to the present invention, any polyol conventionally used in the production of rigid, semi-rigid or flexible urethane foams can be used as the polyol other than the above-mentioned adduct. Examples of such polyols include polyester polyols, polyether polyols, polyester polyether polyols, and graft polyols.

More specifically, polyester polyols include, for example, glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, pentane glycol, and hexane glycol, or polyols such as triols such as trimethylolpropane and glycerin; Examples include those obtained by condensation reaction with dicarboxylic acids such as adipic acid, sebacic acid, isophthalic acid, and phthalic acid.

Examples of polyether polyols include glycerin, trimethylolpropane, l-liethanolamine,
pentaerythritol, diglycerin, sorbitol,
Those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc. to polyols such as sucrose,
Alternatively, examples may include those obtained by adding the above-mentioned alkynone oxide to amine compounds such as ammonia, monoethanolamine, jetanolamine, ethylenediamine, 4,4''-diaminosyfuconinylmethane, and tolylene diamine. I can do it.

As the polyester polyether polyol, the above-mentioned polyether polyol can be used, for example, adipic acid,
Examples include those obtained by reacting with dicarboxylic acids such as sebacic acid, isophthalic acid, and phthalic acid.

In addition, as the graft polyol, a monomer having a polymerizable unsaturated group in the polyether polyol as described above,
For example, those obtained by polymerizing styrene, acrylonitrile, etc. can be mentioned.

These polyols may be used alone or as a mixture of two or more.

Using the polyol composition according to the invention, rigid polyrl
To produce z-rethane foam, the equivalent ratio of isocyanate groups in the polyisocyanate used to active hydrogen in the polyol composition (NCOlo H) is 0.8.
The polyisocyanate-1. is reacted with the polyol composition such that the polyisocyanate-1.

Furthermore, in the production of rigid urethane foam, catalysts and blowing agents are used, and if necessary, surfactants or foam stabilizers, stabilizers, colorants, etc. are used.

The above-mentioned catalyst is not particularly limited, and any conventionally known catalyst can be used. For example, with an amine catalyst! , 1-liethylamine, tripropylamine, tributylamine, I-lioctylamine,
hexadecyldimethylamine, N-methylmorpholine,
N-ethylmorpholine, N-octadecylmorpholine,
Monoethanolamine, jetanolamine, l-jetanolamine, triisopropanolamine, N-methyljetanolamine, N,N-dimethylethanolamine, diethylenetriamine, N, N, N', N'
-tetramethylethylenediamine, N, N, N', N
'-tetramethylpropylenediamine, N, N, N',
N“-tetramethyl-1,3-butanediamine, N,N
, N',N'-tetramethylhexamethylenediamine,
Bis(2-(N.

N-dimethylamino)ethyl]ether, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, N,N,N',N"-bentamethyldiethylenetriamine, 7 triethylenediamine, formate of triethylenediamine Examples include various salts such as, oxyalkylene adducts of amino groups of primary or secondary amines, and the like.

Examples of organometallic catalysts include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin dichloride, lead octoate, lead naphthenate,
Examples include nickel naphthenate and cobalt naphthenate.

These catalysts may be used alone or as a mixture of two or more. The amount used is usually 0.001 parts by weight per 100 parts by weight of the compound having active hydrogen in the composition.
A range of 5 parts by weight is preferred.

In addition, as blowing agents, water and various halogenated hydrocarbons such as trichlorofluoromethane, dichlorodifluoromethane, methylene chloride, 1-dichlorotrifluoroethane, dibromotetrafluoroethane, trichloroethane, hentane, n-hexano, etc. The following aliphatic hydrocarbons can be mentioned. These blowing agents can also be used alone or as a mixture of two or more. Usually water is 0.05 to 2% by weight, preferably 0.05% to 2% by weight, based on the total amount of active hydrogen compound including polyol and polyisocyanate.
．． It is used in a range of 2 to 1.0% by weight. In addition, halogenated hydrocarbons are 0 to 12% based on the total amount of active hydrogen compounds including polyols and polyisocyanates.
Used within the range of

As the foam stabilizer, a conventionally known ordinary organic gay fiber surfactant is used. As a specific example, for example, L-520, [2-532, L-540 manufactured by Nippon Unicar ■
,L-544,■,-550,L3550,L,-3
600, L-3601, L-5305, L-5305,
L-5307, L-5309, L-5710, L-57
20, L-5740M, etc., and 5 made of Toray silicone ■
H-190, 5H-192, 5H-194, 5H-2O
0゜5RX-253, 5RX-274C, 312961
, 5F-2962, 5RX-280A, 5RX-294
A, etc., F-If4, F-121 made by Shin-Etsu Silicone 1m
, F-122, F-220, F-230, F-258,
F-260B, F-317, F-341, F-60
1, F-335, etc. These foam stabilizers are usually added to 100 parts by weight of the total amount of the compound having active hydrogen and the polyisocyanate in the composition.
The range is from 0.25 to 2 parts by weight.

As described above, according to the present invention, the polyol component contains a predetermined amount of ethylene oxide and/or propylene oxide adduct to resorcin, catechol, cresircin, etc. as described above in a specific ratio. By using the composition, it is possible to obtain a rigid urethane foam that has excellent mechanical strength and improved brittleness and heat resistance.

Examples - The present invention will be explained below by giving examples of the present invention together with reference examples showing production examples of the above-mentioned adducts used in the present invention, but the present invention is not limited in any way by these examples. do not have.

Reference Example 1 3 kg of resorcinol was charged into a pressurizable reaction container equipped with a thermometer and a stirrer, and then 30 g of potassium hydroxide flakes were charged, and the inside of the reaction container was replaced with nitrogen.
Heating to a temperature of 20-130'C dissolved the potassium hydroxide.

While maintaining the temperature of the mixture at 1.10 to 130°C, 24.4 kg of ethylene oxide was added to it over 8 hours, and after further stirring at the above temperature for about 1 hour,
The slight remaining unreacted ethylene oxide was stripped off with nitrogen. The reaction mixture was then heated to 90-11
After cooling to a temperature of 0 ° C., adding a small amount of water and 200 g of synthetic magnesium silicate, and stirring for about 1 hour,
Magnesium silicate was removed by filtration, dehydrated, and
21 g of t-butylhydroxytoluene was added.

The polyol thus obtained was a pale yellow viscous liquid containing 0.02% water, a hydroxyl value of 111, a pH of 6.9, and a total amount of ethylene oxide added of 20.2 mol per mol of resorcinol. Ta.

Reference Example 2 In a reaction vessel similar to Reference Example 1, 3 kg of catechol and 45 g of potassium hydroxide flakes were charged, and after the potassium hydroxide was dissolved, nitrogen was blown into the reaction vessel under reduced pressure for dehydration.

To this mixture first add 3 kg of propylene oxide.
added over a period of time, then ethylene oxide io
b was added for 7 hours to react, and thereafter, Reference Example 1
was treated in the same manner as above, containing 0.03% water, hydroxyl value 157, pH 6.8, total amount of ethylene oxide added per mol of catechol: 8.4 mol, total amount of added N of propylene oxide: 4.4 mol. The adduct was obtained as a pale yellow viscous liquid.

Example 1.2 and Comparative Example 1 A composition of the formulation shown in Table 1 was prepared, and 1OQ consisting of iron was prepared.
A mold of Oa+5×250×10 mm was heated to 50±5° C. and heated and foamed for 3 minutes using a foaming machine manufactured by Hennecke 1 to produce a rigid urethane foam. Table 1 shows its physical properties.

In Table 1, polyol A is a propylene oxide adduct of sucrose glycerin (hydroxyl value 460);
Polyol B is an ethylene oxide adduct of trimethylolpropane (hydroxyl value 920), and polyol C is
The ethylene oxide adduct (hydroxyl value 111) to resorcinol obtained in Reference Example 1, Polyol D indicates the ethylene oxide propylene oxide adduct (hydroxyl value 157) to catechol obtained in Reference Example 2.

In addition, polyisocyanate "C" is polyphenylene polymethylene polyisocyanate (Japan Polyurethane)
Millionate MR-200) was used.

In physical property measurements, the bending strength and bending modulus were 13X
Prepare a test piece of ilOX 10m+ (thickness), span 5
Measured at 0.8 tra+. In addition, the compressive strength is 3
A test piece of 0x30x10 (thickness) was prepared 7 and compressed by 30% in the thickness direction.

Next, the obtained hard foam was left at a temperature of 100'C for 1000 hours, and then the bending strength, bending elastic modulus and compressive strength were measured in the same manner and shown as the physical properties after the durability test.

The hard urethane foam according to the present invention has an excellent balance between strength and brittleness, has excellent heat resistance, and shows no deterioration in physical properties even after a durability test.

ζ--;, 5. :,, Mi=+

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents an ethylene group or a propylene group, and the two groups containing this R are in the meta or ortho position with respect to each other. m and n are numbers larger than 1, m+n=3 to 40
It is. R' represents hydrogen or a lower alkyl group. ) The polyol represented by 20 to 50 of the polyol component
% by weight of a polyol composition for rigid urethane foam.