JPS61200116A - Production of modified polyurethane - Google Patents

Abstract

PURPOSE:To obtain a modified polyurethane giving a sealant having low modulus and excellent weatherability, by reacting a polymeric polyol composed of a polyol and an ethylenic unsaturated monomer with an organic polyisocyanate and an isocyanato organic silane. CONSTITUTION:The objective modified polyurethane is produced by reacting (A) a polymeric polyol composed of (a) a polyol (preferably a combination of a high-molecular weight polyol such as polyether polyol and a low-molecular weight polyol such as ethylene glycol) and (b) an ethylenic unsaturated monomer [preferably acrylonitrile, [methlacrylic acid (salt) and their derivatives] with (B) an organic polyisocyanate (preferably hexamethylene diisocyanate, etc.) and (C) an isocyanato organic silane (preferably gamma-isocyanatopropyltrietho xysilane, etc.). The molar ratio of the OH of the component A to the NCO of the components B and C is preferably 1:1. The reaction is carried out prefer ably by reacting the component A with the component C, and reacting the product with the component B.

Description

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

[Conventional technology]

Conventionally, as silicon-terminated polyurethane, polyurethane prepolymer having terminal active hydrogen atoms is used as isocyanate W.
A polymer obtained by reacting with ill silane is known (Japanese Unexamined Patent Publication No. 58-29818).

However, when this polymer is applied to a sealant, it is not satisfied (ζ) as a low modulus sealant that can easily follow the movement of joints, which is a recent demand.It is also not fully satisfied in terms of weather resistance.

[Problem that the invention seeks to solve]

The present inventors conducted extensive research to find a method for producing modified polyurethane that would yield a sealant with a lower modulus and better weather resistance than when applying sealant Cζ, and arrived at the present invention.

[Means for solving the problem]

The present invention is a method for producing a modified polyurethane, which is characterized by reacting a polymer polyol from a polyoleate or a tylenically unsaturated monomer, an in-house polyisocyanate, and an isocyanate organic silane.

In the present invention, polymeric polyols can be incorporated by polymerizing ethylenically unsaturated monomers in the polyol. Examples of the above-mentioned ethylenically unsaturated monomers include the following.

(a) Acrylic acid or its salts and derivatives thereof; (1) Acrylic acid or its salts; The number of carbon atoms is usually 1
~20. Preferably 1 to 10) ester; aminoalkyl (meth) such as dimethylamine ethyl methacrylate
Acrylate; (meth)acrylic acid amide; preferably methyl methacrylate.

n-butyl methacrylate and acrylonitrile (b) Aromatic vinyl monomers: styrene, α-methylstyrene, etc. (C) Olefinic hydrocarbon monomers: ethylene, propylene, butadiene, isobutylene, isoprene, 1
4-Pentadiene, etc. (d) Hinyl ester alone: vinyl acetate, etc. (e
) Vinyl halide monomers: vinyl chloride, vinylidene chloride, etc. (f) Vinyl ether monomers: vinyl methyl ether, etc. (g) Ethylenically unsaturated monomers having a hydrolyzable silyl group: hydrolyzable silyl group (halosilyl , alkoxysilyl,
Acyloxysilyl, amidosilyl.

Aminoxysilyl, alkenyloxysilyl.

Vinyl-2(meth)acryloxyalkyl-2(meth)acrylamidoalkyl- or allyl-compounds having groups such as aminosilyl, oximesilyl, thioalkoxysilyl, etc. For example: a) Hydrolyzable silyl group-containing (meth)acrylic Roxyalkyl compound: (meth)acryloxyalkyl (alkyl group: C1-4
) Alkoxysilanes such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, etc.; (meth)acryloxyalkyl (
Alkyl groups: C+ -4) Halosilanes such as γ-methacryloxypropylmethyldichlorosilane.

γ-Acryloxytrichlorosilane) Hydrolyzable silyl group-containing vinyl compounds: vinyl alkoxysilanes such as vinylmethyldimethoxysilane,
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, etc.;
Vinylhalosilanes such as vinyldichlorosilane: preferably hydrolyzable silyl group-containing (meth)acryloxyalkyl compounds, particularly preferably γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane, which are ethylenically unsaturated monomers. Among the mercury, the preferred one is (
It is a monomer of a).

Polyols used in the production of polymer polyols include high molecular weight polyols such as polyether polyols, polyester polyols, polyester ether polyols, polybutadiene polyols and low molecular weight polyols.

Examples of polyether polyols include compounds having a structure in which alkylene oxide is added to an active hydrogen-containing compound such as low-molecular polyols, amines, polyhydric phenols, and polycarboxylic acids, and ring-opening polymers of alkylene oxide.

The above-mentioned low molecular polyols include ethylene glycol,
Propylene glycol, 1.4-f tanediol, 1
．． 6-hexanediol, diethylene glycol, neopentyl glycol, bis(hydroxymethyl)cyclohexane, bis(hydroxyethyl)senzene, glycerin, trimethylolpropane, pen polyerythritol, sorbitol.

Examples include 4- to 8-hydric alcohols such as sucrose.

Amines include methylamine and ethylamine.

Aliphatic monoamines such as propylamine, butylamine, decylamine; cycloaliphatic monoamines such as cyclohexylamine; araliphatic monoamines such as benzylamine; aromatic monoamines such as aniline, toluidine, naphthylamine; ethylenediamine, trimethylenediamine, hexamethylenediamine , aliphatic polyamines such as diethylenetriamine; heterocyclic polyamines such as piperazine, IN-aminoethylpiperazine; phenylenediamine, tolylenediamine, xylylenediamine.

Diphenylmethanediamine, polyphenylmethanepolyamine, diaminotoluene, diethyltoluenediamine,
Aromatic polyamines such as methylene dianiline, methylene bis orthochloroaniline, and monoethanolamine, jetanolamine.

triethanolamine, triisopropanolamine,
Examples include alkanolamines such as butanolamine.

Examples of polyhydric phenols include polym7 enols such as catechol, resorcinol, pyrogallol, and hydroquinone, as well as bisphenols such as bisphenol A and bisphenol F. Examples of polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipine, sebacic acid, maleic acid, and fumaric acid; 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.

Examples of the alkylene oxide mentioned above include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, etc., and one or more of these may be used. The alkylene oxide may be added to the compound containing active water by a conventional method, and when two or more alkylene oxides are added, either a block or random addition method may be used.

Examples of ring-opening polymers of alkylene oxide include ring-opening polymers of tetrahydrofuran such as polytetramethylene glycol (Japanese Unexamined Patent Publication No. 58-29816).

Polyether polyols include polycarboxylic acids (aliphatic saturated or unsaturated polycarboxylic acids such as adipine, azelaic acid, dodecanoic acid).

Maleic acid, fumaric acid, itacone, dichloromethane; aromatic polycarboxylic acids such as phthalic acid.

isophthalic acid) and the above-mentioned low-molecular-weight polyol or polyether polyol, and polycaprolactone polyol, such as an initiator [glycol (ethylene glycol, etc.)
, triol, etc.] as an ester and (substituted) caprolactone (ε-caprolactone, α-methyl-ε-caprolactone, ε-methyl-ε-caprolactone, etc.)
Examples include polyols obtained by addition-polymerizing in the presence of a catalyst (organometallic compound, metal chelate compound, fatty acid metal acylated product, etc.). Further, the polyester ether polyol includes a linear or branched polyester ether having an OH group in the molecular chain obtained by esterifying the polycarboxylic acid and the polyether polyol, or a mixture of this and the low-molecular-weight polyol; Addition reaction of alkylene oxide (e.g. ethylene oxide, propylene oxide, etc.) to polyester having a carboxyl group and/or Of'i group at the terminal.
Examples include polyethers obtained by

As polybutadiene polyol, JP-A-55-98
No. 220, JP-A-56-84715, JP-A-58-5
No. 7413, each publication 8, and Sealants (written by Damsis).

Reinhold Publishing, 1967) (7) 164~
Examples include the polyols described on page 165. The hydroxyl value of this product is usually 50 to 100.

In addition, (this general formula H (J -L-SS (IVI-bs) n-L-
OHtl+ (wherein L and 1 are each a divalent aliphatic group, and n is an integer from 1 to 100)
It is also possible to use a similar poly(1) thiol compound in which 01-1 of the above polyol is changed to SR.

Preferred among the polymeric polyols are polypropylene/glycol, polytetramethylene glycol, and polycapropylene glycol.

The equivalent weight of the polymeric polyol is usually 200 to 5,000, preferably 400 to 4,000. Among the low-molecular-weight polyols, in the category of polyether polyols, the same Cfr as low-molecular-weight polyols can be used.

Among polyols, preferred are polyols (or polymer polyols) and combinations of low-molecular polyols (the amount of molecular polyol is 0.001 to 30% by weight vs. polymer polyol).The average equivalent weight of the polyol (or a'tan 31-25
00. Preferably it is 100-2000.

When polymerizing the ethylene infusion monomer in a polyol, the proportion of the polyol and the ethylenically unsaturated monomer in Cζ can be varied over a wide range; Ethylenically unsaturated monomer (or polymer) usually 2 to 70 parts by weight, preferably 5 to 70 parts by weight
It is 40 parts by weight.

The method for producing a polymer polyol from a polyol and an ethylenically unsaturated monomer may be any known method, for example, polymerizing an ethylenically unsaturated monomer in a polyol in the presence of a polymerization catalyst (such as a radical generator). Method (U.S. Pat. No. 3,883,351).

Japanese Patent Publication No. 39-24737, Japanese Patent Publication No. 47-47999, Japanese Unexamined Patent Publication No. 50-15894) or a polymer obtained by previously polymerizing the above monomers and a polyol composition in the presence of a radical generator, An example is a method of graft polymerization (Japanese Patent Publication No. 47-47597). The former method is preferred.

The reaction (fourth cup) temperature is usually 50 to 170°C, preferably 9
The temperature is 0 to 150°C. Polymerization catalyst used in polymerization reaction (
As the radical generator), azo compounds, peroxides, depopulated monosalts, perborates, etc. can be used, but azo compounds are practically preferred. The amount used is also set aside, preferably 01~
1.5 parts by weight. The above polymerization can also be carried out in the presence of a solvent such as toluene, xylene and the like.

The hydroxyl value of the polymer polyol is usually 1 to 140. Preferably it is 5-112.

Beampolymer polyols consist of 50-98% by weight of a polyol and 2-50% by weight of an ethylenically unsaturated monomer grafted or dispersed in the polyol.

Isocyanate silane used in the invention, -
(In the formula, 1<1 is a divalent organic group, 1 (2 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R3 is a carbon number of 1 to 4. and a is an integer of 1-3).

Examples of R+ include those represented by -A- or -QN)icUX-A-. In the above, A is an alkylene group, preferably a lower alkylene group having 2 or more carbon atoms (especially f and 3 or more). Specifically -(CH2)
--(C1-iz) etc.

j Q is a diisocyanate residue, and the diisocyanate is an aromatic diisocyanate (2,4- or 2,6-
- tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, etc.) and 13i: + = t
, diisocyanates (hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, hydrogenated 1"Dl, hydrogenated T'L)1, etc.).

X is the residue of an active hydrogen-containing group -X-M, N'H.

Examples include 0 and S.

Examples of the alkyl group having 1 to 4 carbon atoms in R2 and R3 include a methyl group and an ethyl group.

a is preferably 2 or 3.

Preferred isocyanate organic silanes represented by the general formula (1) are r-isocyanatepropyltriethoxysilane and γ-isocyanatepropyltrimethoxysilane.

The organic polyisocyanates used in the present invention include aliphatic polyisocyanates having 2 to 12 carbon atoms (excluding carbon in the NGO group), alicyclic polyisocyanates having 4 to 15 carbon atoms, and aromatic polyisocyanates having 8 to 12 carbon atoms. Aliphatic polyisocyanates, aromatic polyisocyanates having 6 to 20 carbon atoms, and modified products of these polyisocyanates (modified products containing carposiimide groups, all uretdione groups, uretoimine groups, urea groups, biuret groups, and/or incyanurate groups) objects, etc.) can be used.

Such polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate (MIJI).

Dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate,
2,6-Diucyanate methyl caproate.

Bis(2-isocyanatoethyl) fumarate.

Bis(2-isocyanatoethyl)carbonate.

2-Isocyanate ethyl-2,6-dicyanate hexanoate: Isophorone diisocyanate (IPL
) I), dicyclohexylmethane diisocyanate (hydrogenated 1vtDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated 'I'DI), bis(2-isocyanateethyl) 4-cyclohexene-1,2-dicarboxylate; Xylylene diisocyanate, diethylbenzene diisocyanate; 1fLJI water modified product, l)'l)1
Tolylene diisocyanate (TDI)
), Crude %・4 Tvr, Diphenylmethane diisocyanate (RED I) e Polyphenylmethane polyisocyanate (PAPL: Crude 9 ML) I
) ) modified IVIDI' (carposiimide modification etc.), naphthylene diisocyanate; and these 2 (
Examples include overlapping mixtures.

Among these, preferred in terms of weather resistance are aliphatic diisocyanates and anal cyclic diisocyanates.
Particularly preferred are hexamethylene diisocyanate and isophorone diisocyanate. TDI is preferred for applications where weather resistance is not an issue.

When reacting with a polymer polyol, an organic polyisocyanate, and an isocyanate-organosilane, the molar ratio of the hydroxyl group of the polymer polyol to the NCO of the organic polyisocyanate and isocyanate-organosilane is usually 09.:1.
1 to 1.1:0.9, preferably substantially 1:1.

The amount of isocyanate organosilane greatly influences the moisture curability of the product and is therefore determined according to the desired moisture curability.

The molar ratio of organic polyisocyanate to isocyanate-organosilane is usually 9:1 to 1:9. Preferably 8:2-2:
It is 8. The reaction between the polymeric polyol, organic polyisocyanate and isocyanate blind silane is conducted under anhydrous conditions to prevent hydrolysis of the alkoxysilane. The reaction temperature for urethanization is generally 0 to 150°C, preferably 2
The temperature is 5 to 90°C.

The reaction can be carried out, if necessary, in the presence of an organic solvent inert to isocyanate groups. This organic solvent includes aromatic hydrocarbons (toluene, xylene, etc.),
Ketones (methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate.

(n-butyl acetate, etc.) and mixtures of two or more thereof. If necessary, metal catalysts such as diptyltin dilaurate, stannath-2-ethylhexoate, iron-acetylacetonate; amine catalysts such as triethylenediamine, N-methylmorpholine, etc. can also be used as the catalyst. The fecal dose is typically 0005-02% of the total weight based on the polymer.

The reaction of the polymeric polyol, organic polyisocyanate and isocyanate-organosilane can be carried out simultaneously or in any order. For example, the polymer polyol and the organic polyisocyanate may be reacted first and then the isocyanate organosilane is reacted, or the polymer polyol and the isocyanate organosilane may be reacted and then the useful polyisonanate may be reacted. Alternatively, the polymer polyol, organic polyisocyanate, and isocyanate-paid silane may be reacted simultaneously.
This is the point at which detection becomes impossible.

Among these reaction methods, preferably the polymer polyol is reacted with the incyanate organic silane, and then the organic polyisocyanate is reacted. This is because a sealant with a lower modulus can be obtained in this case than in the case where a polymer polyol and an organic polyisocyanate are reacted and then an isocyanate organic silane is reacted.

The molecular weight of the modified polyurethane obtained in this way is usually 1,000 to 30,000. Preferably 2,000-2
Q, 000. The number of silyl groups is usually 2 or more, preferably 2 to 4. The silicon content of the modified polyurethane is usually 0.5 to 5.2% by weight, preferably 1 to 4% by weight. When the silicon content is 0.5% by weight, the curing speed of the modified polyurethane decreases.

Moreover, when the silicon content is more than 52%, the number of silyl groups is large and the crosslinking density becomes high, making it extremely brittle.

When the modified polyurethane in the present invention is exposed to fζ in the atmosphere, it forms a network structure and hardens at room temperature. The curing rate varies depending on the atmospheric temperature, relative humidity, and the type of hydrolyzable group. Specifically, the higher the temperature and humidity of 1ζ, the higher the curing rate, and the higher the number of hydrolyzable groups, or in the case of an alkoxy group, the lower the number of carbon atoms, the higher the curing rate.

When curing the silyl group-containing modified polyurethane of the present invention, a curing accelerator may be used if necessary. Examples of curing accelerators include titanates, amines, organic tin compounds, and acidic compounds, such as flukyl titanate and tin octylate.

Metal salts of carboxylic acids such as schiftyltin dilaurate and dibutyltin maleate, amine salts such as cyphthylamine-2-hexoate, and others JP-A-58-19361
The cured piece described in the above publication is exemplified by medium I.

The amount of curing accelerator added is usually 0,001 to 20% by weight based on the modified polyurethane.

The modified polyurethane in the present invention (ζ) has a filler for fences,
It is possible to mix pigments and additives (ultraviolet absorbers, heat resistance improvers, leveling agents, anti-sag agents, etc.). Specifically, the method described in JP-A-58-19861 can be used. Furthermore, a storage stabilizer can be added to improve stability during storage.

Examples of such storage stabilizers include conventionally known silanes having a hydrolyzable silyl group such as methyltrimethoxysilane, silicates, and γ-methacryloxypropyltrimethoxysilane, methyl orthoformate, and ethyl orthoformate. β of formic acid esters, acetylacetone, etc.
-One or more types of diketones can be used.

The modified polyurethane in the present invention can be used for various inorganic and organic materials. The details are JP-A-58-1
No. 9361 describes the violation of Cζ.

[Embodiment 4] Examples (hereinafter, the present invention will be explained based on the 1ζ theory) will be described below, but the present invention is not limited thereto. Parts and percentages in the examples are based on weight.

Example 1 Polypropylene glycothermal (molecular weight 4000) 60
0 g was put into a Kolben and the temperature was raised to 100°C. 32 g of n-butyl methacrylate and 0.0 g of abbisisobutyronitrile.
A solution containing 3 g was added dropwise over 1 hour.

After reacting at the same temperature for 2 hours, 0.15 g of azobisisobutyronitrile was added and the reaction was further continued for 1 hour.

After that, it was cooled to 80℃ and the isophorone diisocyanate 22
．． 2 g of γ-isocyanatepropyltriethoxysilane and 2 g of octylic acid were added and reacted at the same temperature for 5 hours. Measure the infrared absorption spectrum 22
It was confirmed that absorption of rJCO disappeared at 50 cyn. The viscosity of the silicone-modified polyurethane obtained was 34.500 cps (25°C).

Example 2 The methacrylic acid n-butyl of Example 1 was converted into methacrylic acid n-
A similar reaction was carried out by replacing methyl with silicone-modified polyurethane fat (viscosity a: 6,200 cps).

Example 3 Polypropylene glycol (molecular weight 4
000) 32g n-butyl methacrylate in Google
was polymerized to obtain a polymer polyol. Thereafter, the mixture was cooled to 80°C, and 24.7 g of γ-isocyanatepropyltriethoxysilane and 02 g of tin octylate were added thereto and allowed to react for 2 hours. After confirming that the absorption at 2250 cm in the infrared absorption spectrum was less than the minute axis, 222 g of isophorone diisocyanate was added and reacted for 4 hours at the same temperature.The infrared absorption spectrum showed that the absorption of NGO at 2250 cm' was gone. Check the modified polyurethane (viscosity 38,500
cps) was obtained.

Reference example 1 Polypropylene glycol l 4ooo) 6oog
was added to Kolben 1ζ and heated to 80°C, and 22.2 g of isophorone diisocyanate and 0.2 g of octylic acid J were added.
was added and reacted at the same temperature for 4 hours. After confirming that the absorption of INC (J) of 2250 cm' in the infrared absorption spectrum disappeared, 24.7 g of γ-isocyanatepropyltrimethoxysilane was added and reacted for 2 hours. Obtained silicone-modified urethane: Viscosity of sealant is 49,100Cp (
It was 25°0.

Reference Example 2 A homopolymer of n-butyl methacrylate (molecular weight: 8000) was added to 100 g of the modified polyurethane obtained in Reference Example 1.
5 g were mixed and stirred, but when the mixture was left to stand, it separated.

Test Example 1 20 g of each resin, 25 g of calcium carbonate, 5 g of dioctyl phthalate, and 0.1 g of dibutyl dilaurate were
The mixture was placed in a QOml beaker and mixed using a glass rod Cζ for about 5 minutes. Spread the mixture on a glass sheet [94 m inside]
The surface of the mold was made clear by placing it in a tube sprayed with Daifree A-741 (a fluorine-based mold release agent manufactured by Daikin Industries). After leaving at room temperature for 12 hours, 70℃ x 3 hours
The cure was repeated 10 times at room temperature for 3 hours. The sheet was peeled off from the glass and observed with a JISK-6801 eye (
The irradiation conditions were a temperature of 50°C and a rainy season time of 12 minutes and 760 minutes). The results are shown in Table-1.

Table 1 [Effects of the Invention] The modified polyurethane obtained by the present invention has (1) excellent performance such as low modulus, elongation, and weather resistance when applied as a sealant.

Conventional silicon-terminated polyurethanes include those obtained by reacting isocyanate-terminated polyurethane with a specific silane coupling agent having active hydrogen (Japanese Patent Publication No. 40711/1983), and polyurethane prepolymers having terminal active hydrogen atoms with isocyanate organic silane. There is a polymer obtained by the reaction (Japanese Unexamined Patent Publication No. 58-29818), which is used in sealants. All of these are insufficient in terms of low modulus and weather resistance, and especially when an amine thread silane coupling agent is used for the former, the temperature at 90°C to 100°C
High temperature stability is not satisfied.

The present invention improves these points.

(21) The modified polyurethane obtained in the present invention can be used as a room-temperature curable paint or coating agent because it has the above-mentioned effect of being able to produce a modified polyurethane having characteristics such as cross-linking at room temperature and forming a network structure from moisture molecules ζ in the atmosphere. ,glue,
Sealants, casting materials, etc. cost 100 yen.

Claims (1)

[Scope of Claims] 1. A method for producing a modified polyurethane, which comprises reacting a polymer polyol made from a polyol and an ethylenically unsaturated monomer, an organic polyisocyanate, and an isocyanate organic silane. 2. Claim 1 in which a reactant having an excess of active hydrogen atoms obtained by reacting a polymer polyol made of a polyol and an ethylenically unsaturated monomer with an isocyanate organic silane is reacted with an organic polyisocyanate. Manufacturing method described in section. 3. The manufacturing method according to claim 1 or 2, wherein the polyol is a polyol selected from the group consisting of polyether polyol, polyester polyol, polybutadiene polyol, and low-molecular polyol. 4. The production method according to any one of claims 1 to 3, wherein the isocyanate organic silane is a silane having an isocyanate group and at least one hydrolyzable alkoxy group bonded to silicon. 5 The silane having an isocyanate group and at least one hydrolyzable alkoxy group bonded to silicon is γ-
Isocyanate propyltriethoxysilane or γ-
The manufacturing method according to claim 4, which is isocyanatepropyltrimethoxysilane.