JPH03167254A - Moisture-curing composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. easily produced and excellent in the moiture-curing properties, adhesive properties, etc., by using, as the effective component, a polyether wherein a hydrolyzable silyl group and a polyoxyalkylene main chain are linked by a specific group. CONSTITUTION:A polyoxyalkylene having a terminal hydroxyl group is subjected to the addition reaction with allyl glycidyl ether to give a polyoxyalkylene having a terminal group of formula I. The resulting polyoxyalkylene is further reacted with a hydrogenated silicon compd. (e.g. chlorodimethylsilane) having a hydrolyzable group directly attached to the silicon atom to produce a polyether wherein a terminal hydrolyzable silyl group and a polyoxyalkylene main chain are linked by a group of formula II. Then, the polyether, if necessary compounded with a plasticizer, a filler, etc., is used as the effective component to give the title compsn.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides an effective method for producing a polyether in which a terminal hydrolyzable silyl group and a main chain polyoxyalkylene are bonded by an ether group having a hydroxyl group. The present invention relates to a moisture-curable composition.

[Prior art]

Polyethers, which have a hydrolyzable silyl group at the end and whose main chain is polyoxyalkylene (alkylene oxide polymer), are produced by producing polyoxyalkylene having an allyl group at the end, and then attaching the hydrolyzable group to the silicon atom. X is a hydrolyzable group, and a is an integer of 0 to 2. ) using a platinum-based catalyst, and is known as an inexpensive silicon-based LTC splittable moisture-curable composition that has been established in terms of performance. (
(Special Publication No. 5B-41291, Japanese Patent Publication No. 60-6747)
In the production of such polyethers, it is difficult to obtain the intermediate raw material polyoxyalkylene having an allyl group at the end, so various production methods are known. For example, (1) alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide are mixed with an addition base such as allyl alcohol and propylene glycol in a 0.
A polyoxyalkylene having a hydroxyl group at the end obtained by polymerization in the presence of 1 to 1% potassium hydroxide is then reacted with allyl isocyanate or allyl chloroformate to form an allyl urethane group or allyl carbonate at the end. Based method (Special Publication No. 45-36319
(Japanese Patent Publication No. 48-36960), (2) The alkylene oxide and the addition substrate are
There is a method (Japanese Patent Publication No. 56-5249) in which polymerization is carried out in the presence of a large amount of potassium hydroxide (wt%), and then a desalting reaction is carried out with an allyl halogen compound such as allyl chloride.

[Problem to be solved by the invention]

However, the polyether produced by method (1) has problems such as high viscosity and difficulty in practical use, and poor weather resistance of the cured product, so method (2) has been proposed. On the other hand, production method (2) is more practical than method (1), but because it contains a large amount of potassium hydroxide, it takes a lot of effort to neutralize and desalinate, and it also causes a large yield loss. There were still some points to improve.

The purpose of the present invention is to overcome the above-mentioned drawbacks during the production of intermediate raw materials (allyl group-containing polyoxyalkylene) that are problems in polyether production, and to add hydration to the terminals to improve performance such as moisture curing properties and adhesive properties. The object of the present invention is to provide a polyether having a decomposable silyl group.

[Means to solve the problem]

The present inventors have completed the present invention as a result of intensive research to solve the above problems.

That is, the present invention provides a moisture-curable composition containing as an active ingredient a polyether having a hydrolyzable silyl group at the end and a main chain consisting of polyoxyalkylene. The chain polyoxyalkylene is 0■ -Cl{z-CHz-CHgO-Cut-CH-CHg
The present invention relates to a moisture-curing composite sole characterized in that it uses polyethers bonded by one group.

The polyether used in the composition of the present invention uses polyoxyalkylene as a starting material. This polyoxyalkylene is usually easily produced by addition polymerizing alkylene oxides to an addition substrate having active hydrogen at 60 to 120°C in the presence of 0.1 to 1.0% by weight of alkali metal hydroxide. can get.

As the alkali metal hydroxide, sodium hydroxide and potassium hydroxide are typical, and when propylene oxide is used as the alkylene oxide, potassium hydroxide is mainly used. The amount used can be 0.1% by weight or more of the raw polyoxyalkylene, but if a large amount is used, it will be difficult to control the reaction temperature and the molecular weight of the polyoxyalkylene, and the alkali metal used will be difficult to control. Since a large amount of salt is generated when neutralizing hydroxide, from the viewpoint of resource and energy conservation, it is usually 0.1 to 1. 0%
A range of is good. The reaction temperature is also preferably in the range of 90 to 115°C in order to ensure quality reproducibility and shorten polymerization time.

Additional bases include allyl alcohol, ethylene glycol, propylene glycol, bisphenol A1 bisphenol F1 glycerin, trimethylolpropane,
In addition to pentaerythritol and sorbitol, relatively low molecular weight polyalkylene glycols such as polyethylene glycol and polypropylene glycol are also used. For the purposes of the present invention, glycols having a difunctionality or less are preferred, and the use of allyl alcohol is most preferred.

Examples of alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. Although ethylene oxide has the effect of imparting hydrophilicity, the content is preferably 0 to 20% by weight in consideration of storage stability, which is an operational aspect of the moisture-curable composition, and physical properties of the cured product.

The polyoxyalkylene used in the present invention is one obtained by the above production method (alkali metal hydroxide 0.
In addition to using commercially available polyoxyalkylene mixed and dissolved with an appropriate amount of alkali metal hydroxide, it is also possible to use commercially available polyoxyalkylene. By adding allyl glycidiether to such a polyoxyalkylene with a terminal hydroxyl group containing an alkali metal hydroxide and adding it under the same reaction conditions as in the polymerization reaction, OH CHx=CI-CHz-0-CHz is added to the terminal. A polyoxyalkylene having -C}I-CHz one group .( 1 1) is obtained. It is sufficient that the amount of allyl glycidyl ether used is at least the stoichiometric amount based on the hydroxyl group in the polyoxyalkylene.

The polyoxyalkylene having an allyl group shown in (1) above can also be obtained by adding shrimp chlorohydrin to a polyoxyalkylene terminal having a hydroxyl group (desalting reaction) to make the terminal an epoxy group, and then adding allyl alcohol. It can also be obtained by forcing people to do something. The obtained allyl group-containing polyoxyalkylene is then reacted with a hydrolyzable group on a silicon atom according to a conventional method. As a result, the hydrolyzable silyl group at the end and the polyoxya O
H Lukylene is -CHz-CHt-CH! O-CHt-C
A polyether bonded by H--CHt- groups is obtained.

Examples of the silicon hydride compound include halogenated silanes such as chlorodimethylsilane, dichloromethylsilane, and trichlorosilane, alkoxysilanes such as methyldimethoxysilane, methyldiethoxysilane, trimethoxysilane, and dimethoxysilane, and methyldiacetoxysilane. Examples include acyloxysilanes such as bis(dimethylketoximate) and ketoximate silanes such as bis(dimethylketoximate) methylsilane, and alkoxysilanes are particularly preferred. In order to avoid the generation of hydrogen, it is preferable to use the compound by converting it into a group such as alkoxy, acyloxy, ketoximate, amide, acid amide, or [anoxy].

The silyl group-containing polyether used in the present invention is easily cured in the presence of any water or moisture, but in order to accelerate its curing, a catalyst for siloxane condensation such as alkyl titanate, tin octenoate, diptyltin dilaurate, etc. is used. It can be mixed into a state suitable for practical use. In order to further increase the stability of polyether, it is an effective means to mix 1 to 10% of a solvent such as methanol or ethanol. To make it suitable for practical use, it is also possible to increase the elongation of the cured product by using a plasticizer filler, etc. For example, 0 to 100% of a plasticizer such as dioctyl phthalate and 0 to 300% of a filler such as silica, calcium carbonate, clay, or tarta are mixed with the main component of polyether to create a sealant or flooring material. It can be used for applications such as timber and wall materials. In addition, a coating formed by mixing this composition with an isocyanate composition has a particularly high tensile strength because the isocyanate crosslinks with the hydroxyl group contained between the terminal hydrolyzable silyl group and the polyoxyalkylene main chain. Shows strength. [Example] Example 1 In an autoclave with a stirrer, 2g of polyethylene glycol with a molecular weight of 200 and 95% KOH4-O were added.
100 gr of grs propylene oxide was charged with nitrogen substitution, and the temperature was raised to 100°C. Thereafter, 584 gr of propylene oxide was added dropwise and reacted for 15 hours to obtain alkylene oxide polymer A having a hydroxyl value of 19.

After the above reaction, additionally 30 gr of allyl glycidyl ether
After mixing and reacting at 110°C for 8 hours, three cabinets of Hg
The low boiling point substances were removed by treatment at a reduced pressure of 3 hours. After that, 20 gr of aluminum silicate was mixed and heated to 100℃.
The aluminum silicate was treated in a furnace for 5 hours, and the furnace liquid was depressurized to 3 mmHg for 1 hour to obtain allylated polyether B of 690 gr.This material had a hydroxyl value =
2 2. 3. Iodine value = 2 5. It was 2.

5 gr of ethanol was mixed with 100 gr of allylated polyether B, and 5 gr of methyldiethoxysilane was mixed. Ogr,
The mixture was reacted for 8 hours at 80° C. under 0.00005 gr of chloroplatinic acid. After the reaction, the iodine value was reduced to 0.
9 was confirmed. This is designated as silylated polyether C.

Example 2 To the alkylene oxide polymer A780gr of Reference Example 1,
Mix 30 gr of epichlorohydrin and add 20 gr of 95
%KOR was added, and the temperature was raised to 90° C. over 1 hour, followed by a reaction for 8 hours. Thereafter, 15g of allyl alcohol was mixed, and the mixture was allowed to react for 5 hours under reflux at 100°C. Thereafter, the solution was neutralized to pH 4 with hydrochloric acid, and filtered using aluminum silicate as a 1% additive to the resin. this thing 3
Treated under reduced pressure at mmHg for 2 hours, hydroxyl value = 2 4.
5. Allylated polyether D80 with iodine value = 27.3
I got 5gr. Mix 5 gr of methanol with 100 gr of allylated polyether D, 4.5 gr of methyldimethoxysilane and 0.00005 gr of chloroplatinic acid under sealed condition 80
The reaction was carried out at ℃ for 8 hours. After the reaction, the iodine value was reduced to 1. 1 was confirmed. This is called silylated polyether E. Example 3 Allyl alcohol I in a 1 liter autoclave with stirrer
gr, 2.5 gr of 95% KOH, and 100 gr of propylene oxide were charged with nitrogen substitution, and the temperature was raised to IIO°C. Thereafter, 310 gr of propylene oxide was reacted dropwise over 15 hours at 1OO''C to obtain alkylene oxide polymer E having a hydroxyl value of 17.3.

After the above reaction, 17gr of allyl glycidyl ether was mixed and reacted at 110°C for 7 hours, then neutralized with 2gr of 80% formic acid aqueous solution at 80°C for 2 hours, and then heated in a furnace using aluminum silicate as an auxiliary agent. I passed. Then 310g
Allylated polyether F402gr having a hydroxyl value of 21.5 and an iodine value of 36 was obtained by reducing the pressure at 100°C for 5 hours. For 100 gr of allylated polyether F, 6 gr of methyldichlorosilane, 0.00005 gr of chloroplatinic acid,
Isopropanol Igr was mixed and reacted at 90°C for 2 hours. At 40°C, 15g of a propylene oxide solution containing 30% methanol was added dropwise over 30 minutes, and the reaction was continued for another 2 hours. The pressure was reduced to 10 mHg for 1 hour to remove iodine. Value 0.8
A silylated polyether G was obtained. Silylated polyether C obtained in Examples 1 and 2.3,
100g of each of E and G, log xylene, 10g of ethyl alcohol, and 200g of dried calcium carbonate.
(Nitto Funka K's NS-200) and 50 g of dioctyl phthalate were added and kneaded homogeneously at room temperature using a planetary mixer (manufactured by Inoue Seisakusho K.K.), which is a kneading device designed to prevent moisture from entering. I got it. [Test method] (1) Among the test items, the initial viscosity is 25% for the mixture immediately after production.
The temperature was adjusted to below ℃ and measured using a BH type rotational viscometer. Also, 5
To measure the viscosity after 10 days at 0°C, the mixture was placed in a tightly closed metal container and left at 50°C for 10 days, then the temperature was adjusted to 25°C and the viscosity was measured. (2) Hardness, tensile strength, and elongation at break were determined by producing a sheet with a thickness of 2III under standard conditions (hereinafter the same conditions), and after curing for 14 days under the same conditions, JIS-K-
Measured using the method shown in 6301 (Vulcanized Rubber Physical Test Method). (3) Ildlllll strength is 15Xl5C
The sample was poured onto an Im aluminum plate (degreased with xylene) to prepare a 2U thick sheet, which was further cured for 14 days.

2. Cut the sample with a cutter. Cut into 5 cs width and 2.5
Create a tanzak with X15 value, JIS-K-6301
(Vulcanized rubber physical test method). <<4>> Dryness to the touch was determined by checking the presence or absence of tackiness on the surface of the sheet by touching it with a finger 48 hours after the sheet was prepared as described in the above-mentioned Example 2.

《5》 For weather resistance, use the above-mentioned sheet with Weathermeter 2.
The surface condition after 50 hours of irradiation was observed.

The test results are shown in Table-1. Table 1 From Table 1, it can be seen that the assembled bottom of the present invention is particularly excellent in adhesiveness, weather resistance, and storage stability! I got L'2.

[Effects of the present invention]

The terminal hydrolyzable silyl group and the main chain polyoxy 011 I alkylene are -CHz-CH2-CHgO-CTo-
The composition of the present invention, which contains a polyether bonded by one CI-CHZ group as an active ingredient, is extremely easy to manufacture and has excellent performance.

Claims (1)

[Scope of Claims] 1. In a moisture-curable composition containing as an active ingredient a polyether having a hydrolyzable silyl group at the end and a main chain of polyoxyalkylene, the polyether contains a hydrolyzable silyl group at the end. A moisture-curable composition characterized in that it uses a polyether whose main chain is polyoxyalkylene and which are supplied by ▲Mathematical formula, chemical formula, table, etc.▼.