JPS5912947A - Material for novel foam - Google Patents

Abstract

PURPOSE:To provide titled material of markedly improved heat, freeze, weather, and moisture yesistance and significantly reduced problems on safety and health, useful for thermal insulators, cushioning materials, sound absorbing materials, vibration insulators, etc., consisting mainly of a hydrolyzable-silicon group-contg. organic polymer. CONSTITUTION:The objective material con be obtained by incorporating (A) an organic polymer consisting of a polyether with its backbone chain preferably having a recurring unit of formula: -(R'-O)-(R' is divalent alkylene), and also containing, in one molecule, at least one hydrolyzable silicon group (a functional group containing, on the silicon atom, hydride group, halogen group, etc.) with, if required, (B) a filler (e.g. a silica powder), flame-retardant, foam stbilizer, pigment, etc., and pref. further with (C) a curing catalyst (e.g. tin octylate).

Description

[Detailed description of the invention] The present invention relates to materials that provide novel foams.

Types of foam materials can be divided into thermoplastic foam materials and thermosetting foam materials, and polyethylene is the thermoplastic foam material.

Polypropylene, polystyrene, polyvinyl chloride.

ABS resin, ionomer, cellulose acetate, etc. are used as thermosetting foam materials, but phenolic resin is used as a thermosetting foam material.

Known examples include urea resin, epoxy resin, silicone resin, polyurethane resin, and latex rubber foam.

The present invention provides hydride groups, halogen groups,
A main body containing at least one hydrolyzable silicon group in one molecule, which is a functional group having a group selected from an alkoxy group, an alkenyl group, an acyloxy group, a ketoxime group, an amino group, an aminooxy group, an amide group, and a mercapto group. A polyether whose chain has a repeating unit represented by the formula (R1 is a divalent alkylene group) or an organic polymer having a main chain selected from 1,2-polybutadiene, 1,4-polybutadiene, and polyester. It is a material for foam made of.

Further, when polyether is selected as the material of the present invention, a liquid material having a molecular weight of 300 to 15,000 is preferable from the viewpoint of convenience in handling.

-B(1-o→ As a specific example, for example, -CH2CH
20-2 -OH-OH2-0-, -cn-cn2-o-.

-CH2CH2CH2CH20- and the like. In the polyether main chain, not only one type of these repeating units is bonded, but also two or more types of repeating units are bonded in a mixed form. Polyethers manufactured as such oxides, propylene oxides,
It can be obtained using methods such as cationic polymerization and anionic polymerization using butylene oquinide, tetrahydrofuran, and the like as raw materials.

Examples of methods for incorporating hydrolyzable silicon groups into organic polymers include the following methods. For example, at the end of the molecule (
0cea''-cn=cn2 (wherein, R2 is a divalent hydrocarbon group, n is O or 1), and the main chain is %R1-0→(al is a divalent hydrocarbon group, n is O or 1). For example, polyoxyalkylene having chemically bonded repeating units of the formula HS : L'r , X is a hydrolyzable group, a is 0.1 or 2)
It can be easily obtained by combining the silicon hydride compounds represented by by an addition reaction in the presence of a platinum-based catalyst.

Examples of organic polymers containing at least one hydrolyzable silicon group in one molecule of the present invention include, for example, Japanese Patent Publication No. 44-1
2437, Special Publication No. 45-11819° Special Publication No. 45-3
631'9. Tokuko Sho 46-30711
2154, JP 48-36960° JP 47-1
389. Japanese Patent Publication No. 48-62898.

Japanese Patent Publication No. 50-156i99. JP-A-51-73561
゜Unexamined Japanese Patent Publication No. 54-6096, Unexamined Japanese Patent Application No. 54-37184゜Unexamined Japanese Patent Application No. 55-82123. Japanese Patent Publication No. 55-123620
.

JP-A-55-125121, JP-A-55-13102
1.

Japanese Patent Publication No. 55-131022. Japanese Patent Publication No. 55-135335
．． .

Japanese Patent Publication No. 55-135136. Japanese Patent Publication No. 55-137129
Examples include the polymers described in . These polymers may be used alone or in combination of two or more.

Even if the organic polymer of the present invention is initially liquid, it is cured by chain extension and crosslinking due to moisture contained therein or moisture in the air. Since it is desirable that the final foam be crosslinked, it is desirable to select a material that undergoes a crosslinking reaction as a hydrolyzable silicon group. In some cases, it may also be possible to mix a cross-linking agent and then subject it to foaming and molding. In any case, it is preferable that the material of the present invention is ultimately crosslinked.

Next, the foaming method will be described. The foaming method is not particularly limited, and various foaming forms are possible. For example, volatile hydrocarbon compounds (propane.

butane, etc.) or a halogenated hydrocarbon compound (trichloride, fluoromethane, methylene chloride, etc.) and vaporize the hydrocarbon compound or halogenated hydrocarbon compound by reducing pressure or heating to generate foam. A foaming method that utilizes physical properties such as a foaming method, a method that adds an incyanate compound and water and generates carbon dioxide gas bubbles by the reaction of the two, and a method that adds a silicon hydride compound and alcohol and generates H2 gas bubbles by the reaction of the two. Foaming methods that utilize chemical properties, such as a method that uses nitrogen gas generated by decomposition of a 4-azo compound, and mechanical foaming methods, such as a method that utilizes air drawn in by mechanical stirring as a foam. , and others.

The organic polymer of the present invention can also be used in combination with a so-called polyurethane foam material.

In this case, it is preferable to blend the foam material of the present invention with a urethane resin based on polyether, polybutadiene, or polyester polyol to obtain a new foam material. In this case, it is not necessarily necessary to add a substance to serve as a foaming source, and a carbon dioxide gas foaming method based on a reaction between water and incyanate can be used.

As the molding method, various methods for molding urethane foam can be used. Batch type and continuous type are possible.

So-called slab foaming methods, cast molding methods, and injection molding methods are possible. Although molding can be performed at room temperature, a heating method is preferable to increase production speed.

The organic polymer of the present invention may be used as necessary with fillers such as glass fiber, silica powder, mica powder, rubber granules, calcium carbonate, barium sulfate, and wood flour, flame retardants such as phosphorus-based and halogen-based Foaming agents, pigments, etc. may be added to the composition for foaming and molding. Further, in order to impart mechanical strength, various hydrolyzable silicon compounds as crosslinking agents may be added. As the hydrolyzable silicon compound, for example, M e S
1 (OM e ) B +CH2=CH2=CH81(
O1, Etsi(OMe)8, EtSi(OEt)3.
5i(OEt)4, phenyl 5i-(OEt)8, and partial hydrolysis products thereof.

The organic polymer of the present invention is preferably crosslinked when it becomes the final foam, but in order to increase the crosslinking rate,
Alternatively, it is desirable to mix a curing catalyst in advance in order to increase the rate of chain extension.

Examples of curing catalysts include metal carboxylates such as tin octylate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, and dioctyltin dilaurate, and amines such as laurylamine, di-n-hexylamine, and hexamethylene diamine. . These curing catalysts are preferably used in an amount of 01 to 5% by weight based on the total weight of the polymer.

The obtained foam is useful as a heat insulating material, a cushioning material, a sound absorbing material, a vibration isolating material, an artificial leather shoe, and a casting material. Since it is cured by moisture such as moisture, it is similar to polyurethane foam in that sense, but it is significantly different from polyurethane foam in terms of crosslinking (or chain length extension) method and physical properties. That is, in the second aspect of the present invention, crosslinking (or chain length extension)
The points are bonded by 18i-0-8i bonds (siloxane bonds). In addition, the disadvantages of polyurethane such as heat resistance, cold resistance, weather resistance, durability, moisture resistance, and safety and health problems such as unpleasant odor during combustion are greatly improved.

Examples and reference examples are described below.

Reference Example 1 320 g of diol type polyoxypropylene glycol (Sanyo Kasei pp-4000) with an average molecular weight of 3200 was placed in a pressure-resistant autoclave with an internal volume of 11 that was replaced with N2, and 40.81 g of powdered NaOH (purity 98%) was added. The mixture was warmed to 60°C and stirred for 1 hour. Subsequently, 776 g of bromochloromethane was added, and the mixture was stirred at 60°C for 10 hours. Then, 9.29 g of allyl chloride was added and the reaction was continued for an additional 10 hours.

After cooling, the contents were taken out and transferred to a No. 81 separable flask. 1.54 of n-hexane was added to this and stirred to make it homogeneous. After that, add 1.5Jl of 3 weight sulfuric acid water. 7
JIli" and stirred for 1 hour. After standing for 1 hour, it was separated into two layers, a transparent hexane layer and an aqueous layer. At this time, the pH of the aqueous layer
H was 6 or less. Separate and remove the hexane layer,
' By removing n-hexane in an evaporator, a polyether (4) having an average molecular weight of s'ooo and having 94% of the terminals converted to allyl ether was obtained.

30.0 g of this allyl-terminated polyale was placed in a pressure-resistant autoclave of 0.1 N and replaced with 0.03 g of isopropyl alcohol 10% by weight solution of chloroplatinic acid and mixed uniformly.
g was added, the temperature was raised to 90'C, and the mixture was stirred for 4 hours.

Gas chromatography of the reaction mixture, infrared absorption spectrum and elemental analysis of the product after low boiling point substances were removed in vacuum revealed that it was a polyether polymer with 90% of the terminals silylated (
6) was confirmed to be generated.

Reference Example 2 Triol-type polyoxyprobile/glycol 320f with an average molecular weight of 4500 was placed in a N2-substituted 11 pressure autoclave, and powdered NaO11 (purity 9
8) was added and stirred at 60°C for 1 hour. Then, 10.1 f of allyl chloride was added and the mixture was further stirred for 10 hours. Hexane/water purification was then carried out in the same manner as in Reference Example 1 to obtain a polyether (C) in which 96% of all terminals were converted to allyl ether.

This polyether (c) 3o o y was placed in a N2-substituted 0,51 pressure autoclave, and 03g of a solution of chloroplatinic acid in isopropyl alcohol lO'lrC was added, and after uniform mixing, 30g of trimethoxyhydrosilane was added.
was added and reacted at 90°C for 2 hours. It was confirmed from gas chromatography of the reaction mixture, infrared absorption spectrum after vacuum removal of low boiling point substances, and elemental analysis that a polyether polymer (T) in which all terminal 87 groups were trimethoxynolylated was obtained. .

Reference Example 3 290 g of diol type polyoxypropylene glycol with an average molecular weight of 3200 and 30 g of triol type polyoxypropylene glycol with an average molecular weight of 4000 were mixed with N
Powder N
After adding 409 kg of a OH and stirring at 60°C for 1 hour, 7.6 da of bromochloromethane was added and the mixture was further stirred for 10 hours. Then, 9.29 g of allyl chloride was added and the reaction was continued for a further 10 hours. Thereafter, hexane/water purification was carried out in the same manner as in Reference Example 1 to obtain a polyether ((t)) having an average molecular weight of 9,200 and in which 90% of all terminals were converted to allyl ether. 300 g of this allyl-terminated polyether was transferred to a 0.51 pressure autoclave substituted with N2, and 0.39 g of a 10% (by weight) solution of chloroplatinic acid in isopropyl alcohol was added. After uniformly mixing, 110 g of methyldimethoxyhydrone was added. 90
Stirred at °C for 3 hours. The results of gas chromatography of the reaction mixture, infrared absorption spectrum after removing low-boiling substances in vacuum, and elemental analysis confirmed that 84% of all terminals were silylated polyether polymer (power was obtained).

Example 1 1,1,1,3,5,7°7.7- as a blowing agent was added to 100 parts by weight of the silyl-terminated polyether 03) obtained in Reference Example 1.
Add 5 parts by weight of octamethyltetrasiloxane (H-Oil2 manufactured by Toshiba Silicone) and 4 parts by weight of a mixture of tin octylate and laurylamine (3:1 by weight) as a curing catalyst, mix uniformly, and leave at room temperature. When left to stand, the mixture continued to foam while generating hydrogen gas, and an elastic foam was obtained after 1 hour. When the specific gravity was measured, it was 018.

Example 2 A foam was obtained in the same manner as in Example 1 except that the silyl-terminated polyether (6) obtained in Reference Example 2 was used.

Specific gravity was 023.

Example 3 The silyl-terminated polyether (filo) obtained in Reference Example 3.

5 parts by weight of methylene chloride and a mixture of tin octylate and laurylamine (3:1 by weight ratio) as a curing catalyst.
) was added and mixed uniformly, the mixture was placed in a container whose degree of vacuum can be adjusted, and the pressure was reduced to vaporize and foam methylene chloride. When taken out after 1 hour, an elastic foam with a specific gravity of 0.13 was obtained. - Example 4 Silyl-modified polyether (T) 10 obtained in Reference Example 3
0 parts by weight, urethane prepolymer 10 of triol type polyoxypropylene glycol (molecular weight 3000)
0 parts by weight were mixed to obtain a transparent liquid. 3 parts by weight of water and 2 parts by weight of dibutyltin laurate were added and mixed, and the mixture was placed in a mold and heated at 200°C for 15 minutes. After cooling, the mold was removed and an elastic foamed product was obtained.

Reference example 4 300g of 1,2-polybutadiene with a molecular weight of 2000 was
The mixture was placed in a 2-substituted pressure autoclave, 40 f of methyldimethoxysilane and 0.3 g of a 10% by weight solution of chloroplatinic acid in isopropyl alcohol were added, and the mixture was reacted at 906C for 2 hours. gas chromatography, infrared absorption spectrum,
From elemental analysis, it was confirmed that almost the entire amount of the 7 runs was bonded by addition reaction, and silyl-modified polybutadiene (0) was obtained.

Example 5 Silyl-modified polybutadiene CG) 100 obtained in Reference Example 4
4 parts by weight of the curing catalyst used in Example 1 and 5 parts by weight of H oil were added to the parts by weight, mixed uniformly, and left at room temperature to obtain a foam.

Example 6 100 parts by weight of the silyl-modified polybutadiene (0100 parts by weight) obtained in Reference Example 4 was mixed with 100 parts by weight of polybutadiene-based urethane prepolymer (MDI modified product of Pony bd R-45M manufactured by Idemitsu Petrochemical Co., Ltd.).To this was added 3 parts by weight of water. 1 part by weight and 2 parts by weight of dibutyltin dilaurate were added and mixed, placed in a mold and heated at 200°C for 15 minutes.After cooling, the mold was removed to obtain an elastic foam.

Example 7 A N2-substituted stirrer was used in a pressure-resistant reaction vessel with a molecular weight of 700.
7009 of a block copolymer of polycaprolactone and polypropylene oxide [polycaprolactone/polypropylene oxide = 1/6 (weight ratio)] was taken.

The block copolymer has one molecule, and the end of the molecule is
.

1 70%, CH2=C■ (CH2O- group is 20%, HO-
The group consists of 10%. Methyldiacetoxysilane 329 was added under a N2 stream, followed by addition of a 0.2- to 10-weight solution of isopropanol chloroplatinic acid, and the mixture was heated at 90°C.
The mixture was allowed to react for 6 hours. After the reaction was completed, the Tsubo residue was removed under reduced pressure to obtain a polymer having a total number of groups of 75 including the terminal groups. 1 part by weight of Freon, 1 part by weight of dibutyltin dilaurate, and 1 part by weight of water were added to 100 parts by weight of the polymer, mixed, and left in a vacuum source for one day.
A strong foam was obtained.

Patent applicant Kanebuchi Chemical Industry Co., Ltd. Agent: Patent attorney Makoto Asano - 13'-

Claims (1)

[Scope of Claims] A foam material comprising an organic polymer containing at least one hydrolyzable silicon group in 11 molecules. 2 The hydrolyzable silicon group has a group selected from a hydride group, a halogen group, an alkoxy group, an alkenyloxy group, an acyloxy group, a ketoxime group, an amino group, an aminooxy group, an amide group, and a mercapto group on the silicon atom. A foam material according to claim 1. 3 The main chain of the organic polymer is essentially 2(R1-(1v
The foam material according to claim 1, which is a polyether having a repeating unit represented by a divalent alkylene group. 4. The foam material according to claim 1, wherein the hydrolyzable silicon group has an alkoxysilyl group on the silicon atom. 5. Foam material consisting of an organic polymer containing at least one hydrolyzable silicon group per molecule and a urethane resin based on polyether or polybutadiene or polyester polyol.