JPS58162626A - Production of polyurethane - Google Patents

Abstract

PURPOSE:The reaction between an organic polyisocyanate and a polyol composition containing a high-molecular polyol, a low-molecular active hydrogen compound and a sulfur-containing surfactant is carried out to give polyurethane with good operability. CONSTITUTION:The reaction of an organic polyisocyanate, e.g., a modified polyisocyanate with a polyol composition containing a high-molecular polyol such as polyether polyol, a low-molecular hydrogen compound such as ethylene glycol and a sulfur-containing anionic surfactant such as a sulfonate anionic surfactant, e.g., sulfosuccinic ester salt and/or sulfate salt type anionic surfactant such as alkylsulfat ester salt is carried out in the presence of a catalyst such as a tertiary amine, when necessary, along with a foaming agent such as water and/or flon 11 to give the objective polyurethane. EFFECT:The product shows high storage stability.

Description

[Detailed description of the invention] The present invention relates to a method for producing polyurethane.

Conventionally, it has been known to produce polyurethane by reacting a high-molecular polyol and a low-molecular active hydrogen compound with an organic polyisocyanate, and methods for reacting these include (1) a method of simultaneously mixing and reacting all components; (
2) A stepwise mixing method (i.e., a method in which a polymer polyol and a polyisocyanate are reacted to form a prepolymer, and then chain extension or crosslinking is performed using a low-molecular active hydrogen compound); There is a method of mixing a low-molecular active hydrogen compound in advance and reacting it with a polyisocyanate. Among these methods, methods (1) and (2) involve a phase between a high-molecular polyol and a low-molecular active hydrogen compound. Although solubility is not a problem, in the method (3), the high molecular polyol and the low molecular active hydrogen compound may be separated due to poor compatibility.
There is a problem in that the viscosity of the mixture increases abnormally, resulting in loss of fluidity and significant loss of workability.

The inventors of the present invention have conducted extensive studies on a method for producing polyurethane that does not have the above-mentioned problems, and as a result, have arrived at the present invention. That is, the present invention uses an organic polyisocyanate φ) and a polyol composition φ) containing a high molecular polyol (a), an IZ low molecular active hydrogen compound (b), and a sulfur-containing anionic surfactant (C), if necessary. 2. This is a method for producing polyurethane, which is characterized by carrying out the reaction in the presence of a blowing agent.

Examples of the sulfur-containing anionic surfactant used in the present invention include sulfonate type anionic surfactants and/or sulfate ester salt type anionic surfactants. Examples of the sulfonate salt type anionic surfactant and the sulfate salt type anionic surfactant (e) include the following compounds.

■ Sulfonate type anionic surfactant (1) Alkylbenzene sulfonate Alkylbenzene sulfone having one and/or a plurality of branched or straight chain alkyl groups, usually having 8 to 20 (preferably 10 to 18) carbon atoms In the case of salts, such as alkali metals (sodium-potassium, etc.), ammonium, and amines (alkanolamines such as mono-, di-, and triethanolamines,
In addition to the salts of lovanolamine tt) (the same applies to the salts of the following activators), it also includes salts of alkaline earth metals (calcium, magnesium, etc.) (2), fluphosuccinate salts, dialkyl sulfosuccinate salts :The number of carbon atoms in the aryl group is usually 6 to 6.
20. The alkyl group also contains a cycloalyl group. / or alkylnaphthalene sulfonate.

The same description will be used below. Linaphthalene sulfonic acid or naphthalene sulfonate having one and/or a plurality of alkyl groups having a carbon number of usually 1 to 18, and its polymerine condensate (degree of condensation is usually 1 to 20, preferably 1 to 8), etc. (4) Alkanesulfonate, etc. having an alkyl group, usually having 8 to 20 carbon atoms (5) α-olefin sulfonate, usually having 1 carbon number
Sulfonic acid sodium salts of α-olefins 5 to 18 (6) Fatty acid amide sulfonate Igein IT (I, G,), etc. (7) Lignosulfonate (sodium salt, etc.)
Petroleum salts, phonates (sodium salts, etc.), etc. (8)
Alkyl Substituted Aryl Ether Sulfonate Among these sulfonate type anionic surfactants, the sulfonate type anionic surfactant described in section (2) is preferred.

■ Sulfate ester salt type anionic surfactant (1) Alkyl sulfate ester salt Straight chain and/or branched sulfate ester salts of saturated and/or unsaturated alcohols with carbon number of 6 to 20 (preferably 12 to 18), etc. (2) Polyoxyalkylene alkyl sulfate salt A linear and/or branched saturated and/or unsaturated alcohol having 2 to 4 carbon atoms (AO ) Adduct sulfate ester salt, etc. (3) Polyoxyalkylene alkylaryl ether sulfate salt AO adduct of alkylphenol or alkylnaphthol having at least one alkyl group having 8 to 12 carbon atoms (the number of moles of AO added is usually 2 to 1) 50. Preferably 2~
20) Nisthyl sulfate salt, etc. (4) Higher fatty acid ester sulfate ester salt, saturated and/or unsaturated fatty acid monoglyceride sulfate ester salt, etc., having carbon atoms of 10 to 20. (5) Higher fatty acid alkylolamide sulfate ester salt, carbon number 10 to 20. (6) Sulfated oil, highly sulfated oil, sulfated fatty acid ester and sulfated fatty acid funnel oil, sulfated sodium salt of butyl oleate, olein Sulfated sodium salts of acids, etc. (7) Sulfated olefins Sulfated sodium salts of α-olefins having 12 to 18 carbon atoms, etc. Among these °C sulfate ester salt type anionic surfactants, preferred are (1) and (2). ) is a sulfuric acid ester salt type anionic surfactant described in the section.

A sulfonate type anionic surfactant and a sulfate ester salt type anionic surfactant can be used together.

For the sulfonate salt type and sulfate ester salt type anionic surfactants, polymeric surfactants can also be used, but low molecular weight surfactants (for example, those with a molecular weight of usually 50
00 or less, preferably 8000 or less).

For details on sulfonate type anionic surfactants, see JP-A-56-125488, page 678. For details on alkyl-substituted aryl ether sulfonates, see JP-A-55-76668, pages 852-853. Details of the sulfate ester salt type anionic surfactants are described on page 672 of JP-A-56-125487.

Low molecular weight active hydrogen compound (b) used in the present invention
Examples include low-molecular polyols (triethanolamine,
ethylene glycol, 1,4-butanediol, diethylene glycol, trimethylolpropane, glycerin, etc.), polyamines (tolylene diamine, xylylene diamine, diaminodiphenylmethane, hydrogenated diaminodiphenylmegne, methylenebis-〇-chloroaniline,
Isophorone diamine, piperazine, aminoethylpiperazine), amino alcohol (monoethanolamine).

(e.g., jetanol, amine, etc.) and mixtures of two or more thereof. Among these, preferred are low-molecular polyols, and particularly preferred are ethylene glycol and 1,4-butanediol.

Examples of the polymer polyol (a) used in the present invention include those conventionally used in the production of polyurethane. For example, polyether polyol-1 described in Japanese Patent Application No. 56-4506.

Examples include polyester polyol, polyether esteflet polyol 9 polymer polyol axis, and mixtures of two or more of these. Among these polymer polyols, preferred are polyether polyols and polymer polyols, and particularly preferred is polyether polyol 4.

The zero value of high-molecular polyols has a wide range (for example, 10 to
500). When producing flexible polyurethane, OH- is usually 10-100, preferably 16-70. Particularly preferably 20 to 40. Usually 200 or more for hard polyurethane.

Preferably, those having an OH value of 400 or more are used.

For semi-rigid polyurethane production, the OH value is usually 20.
~150. Preferably it is 26-100.

In addition, for semi-rigid materials, flexible polyurethane materials (low OH
It can also be used in combination with hard (high OH value) and hard (high OH value). O
If the H value is less than 10, the viscosity will be high and the workability of polyurethane production will be poor. When the 0■ value exceeds 100, the temperature characteristics of polyurethane deteriorate. The molecular weight of the polymer polyol is usually 1000 or more, preferably 8000 to 7.
It is 000.

Also, among the polymer polyols, those having primary OH at the terminal are preferable. The terminal primary OH content is usually 20% or more, preferably 8096 or more, and particularly preferably 40 to 80%. Polymer polyols containing terminal primary 0■ contain oxyethylene chains at the terminals (tipped type, balanced type, run, dumb chip type)
The content thereof is usually 5 to 40% by weight, preferably 10 to 80% by weight. By using a polyol having a terminal oxyethylene chain content within the above range, when polyurethane is molded and cured by, for example, the Reaccidine injection molding method (RIM method), a molded product with good initial strength upon demolding can be obtained, and a good molded product can be obtained. A molded product with good physical properties can be obtained. If the content of terminal oxyethylene chains is less than 5%, the initial strength during demolding is low and problems such as breakage of the molded product are likely to occur. If it exceeds 40%, the appearance of the polymer polyol becomes poor (turbidity and ) The moisture resistance of the molded product becomes extremely poor.

In the polyol composition of the present invention, surfactant (0)
The content of is in the composition [total of (a), (b) and (e)].

It is usually 0.5 to 5% by weight, preferably 0.8 to 8% by weight. If the content is less than 0.5% by weight, the compatibility between the high-molecular polyol (&) and the low-molecular active hydrogen compound (b) will be insufficient, and when polyurethane is produced using a polyol composition of more than 5% by weight, It causes negative effects such as deterioration of physical properties.

The amount of (a) in the low molecular weight active hydrogen compound is 10 by weight.
Usually 0.1 to 50 parts per 0 parts, preferably 15 to 4 parts
There is 0 part c. (b) is a combination of low molecular weight polyols
(a) to.

(b> is a polyamine or amino alcohol, the weight ratio of (a) is smaller than the above, and usually 0.0 parts to ioo parts). 1 to 20 parts, preferably 0.5 to 1o
Department.

Also, the equivalent ratio of (a) and (b) is (a) to 1 equivalent (
b) is usually 0.05 to 80 equivalents, preferably 0.2 to 2
It is 5 equivalents. When (b) is a low molecular polyol, (a
) (1)) is usually 6 to 80 equivalents, preferably 10 to 25 equivalents, and in the case of polyamine or amino alcohol, (a) and (b) are usually 0.08 to X equivalent. ~6 equivalents.

Preferably it is 0.1 to 8 equivalents.

The method of incorporating (b) and (e) into (a) is not particularly limited as long as they can be mixed uniformly.

For example, ■, a method of mixing (a) and (C) and then mixing (b), ■, a method of mixing (b) and (e), and then (a)
), ■, method of mixing (a) and (b) and then mixing (e), ■, (a), (b),
Examples include a method of mixing (0). Preferred is method (2). Alternatively, a concentrate is prepared by mixing (C) with a small amount of (a) and/or (b) in advance,
It can also be added to other ingredients. Mixing can be done at room temperature or by heating (usually 40-150°C, preferably 70-150°C).
180°C).

The polyol composition of the present invention is useful for producing and using polyurethane. As the organic polyisocyanate used in the production of polyurethane, those conventionally used in the production of polyurethane can be used. For example, the patent application in 1983
-4505 can be used. Specifically, aliphatic polyisocyanates, cycloaliphatic polyisocyanates, aromatic polyisocyanates, mixtures of two or more thereof, crude products thereof (crude polyisocyanates such as crude TDI, crude MDI, modified polyisocyanates such as liquefied MDI) (Carposiimide modification.

It can also be used as a free isocyanate-containing prepolymer obtained by reacting a polyol with an excess polyisocyanate (TDI, MDI, etc.) or an excess polyisocyanate (TDI, MDI, etc.).

Moreover, these can also be used in combination (for example, a modified polyisocyanate and a prepolymer are used together).

The content of free isocyanate groups in the above-mentioned modified polyisocyanates and prepolymers is usually 9 to 80%, preferably 15 to 80%, particularly preferably 20 to 80%.

Among the organic polyisocyanates (A), preferred are modified polyisocyanates, and particularly preferred are carposiimide-modified MDI, prepolymers of MDI and polyol, and mixtures thereof.

In carrying out the method of the present invention, one blowing agent [water and/or halogen-substituted aliphatic hydrocarbon blowing agent (Freon-
11 etc.)] to produce a foam, or elastomers, sealants, sheets, etc. may be produced without using a blowing agent. Further, if necessary, the reaction can be carried out in the presence of a catalyst (such as a tertiary amine, an organic tin compound, an organic lead compound, etc.), a silicone foam stabilizer, or other auxiliary agents.

The polyurethane production method may be the same as conventional methods, and can also be applied to the one-shot method and prepolymer pouring method.

In producing polyurethane, the ratio (equivalence ratio) of active hydrogen component and organic polyisocyanate is usually determined as follows: clean hydrogen-containing groups (OH, Nu2.Nu, etc.): N■ group: = (o
, s : t, 2) to (1,2: 0.8), preferably (1: 0.95) to (1: 1.15'r
Qhr.

The two polyurethane manufacturing methods of the present invention are particularly useful for molding by the RIM method. A polyurethane molded product can be produced by molding using the RIM method using a conventional method. For example, a polyol composition containing a low-molecular active hydrogen compound, a catalyst, and if necessary a blowing agent (water or Freon 11
), pigment, and foam stabilizer were added and mixed uniformly as liquid A, and as liquid B, an organic polyisocyanate was prepared in advance.

Fill the tank of the high-pressure foaming machine and the B liquid tank.

The injection nozzle of the high-pressure foaming machine and the injection port of the mold are connected in advance, and liquids A and B are mixed with a mixing head and injected into a closed mold, and after curing, the mold is demolded.

Methods other than the RIM method For example, molding other than the RIM method (open mold molding, PVC integral molding method, vacuum molding, etc.)
cold cure and hot cure), slab method,
On-site construction, spray method, injection.

It can also be applied to various methods such as coating and impregnation.

The polyol composition of the present invention can also contain a blowing agent, a catalyst and other auxiliary agents if necessary.

These may be the same as those described in JP-A-56-67829.

Examples of the blowing agent include water and/or halogen-substituted aliphatic hydrocarbon blowing agents. Examples of the catalyst include an 8th class amine catalyst, its organic acid salt, and an organometallic catalyst (tin-based catalyst, mercury acetate, cobalt naphthenate, etc.). Other auxiliary agents include foam stabilizers.

Examples include colorants and stabilizers. The amount of blowing agent in the polyol composition is usually 0 to 20% by weight, preferably 0.
The amount of catalyst is usually 0 to 8% by weight, preferably 0.5 to 2% by weight.7 The amount of other auxiliaries is usually θ to 10% by weight, preferably 0.1 to 2% by weight. %.

The method for producing polyurethane in which a polyol composition and an organic polyisocyanate are reacted in the present invention is a conventional method in which a high molecular polyol and a low molecular active hydrogen compound are mixed in advance and reacted with a polyisocyanate.
The problem of separation due to poor compatibility between the high-molecular polyol and the low-molecular active hydrogen compound has been resolved, and the compatibility has become good. In addition, the viscosity does not increase abnormally, fluidity is lost, and workability is not impaired, and the storage stability is good. Therefore, when polyurethane is produced using this composition, it is not necessary to prepare a compound each time, and work efficiency is improved.

The method for producing polyurethane of the present invention is used for automobile cover covers. Soft fascia, mudguard fender,
It is particularly useful for manufacturing air spoilers and the like.

The present invention will be further explained below with reference to Examples.

The present invention is not limited to this.

Example 1 A polyoxypropylene polyoxyethylene derivative of propylene glycol (terminal polyoxyethylene chain 20% by weight) having a hydroxyl value of 2B was used as a polymer polyol.

Sulfosuccinic acid octyl ester sodium salt was added to the above-mentioned polymeric polyol, and finally ethylene glycol was added and heated to 80-120° C. to uniformly dissolve it to obtain a polyol composition.

Then, DABOOB BL was added to the above polyol composition.
V (manufactured by Sankyo Air Products, 38% dipropylene glycol solution of triethylene diamine), DTD (
dibutyltin dilaurate), Guiflon 1l-U (Daikin Industries, Ltd. Freon-11) and VL-Black #
2000 (black toner manufactured by Fuji Shiki Co., Ltd.).

A dispersion of carbon black (2596 polyoxypropylene glycol dispersion) was premixed in advance to form a liquid A, and Millionaire MTL (modified MDI manufactured by Nippon Polyurethane Co., Ltd.) was used as a liquid B.

High-pressure foaming machine (manufactured by Maruka Kakoki Co., Ltd., MEG-AcMA
5. Mix liquid A and liquid B using a Q type) to a thickness of 0.25
z.

A urethane molded product was obtained by injecting the mixture into a plate-shaped sealed mold having a width of 80 CIR and a length of 50 CIR. The foaming recipe is shown in Table 1, and the physical properties of the molded product and the surface condition of the molded product are shown in Table 2.

Example 2 The operation of the high-pressure foaming machine for liquids A and B used in Example 1 was stopped, and the operation of the agitator in the liquid A and B storage tanks was also stopped).
Each was left at room temperature for 8 days. Thereafter, a urethane molded product was obtained under the same conditions as in Example 1. The foaming recipe is shown in Table 1, and the physical properties and surface condition of the molded product are shown in Table 2.

Comparative Example 1 Except for not using the sulfocoa monophosphate octylate sodium salt in the polyol composition of Example 1,
Solution A was prepared in the same manner as in Example 1.

The table below shows the zero-foaming formulation obtained for urethane molded products under similar conditions.
Table 2 shows the physical property values and surface condition of the molded product.

Comparative example 2 The operation of the high-pressure foaming machine for liquids A and B used in comparative examples 1 and 2 was stopped, and the operation of the agitator in the liquid A and B storage tanks was also stopped).
It was left at room temperature for 8 days. Thereafter, a urethane molded product was obtained under the same conditions as in Comparative Example 1. The foaming recipe is shown in Table 1, and the physical properties and surface condition of the molded product are shown in Table 2.

The molding conditions are as follows.
8) Discharge amount (&g/min): 20 injection time (
see)' 1.281).

Discharge pressure (Jcg/cm), 150 Raw material temperature (0
C) 2) = 40 Mold temperature (°C) Near 0 Demolding time (see): 80 Green strength (see) 8): 90 (1) 1) Both A and B liquids are 150 ktj/c42) A
40°C for both liquid and B liquid 8) Number of seconds until no cracks appear when the molded product is bent 1800 degrees after demolding from the start of injection.

4) JI8-6801, No. 8 dumbbell tensile speed 200 m*/m 1n 5) JTSK-6801B type tensile speed 200fff
f/m1n6) Sample width 251m, span 401m,
Punch diameter 2.5R, pressurization speed IQ II/m! n
7) Sample width 25m, overhang 1001ff.

120°CX 1hr

Claims (1)

[Claims] 1. A polyol composition comprising an organic polyisocyanate (A) and a polymer polyol (a) containing a low-molecular active hydrogen compound (b) and a sulfur-containing anionic surfactant (e). 2. A method for producing polyurethane, characterized in that the sulfur-containing anionic surfactant is a sulfonate-type anionic surfactant and/or a sulfuric acid ester salt-type anionic surfactant. The manufacturing method according to claim 1, which is a surfactant. 8. The manufacturing method according to claim 1 or 2, which contains 05 to 5% by weight of (e). 4.・Nate-type anionic surfactants include alkylbenzene sulfonate, sulfosuccinate ester salt, (
The claim 1 is a compound selected from the group consisting of (alkyl) naphthalene sulfonates and their formalin condensates, alkanesulfonates, α-olefin sulfonates, fatty acid a2F sulfonates, and lignosulfonates. The manufacturing method according to any one of Items 1 to 8. 5. Sulfate ester salt type anionic surfactants include alkyl sulfate ester salts, polyoxyalkylene alkyl sulfate ester salts, polyoxyalkylene alkylaryl ether sulfate ester salts, higher fatty acid ester sulfate ester salts, and higher fatty acid alkylolamide sulfate ester salts. , a sulfated moiety, a highly sulfated oil, a sulfated fatty acid ester, and a sulfated olefin. 6. (a) and (b) (7) Weight ratio is (a):
(b) −100: The manufacturing method according to any one of claims 1 to 5, wherein the value is 1.1 to 50. 7. The manufacturing method according to any one of claims 1 to 6, wherein (b) is a low molecular polyol.