JPH02256687A - Modified silicate composition and polyisocyanate composition containing same composition - Google Patents

Abstract

PURPOSE:To obtain the title stable composition useful for urethane resin having excellent heat resistance and flame retardance, having high compatibility with various kinds of compounds by reacting a specific silicate oligomer with an active hydrogen-containing compound in a specific range. CONSTITUTION:(A) A silicate oligomer obtained by subjecting a tetraalkoxysilane to polycondensation through hydrolysis and dehydration in a range of 0-65 hydrolysis ratio is reacted with (B) an active hydrogen-containing compound having 80-500 molecular weight and one functional group in the range of number of alkoxy groups/number of active hydrogens of 1-15, preferably 10-100 to give the aimed composition. Preferably a polyisocyanate and the aimed composition are uniformly dissolved in the weight ratio of 90/10-10/90.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a modified silicate composition and a polyisocyanate composition containing the modified silicate composition. The modified silicate composition of the present invention has high compatibility with various compounds and is useful for various uses. especially,
The polyisocyanate composition containing the modified silicate composition of the present invention prevents the reaction between incyanate and water and can easily obtain a non-foamed product, and is used in fields that require non-foamed products of urethane resins and urea resins. It is useful in

Prior art> Tetraalkoxysilane or the oligomer obtained by hydrolysis and hydrophilic polycondensation of the same has an inorganic surface (Si%S +
02), organic surface (alkyl group, alkoxy group)
It is a substance that has both of these characteristics, and is used for various purposes. However, if flukoxysilane or its oligomer is modified with an active hydrogen-containing compound and its surface activity (surface tension) is changed, it can be made compatible with various compounds. For example, polyisocyanate compounds are used in the fields of urethane resins and urea resins, which are used in paints, paints, and urea resins, respectively.
Polyisocyanate compositions containing the above-mentioned modified silicate compositions are used in various applications such as adhesives, foams, and binders, but if used in these applications, heat resistance, S flammability, smoke generation properties, etc. can be improved. You can expect it to happen.

However, modified silicate compositions have not hitherto been used for such purposes.

For example, urethane resin and urea resin have heat resistance, flame retardancy,
Various improvements have been made to improve low smoke generation properties, including methods to improve the performance of the resin itself (isocyanurate 7-ohm method) and methods to improve the performance of polyols (ester Methods using polyols, aromatic amine compounds, halogenated polyols, etc.) and methods of adding auxiliary agents (adding phosphoric acid esters, halogenated phosphoric acid esters, phosphorus compounds, organometallic compounds, etc.) There have been no attempts to use polyisocyanate compositions containing modified silicate compositions as raw materials, and no modified silicate compositions with performance suitable for such purposes have been known. .

<Problems to be Solved by the Invention> However, if a silicate oligomer can be appropriately modified using an active hydrogen-containing compound and dissolved in various compounds such as polyisocyanate to form a composition with stable properties, The heat resistance of the molded product obtained using this,
Flame retardancy and low smoke emission properties can be improved.

<Means for Solving the Problems> As a result of intensive studies to obtain a modified silicate oligomer suitable for the above purpose, the present inventors have discovered that tetraalkoxysilane or its hydrolyzed dehydrated polymer can be used in a specific hydrolysis rate range. The present invention was completed based on the finding that a composition obtained by modifying a silicate oligomer obtained by condensation with a specific active hydrogen-containing compound can provide a composition that is highly compatible with various compounds and is stable. .

An object of the present invention is to provide a modified silicate composition useful for various uses, and another object of the present invention is to obtain a urethane resin or urea resin that has excellent heat resistance, flame retardancy, and low smoke emission. An object of the present invention is to provide a polyisocyanate composition containing a modified silicate composition that can be used.

According to the present invention, these objects are achieved by (1) combining a silicate oligomer obtained by hydrolyzing, dehydrating and polycondensing a tetraalkoxysilane with a hydrolysis rate in the range of 0 to 65%, and having a molecular weight of 80 or more and less than 500 and a functional group of 1; Modified silicate composition (2) obtained by reacting a compound containing active hydrogen with an alkoxy group number/active hydrogen number in the range of 1 to 15. Hydrolysis rate of tetraalkoxysilane is 0 to 65%.
A silica oligomer obtained by hydrolytic dehydration polycondensation in a range of
Modified silicate composition (3) polyisocyanate and the modified silicate composition described in (1) or (2) above are reacted in the range of 90/1O-u10/9Q.
This can be easily achieved by using a polyisocyanate composition containing a modified silicate composition which is uniformly dissolved in a weight ratio of .

The present invention will be explained in detail below.

The silicate compound used in the present invention is a tetraalcoxin run represented by the following formula or an oligomer thereof.

R40! i 0R2 0R.

(Here, R1 to R4 may be the same or different and are furkyl groups such as methyl, ethyl, propyl, butyl.) The silicate oligomer is obtained by hydrolyzing and dehydrating polycondensation of the above tetraalkoxysilane monomer. . The reaction is as follows.

The oligomer is produced by adding the required amount of acidic, neutral or alkaline water to the tetraalcoquine silane monomer and removing the alcohol produced by the reaction (produced twice as much in mole as the amount of water added). The hydrolysis rate of the silicate oligomer is a value calculated according to equation (■), and the amount of water to be added is determined by the determined hydrolysis rate.

S i(OR)4 +nH2o−os ico R)s
-z, O.

+21ROH (1) In other words, a tetraalcoquine silane in which all alkoxy groups have been decomposed is expressed as a hydrolysis rate of 100%, and a tetraalkoxysilane in which two alkoxy groups have been decomposed is expressed as a hydrolysis rate of 50%. Hydrolysis is possible up to 100%. However, a product with a 100% hydrolysis rate is a complete S i Ot solid, and the hydrolysis rate is 7.
Anything over 0% is gelatinous or solid, and those with a hydrolysis rate of 65-70% have high viscosity, and furthermore, react with a small amount of moisture in the air and turn into a gel, resulting in poor storage stability and Very difficult to handle.

Accordingly, in the present invention, silicate oligomers with a hydrolysis rate of 0 (ie, tetraalkoxysilane monomer) to 65% are used, preferably silicate oligomers with a hydrolysis rate of 10 to 60%, more preferably 40 to 60%.

In order to solubilize these silicate oligomers in various compounds, such as polyisocyanate, the silicate oligomers are mixed with 8) an active hydrogen-containing compound having a molecular weight of 80 or more and less than 500 and a functional group number of 1 and a flufoxy group number/active hydrogen number ratio of 1 to 15. or b) the silicate oligomer has a molecular weight of 500 or more, preferably 500
~2000 and must be modified by reacting with an active hydrogen-containing compound having a functional group number of 2 or less at a flukoxy group depletion/active hydrogen number ratio in the range of 10 to 100. These active hydrogen-containing compounds used in the present invention include , There are items 1 to ■ shown below.

aop soo' 1. Monohydric alcohol molecule monohydric alcohol with fi80 or more and less than 500, preferably a compound containing an aromatic ring 0 such as phenol,
Benzyl alcohol, 2-phenoxyethanol, 2.
Examples include 4-dimethylphenol.

(2) Polyether , butanol, 7 ethanol, benzyl alcohol, etc. As a monovalent carboxylic acid,
Examples of the 6-alkylene oxide include formic acid, acetic acid, butyric acid, and benzoic acid, such as ethylene oxide, propylene oxide, butylene oxide, and the like.

00V ■Polyether alcohol ■Number of functional groups: 1 Monovalent alcohol or monohydric carboxylic acid to which fullylene oxide is added at least 6 moles or more, preferably 10 moles or more, and the molecular weight is 500 or more, preferably 500 to 1500. , monohydric alcohol,
As the monovalent carboxylic acid and alkylene oxide, those shown in H can be used.

(2) A dihydric alcohol or a dicarboxylic acid with a functional group number of at least 8 moles or more, preferably 10 moles or more, to give a molecular weight of 500 or more, preferably 800 to 2000. As the dihydric alcohol, for example, ethylene Examples include glycol, propylene glycol, butanediol, bis-7enol A, hydroquinone, and catechol. Examples of divalent carboxylic acids include maleic acid, succinic acid, 7-divic acid, 7-talic acid, and guimaric acid. As alkylene oxide, ■
The same one can be used.

■ Boesul Alcohol A dihydric carboxylic acid and a dihydric alcohol are esterified to have a molecular weight of 500 or more, preferably 1000 to 2000.
What was said. As the divalent carboxylic acid, the same ones as in (2) can be used. As the dihydric alcohol, the alcohols shown in (1) and the dihydric alcohol (2) to which fullkylene oxide is added can also be used.

Polyethers and polyester alcohols whose active hydrogen compound has a functional group number of 3 or more cannot be used because the product gels or solidifies when reacted with a silicate oligomer. An active hydrogen compound having a molecular weight of less than 500 and an active hydrogen-containing compound having a functional group number of 2 cannot be used because the silicate oligomer reactant is not compatible with the incyanate and will separate.

In the reaction between an active hydrogen-containing compound and a silicate oligomer, for an active hydrogen compound having a molecular weight of 80 or more and less than 500 and a functional group number of 1, the ratio of the number of alkoxy groups/the number of active hydrogens is 1 to 1.
5, preferably in the range 3-u15 or b) the molecule zs
For active hydrogen compounds having a functional group number of oo or more and 2 or less, the ratio of the number of alkoxy groups/the number of active hydrogens is 10 to 100, preferably 15 to 80. Here, the ratio of the number of alkoxy groups/the number of active hydrogens is expressed by the following formula. is the value represented by .

The alkoxy group equivalent is the number of alkoxy groups in 1 g of silicate oligomer, and in formula (1), if R is a methyl group, the alkoxy group equivalent is given as shown in formula (III) 6 Hydrolysis rate 40 %, since n-0.8, the alkoxy group equivalent is 0.0208. The active hydrogen equivalent is the number of active hydrogens in 1 g of an active hydrogen-containing compound, and is given as shown in formula (IV) using its hydroxyl value.

The active hydrogen content of an active hydrogen-containing compound with a hydroxyl value of 112 is 0.0020.

From the above, if the hydrolysis rate of the silicate oligomer and the hydroxyl value of the active hydrogen-containing compound are known, the reaction ratio between the two can be determined. The reaction method is as follows:
There is a street.

■A predetermined amount of silicate oligomer and a predetermined amount of an active hydrogen-containing compound are placed in a reaction vessel and heated for 60 ^ under a nitrogen atmosphere.
The reaction 9, in which the temperature is raised to 7140°C and the alcohol produced by the reaction is removed, must be carried out until there is no free active hydrogen, that is, until the amount of alcohol produced is at least the same number of moles as the number of active hydrogens added. The alcohol that comes out in the same number of moles or more is alcohol that is produced by condensation between silicate oligomers, so it is important not to remove too much alcohol.Removing too much alcohol will increase the hydrolysis rate of the silicate oligomers. The same is true; if the temperature is increased too much, the entire reaction mixture will turn into a melt or solidify.

A catalyst may or may not be used during the reaction.

If used, the catalysts are conventional esterification catalysts, transesterification catalysts, such as alkyl tins, magnesium acetate,
Calcium acetate, titanate, etc. can be used.

■ A predetermined amount of silicate oligomer and a predetermined amount of an active hydrogen-containing compound are placed in a reaction container, and transferred to 40 under reduced pressure.
The temperature is raised to 20"C and the alcohol produced by the reaction is removed. The alcohol produced and the catalyst are the same as in (2).

In the present invention, a silicate oligomer and a molecular weight of 80 or more and 50
A compound containing one active hydrogen of less than 0 is reacted at an alkoxy group number/active hydrogen number ratio of 1 to 15, preferably 3 to 15. However, if this ratio is less than 1, alcohol will remain and this Alcohol cannot be mixed with incyanate as it will react with it. If this ratio is 15, the amount of active hydrogen-containing compound is too small and the reaction product will not be solubilized in isocyanate. The reaction is carried out at a radical number/active hydrogen number ratio of 10 to 100, preferably 15 to 80, but if this ratio is less than 10, the amount of active hydrogen-containing compound is large, and the reaction product will become deltized or solidified.
If this ratio exceeds 100, the amount of active hydrogen-containing compound is too small and the reaction product will not be solubilized in incyanate.

The modified silicate composition of the present invention obtained by reacting a silicate oligomer with an active hydrogen-containing compound as described above is manufactured by Tokyo Keiki Co., Ltd.! ! The viscosity measured at 25°C using a rotational viscometer (E type) was 0.001 to i, ooo voids, and no reaction with incyanate occurred in the mixing test with incyanate in the examples below. Due to the fact that it has a characteristic that it does not substantially contain active hydrogen. In the present invention, preferred modified silicate compositions have o, ooi to 10
The viscosity of the modified silicate composition is preferably 0.01 to 10.

The modified silicate composition of the present invention can be dissolved in various compounds to form a composition with stable properties.

For example, when it is mixed with various polyisocyanates, a stable composition in which it is uniformly dissolved can be obtained. Polyincyanate compositions containing modified silicate can be used as raw materials for urethane layers and urea resins, which have excellent heat resistance, flame retardancy, and low smoke generation properties.

Next, a polyincyanate composition containing the modified silicate composition will be explained.

The polyisocyanates used in the present invention include - organic compounds having two or more incyanate groups in the molecule, including aliphatic and aromatic polyisocyanate compounds, as well as modified products thereof. . Examples of aliphatic polyisocyanates include hexamethylene diisocyanate, inholone diisocyanate, cyclohexylmethanoisocyanate, and methylcyclohexane diisocyanate, and examples of aromatic polyisocyanates include toluene diisocyanate, nophenylmethane diisocyanate, and polymeric. There are diphenylmethane diincyane F, etc., and modified products thereof include carboimide modified products, prepolymer modified products, etc. 6 Preferred polyisocyanates in the present invention are aromatic polyisocyanates or modified aromatic polyisocyanates. Particularly preferred are diphenylmethanoisocyanate, polymeric diphenylmethanoisocyanate, and modified products thereof. These incyanates are specifically shown below.

Nophenylmethanoisocyanate has the structure shown below.

Polymeric 7-enylmethane diisocyanate is a polymer of the above diphenyl tannoisocyanate, and is an NG
O (%) to 29, 35, viscosity 2500 cps (25°C)
The following are used: Carbodiimide-modified products are those in which carbodiimide bonds are introduced into polyisocyanates using known phosphorus-based catalysts, and prepolymer-modified products are produced by reacting an excess amount of polyisocyanate with a polyol to form incyanate groups at the ends. As the polyol for this prepolymer, all polyols known for use in polyurethane resins can be used.

The mixing ratio of the modified silicate composition and polyincyanate is such that the polyisocyanate/modified silicate ratio is 90/1.
0-10/90 (wt/wt), preferably 8
It is 0/20-40/G O (wt/wt).

Storage and handling of this composition requires careful attention to water. In particular, since modified silicates have higher reactivity with water than incyanate, modified silicates easily react with moisture in the air, producing insoluble silica (SiOz).

Further, other incyanates, silicone surfactants, and organic solvents which are soluble in this composition may be further added and used.6 <Example> The present invention will be specifically explained below with reference to Examples. However, the present invention is not limited to these examples.

Note that the viscosity is a value measured by the method detailed in the text.

Example 1 Tetramethylsilicate oligomer with a hydrolysis rate of 40% and benol alcohol were placed in a reaction vessel at a ratio of alkoxy group number/active hydrogen number = 7.5, and the temperature was raised under a nitrogen atmosphere to react at 100°C. , the resulting methyl alcohol is removed by distillation to obtain a modified silicate (viscosity 0.1
3 poise), and the modified silicate was mixed with polyisocyanate in various proportions. As shown in Table 1, all of the modified silicates were soluble in polyisocyanate.

O1× in Table 1 indicates the solubilized state by visual inspection, ○
is soluble, X indicates separation,! The 4 constant standard is that the modified silicate and incyanate are separated to form two layers. Note that a modified silicate is determined to be soluble if it is hydrolyzed by moisture in the air during the mixing operation and only solid S i O2 is produced.

Example 2 The same compound as in Example 1 was placed in a reaction vessel at the same reaction rate, heated to 80 to 100°C under reduced pressure of 3 to 10 mmHH, and methyl alcohol produced by the reaction was removed to obtain a modified silicate (viscosity 0. Table 1 shows the mixing results of the obtained modified silicate and incyanate. Example 3 Tetramethyl silicate oligomer with a hydrolysis rate of 40% and polyether alcohol (molecular weight 350, hydroxyl value 160) in the same manner as in Example 1 to obtain a modified silicate (viscosity 0.2
Table 1 shows the results of mixing the obtained modified silicate and incyanate.

Example 4 The same compound as Example 1 was replaced with a flukoxy group! /number of active hydrogens=
4, the reaction was carried out in the same manner as in Example 1 to obtain a modified silicate (viscosity: 0.18 voids). Table 1 shows the results of mixing the obtained modified silicate and isocyanate.

Example 5 Addition polymerization polyether polyol (E
/PO=60/40wt%, molecular weight 1400, hydroxyl group 1
ifi80) in a ratio of alkoxy group number/active hydrogen number = 20 in a reaction vessel, and heated to 100° in a nitrogen atmosphere.
React at C and remove the resulting methyl alcohol by distillation to obtain a modified silicate (viscosity 2.10 voids)
Table 1 shows the mixing results of this modified silicate and incyanate.

Example 6 The same compound as in Example 5 was taken into a reaction vessel at the same reaction rate and heated to 80°C under reduced pressure of 3-10 mmHg.

The temperature was raised to 100° C. and methylfurfur produced by the reaction was removed to obtain a modified silicate (viscosity: 2610 voids). Table 1 shows the mixing results of the obtained modified silicate and isocyanate.

Example 7 A tetra/tylsilicate oligomer with a hydrolysis rate of 50% and a polyether alcohol (molecular weight 700, hydroxyl value 80) obtained by adding EO to n-butyl/- were combined into a compound with alkoxy group number/active hydrogen number = 25. The reaction was carried out under reduced pressure in the same manner as in Example 6 to obtain a modified silicate (viscosity 2.0
0 voices).

Table 1 shows the results of mixing the obtained modified silicate and incyanate.

Example 8 A tetramethylsilicate oligomer with a hydrolysis rate of 40% and a polyester polyol (molecular weight 2000, hydroxyl value 56) prepared by reacting 7 nobic acid and 1,4-butanol were prepared in a number of alkoxy groups/number of active hydrogens = 20. Then, the reaction was carried out under reduced pressure in the same manner as in Example 6 to obtain a modified silicate (viscosity: 1.70 voids). Table 1 shows the results of mixing the obtained modified silicate and isocyanate.

Comparative Example 1 The same compound as Example 6 was depleted of flukoxy group/number of active hydrogens=
When 8''C was reacted in the same manner as in Example 6, the reaction product turned into a gelatin-like gelatin midway through the reaction.

Comparative Example 2 The same compound as Example 6 was prepared with the number of alphoxy groups/number of active hydrogens=
200 to obtain a modified silicate (viscosity: 0.11 voids) in the same manner as in Example 6. Table 1 shows the mixing results of the obtained modified silicate and incyanate.

Comparative Example 3 A tetra/tylsilicate oligomer with a hydrolysis rate of 40% and a polyether polyol obtained by adding EO and PO to glycerin (EO/PO=60/40wL%, molecular weight 10
00, hydroxyl value 168) in the same manner as in Example 6, with the number of Furufquin groups/number of active hydrogens = 20, the reaction product turns into a gelatin-like gelatin midway through the reaction.

Comparative Example 4 When a tetramethylsilicate oligomer with a hydrolysis rate of 68% was reacted with the same active hydrogen-containing compound as in Example 6 at the same reaction rate as in Example 6, the reactant solidified midway through. Put it away.

Comparative Example 5 Tetramethylsilicate oligomer with a hydrolysis rate of 40% and polyether alcohol (molecular weight 350, hydroxyl value 160) obtained by adding EO to n-butanol were reacted and modified in the same manner as in Example 6 at the same reaction rate. Table 1 shows the results of mixing the modified silicate and incyanate to obtain a silicate (viscosity: 0.12 voids).

In addition, in the mixing tests shown in Table 1, no exothermic phenomenon or precipitates were observed in any case, and from these results, no chemical reaction occurred, and therefore, none of the modified silicate oligomers contained active hydrogen. It is determined that there is no

Table 1 a) Polyincyanate/modified silicate mixing results <Effects of the invention> According to the present invention described above, a composition that has high compatibility with various compounds, such as polyisocyanate, and has stable properties with these compounds. The present invention provides a modified silicate composition that can provide various products, and the present invention will greatly contribute to the field of manufacturing urethane resins, urea resins, etc.

Claims (3)

[Claims] (1) Hydrolysis rate of tetraalkoxysilane from 0 to 65%
A silicate oligomer obtained by hydrolysis, dehydration, and polycondensation in the range of 1 and an active hydrogen-containing compound with a molecular weight of 80 or more and less than 500 and a functional group number of 1, and the number of alkoxy groups/number of active hydrogens is 1 to 1.
Modified silicate composition made by reacting in the range of 15 (2) Hydrolysis rate of tetraalkoxysilane from 0 to 65%
A silicate oligomer obtained by hydrolytic dehydration polycondensation in the range of 500 or more and an active hydrogen-containing compound having a molecular weight of 500 or more and a functional group number of 2 or less, and the number of alkoxy groups/number of active hydrogens is 10 to 1.
Modified silicate composition made by reacting in the range of 0.00 (3) Polyisocyanate and Claim 1 or 2
90/10 to 10/
Polyisocyanate composition containing a modified silicate composition uniformly dissolved at a weight ratio of 90%