JPS5842619A - Silyl-terminated polymer and its production - Google Patents

Abstract

PURPOSE:To produce a hydrolyzable group-containing polyether which, when cured, can form an elastic body with a high elongation and is useful as an elastic sealant, by reacting a polyether having a specified terminal groups at the molecular terminals with two specified silicon hydride compounds. CONSTITUTION:A polyether containing terminal groups represented by formulaI is reacted with a silicon hydride compound having 2-20 silicon atoms and 2-6 H-Si bonds in the molecule, and a silicon hydride compound represented by formula II, wherein X is a hydrolyzable group, to obtain a polyether having silicon-containing terminal groups represented by formula III, wherein RII is H or a 1-20C monovalent organic group, RIII is a 1-20C bivalent organic group, RIV is a monovalent hydrocarbon group or a triorganosiloxy group, a is 0, 1, 2 or 3, b and b' are each 0, 1 or 2, 1<=a+b+b'<=4, Y is a silanol group or a hydrolyzable group and m is 0-18, and containing siloxane bond units in the main chain.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyether having a silanol group or a hydrolyzable silicon group at its terminal, and a method for producing the same.

The present inventors have already discovered that the terminal is made of one silicon atom,
A method for producing a silyl-terminated polyether having a hydrolyzable group on the silicon atom has been reported (Japanese Unexamined Patent Application Publication No. 1983-1993).
-13768). As a result of intensive studies on this related technology, we have found that it is possible to produce silyl-terminated polyethers whose ends are not composed of two or more silicon atoms and which have hydrolyzable groups on the silicon atoms, and also as materials. It was discovered that a rubber elastic body with high elongation can be obtained by curing, and the present invention was achieved.

That is, the present invention contains at least one siloxane bonding unit on average in the main chain, and at the molecular end, the formula % formula % (1) C where - is hydrogen or a prime number of 1 to 20 Monovalent organic group; - is a divalent organic group having a prime number of 1 to 20; I is the same or different monovalent hydrogenated hydrogen group or triorganosiloxy group; a is 0.1.2. or 3°b and b' are 0, 1 or 2. However, 1≦a+b×bl≦4. iY is a silanol group, or a different or similar hydrolyzable group; m is 0
The present invention provides a polyether having at least one silicon group (an integer selected from 18 to 18).

The polyether can basically be obtained by the following production method. That is, [a polyether containing at least 70% of all terminal groups the terminal group represented by the formula % formula % (2) at the end of the A3 molecule [N hydrogen-silicon bonds in one molecule (N is 2 ~6 integer) and having 2 to 20 silicon atoms [Silicon hydride compound represented by formula 03 (wherein, X is a hydrolyzable group) [A] % [B) and By reacting [C], a silicon group having the formula % (4) at least one end, and at least one siloxane bonding unit in the main chain on average, can be obtained by reacting [C]. It is possible to produce polyethers containing

Furthermore, by converting the X group in formula (4) to a Y group,
A polyether having a terminal group represented by the formula (1) can be produced.

In the present invention, the polyether having the terminal group of the formula (2) represented by the acid component [A] is
, Special Publication No. 46-12154, Special Publication No. 48-36960,
Japanese Patent Publication No. 50-15496, Japanese Patent Publication No. 50-149797
．． JP-A-55-i54095, JP-A-54-6096
It can be manufactured by the method proposed by et al. The polyether main chain is essentially -CH20 having 1 to 4 carbon atoms.
-, -CHz CH20-.

CH3C*Hs 1 - CHCHz O-, -CHzCH* 0H20-,
-CHCHHz O-.

-CCH,O-, -0HCHO+, -CH,CH
, CH2CH2O-CH3CH3, etc., with -0HCH,O- being particularly preferred. In the terminal group represented by formula (2), l is hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and hydrogen is particularly preferred. - is a divalent organic group having 1 to 20 carbon atoms, carbonyl group, divalent hydrocarbon group having 1 to 20 carbon atoms, ether bond, ester bond, carbonate bond,
An organic group having 1 to 20 carbon atoms including a urethane bond, urea bond, amide bond, etc. is preferable. A methylene group is particularly good.

The terminal group represented by formula (2) is particularly preferably an allyl ether group.

In the present invention, the silicon hydride compound represented by CB) is mainly used for the purpose of increasing the molecular weight by reacting with the terminal olefin group represented by the formula (2).CB)
There are N hydrogen-silicon bonds in one molecule (N is 2 to 6
A polyvalent silicon hydride compound having 2 to 20 silicon atoms is used, and the polyvalent silicon hydride compound is preferably an organopolysiloxane compound.

A platinum-based catalyst is used in this reaction.

The organopolysiloxane compound can be any linear, branched, network, or cyclic compound, and the organo group has 1 to 12 carbon atoms selected from alkyl groups, aryl groups, etc.
Particularly preferred are monovalent hydrocarbon groups. Although polyvalent silicon hydride compounds having N hydrogen-silicon bonds may be used alone or in the form of a mixture, engineered silicon hydride compounds having two hydrogen-silicon bonds are particularly preferred. Specifically, for example, 1,1.3.3-tetramethyldisiloxane [■] 1
, 1.1.3.5.7.7.7-octamethyltetrasiloxane 岨] 1,1.3,5-tetraethyldisiloxane ■] 1, η1.5.5.747 nioctaethyltetrasiloxane [■ ]1, 1.5. '5-Tetraphenyldisiloxane [V)1, 1.1.3.5. Otsu 7
, 7-octaphenyltitrasiloxane [■], etc.

H 1 (R)s 5iO3i (R)a' CI)
F'i Methyl group On) R; Ethyl group [V) 1 (i Phenyl group H RR[R']R; Ethyl group [■j 'R'; In the phenyl basic invention, hydrogenation shown by [c) The silicon compound reacts with the terminal olefin group represented by the formula (2) to form (4
) is used to introduce a functional group of the formula into at least one end of the polymer. At this time, a catalyst is required, and platinum compounds such as platinum platinum, chloroplatinic acid, platinum alcohol compounds, platinum olefin complexes, platinum aldehyde complexes, and platinum ketone complexes are effectively used.

In formula (3), I is a monovalent hydrocarbon group of the same or different type having 1 to 2 carbon atoms, such as methyl, an alkyl group such as ethylnato, a cycloalkyl group such as cyclohexylnato, or a benzyl group such as a phenyl group. It further includes a triorganosiloxy group represented by the formula (R')i 5xo-. In the formula, R' represents the same or different monovalent hydrocarbon groups having 1 to 20 carbon atoms.

In formula (3), X represents a different or the same type of hydrolyzable group, including a halogen group, a hydride group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminooxy group, and a mercapto group. group, alkenyloxy group, etc.

Specific examples of the silicon hydride compound represented by formula (3) include trimethylsiloxydichlorosilane, 1, 3.5.
5.5. Otsu 7-hebutamethyl-1,1-dimethoxytetrasiloxane, trimethylsiloxymethylacetoxysilane, bis(diethylketoximate)trimethylsiloxysilane, bis(dicyclohexylketoximate)
Examples include trimethylsiloxysilane.

In the present invention, a silicon hydride compound of formula (3) and a silicon hydride compound of formula (2) are used.
) with a polyether having a terminal unsaturated group, and then further converting some or all of the X groups into Y groups. That is, after reacting a compound in which X in formula (3) is Xl, it is more convenient for production to convert x2 into another X (Xl or a Cτ group such as a droxyl group) by a conventional method. There are many things.

For example, after adding a silicon hydride compound in which X is a halogen group or a hydride group, these groups are preferably converted into a hydroxyl group, an alkoxy group, an acyloxy group, an aminooxy group, an alkenyloxy group, or the like. The conversion may be carried out, for example, by the method described in JP-A-54-6096, or, if necessary, by a method of hydrolysis in the presence of an acid/alkaline solvent.

When the silyl-terminated polyether used in the present invention is exposed to the atmosphere, it forms a three-dimensional network due to the action of moisture and hardens into a solid having rubber-like elasticity. Since the curing rate varies depending on atmospheric temperature, relative humidity, and the type of hydrolyzable group, it is necessary to carefully consider the type of hydrolyzable group when using the resin. As the hydrolyzable groups X and Y, various groups can be used as mentioned above, but alkoxy groups are particularly preferred.

Among the alkoxy groups, a metquine group is more preferred. or,
Preferable results can be obtained if the silyl-terminated polyether of the present invention is stored under anhydrous conditions so that it does not come into contact with water until it is actually used.

In curing the silyl-terminated polyether of the present invention and a composition containing the polymer as an active ingredient, a silanol condensation catalyst may or may not be used. Alkyl titanates if condensation catalysts are used; organosilicon titanates; metal salts of carboxylic acids such as tin octylate, diptyltin laurate and diptyltin maleate, diptyltin phthalate; diptylamine-2-ethylhexoate; Known silanol condensation catalysts such as amine salts such as amine salts, and other acidic and basic catalysts are effectively used. The amount of these condensation catalysts used is preferably 0 to 10% by weight based on the silyl-terminated polymer. When alkoxy groups are used as the hydrolyzable groups X and Y, it is preferable to use a condensation catalyst since the curing rate is slow if this polymer alone is used.

In this case, a tin carboxylate is particularly preferred as the condensation catalyst.

The silyl-terminated polyether of the present invention can be modified by incorporating various fillers. Fillers include reinforcing fillers such as silica, precipitated silica, anhydrous silicic acid, hydrated silicic acid, and carbon black; calcium carbonate, rehydrated magnesium, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite. , organic bentonite,
Fillers such as ferric oxide, zinc oxide, activated zinc white and shirasu balloons; fibrous fillers such as asbestos, split fibers and filaments can be used. If you want to obtain a hardened composition with high strength using these fillers, you can use mainly tum silica, precipitated silica, anhydrous silicic acid, hydrated silicic acid, carbon black, surface-treated am calcium carbonate, calcined silica,
1 to 100 parts of a filler selected from clay, activated zinc white, etc. is added to 100 parts by weight of the silyl-terminated polyether.
Favorable results can be obtained if used within the range of parts by weight. In addition, when it is desired to obtain a cured composition with low strength and high elongation, fillers mainly selected from titanium oxide, calcium carbonate, magnesium acetate, talc, ferric oxide, zinc oxide, and shirasu balloon, etc. Silyl-terminated polyether 1
Favorable results can be obtained if the amount is used in the range of 5 to 200 parts by weight per 00 parts by weight. Of course, these fillers may be used alone or in combination of two or more.

In the present invention, the use of a plasticizer in combination with a filler is effective because it increases the elongation of the cured product and allows a large amount of filler to be mixed. Examples of such plasticizers include commonly used ones, such as phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, and butylbenzyl phthalate; Basic acid esters; glycol esters such as diethylene glycol dibenzoate, pentaerythritol ester, etc.; aliphatic esters such as butyl oleate, methyl acetyl ricinoleate; such as tricresyl phosphate, trioctyl phosphate, octyldiphenyl phosphate, etc. Phosphate esters; epoxy plasticizers such as epoxidized soybean oil, benzyl epoxy stearate, etc.; plasticizers such as chlorinated paraffin can be optionally used alone or in the form of a mixture of two or more types. The amount of plasticizer is
0 to 100 per 100 parts by weight of silyl-terminated polyether
Favorable results are obtained when used within the range of parts by weight.

Fillers, plasticizers, and condensation catalysts are mainly used in the compounded composition containing silyl-terminated polyether as an active ingredient in the present invention, but adhesion promoters such as phenolic resins and epoxy resins, pigments, and anti-aging agents are also used. It also includes the optional use of additives such as ultraviolet absorbers and the like.

The composition of the present invention having a silyl-terminated polyether as an active ingredient can be either a one-part composition or a two-part composition. When used as a two-component composition, for example, it is divided into a component consisting of a silyl-terminated polymer, a filler, and a plasticizer, and a component consisting of a filler, a plasticizer, and a condensation catalyst, and the two components are mixed immediately before use. Use it with good results. When used as a one-component composition, the silyl-terminated polymer, filler, plasticizer, and condensation catalyst are thoroughly dehydrated and dried, then mixed in the absence of moisture, and stored in a cartridge for good storage safety. It can also be used as a one-part composition. ' The composition containing the silyl-terminated polyether obtained in the present invention as an active ingredient is particularly useful as a one-component and two-component elastic sealant, and can be used as a sealant for buildings, ships, automobiles, roads, etc. sell. Furthermore, it can be used alone or with the aid of a primer to adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin moldings, etc., so it can also be used in various types of sealing compositions and adhesive compositions. . Furthermore, it is also useful for food packaging materials, casting rubber materials, molding materials, and paints.

Next, the present invention will be explained by giving examples.

Reference Example 1 Polypropylene glycol with a molecular weight of 2600 (88% of the total terminal groups are 10H groups and 1
Take 260 g of 2% 10CR, CH= ca2 group).

Add 500 ml of toluene, then add 61 ml of sodium metal and react at 120"C for 51 hours. After this,
Add allyl chloride 20f and react at 120°C for 5 hours. After the reaction solution is cooled to room temperature, the formed salt is filtered using a filter aid to obtain a clear p-liquid. After removing volatile components under reduced pressure using an evaporator, the resulting polymer was analyzed. Quantification of hydroxyl groups by hydroxyl value,
By quantifying the unsaturated groups by iodine number and measuring the molecular weight by vpo, it was found that the polymer had a molecular weight of about 2,700, with 98% CH2-CHCH20- groups at the molecular end.
Consists of 2% H〇- groups.

Example 1 810 g of the polymer obtained in Reference Example 1 was placed in a pressure-resistant reaction vessel equipped with a stirrer and purged with nitrogen. Continued CH, CH.

27 g of 3 OH, CH silicon hydride compound and 27 g of chloroplatinic acid catalyst solution (a solution of 1 g of H2PtC, 6 Hz, 8,91 dissolved in 18 g of isopropyl alcohol +/- 160 +/-tetrahydrofuran) were added, and the mixture was reacted at 80"C for 6 hours. As a result of molecular weight measurement, the average molecular weight was approximately 820.
It was 0. Furthermore, as a result of NMR analysis, CH, CH.

I CH, OH.

It was found that there are two molecules in the molecule.

aH, CH.

Following the above reaction, H-sl-o-st (QCHs
A silicon hydride compound 25f having the structure CHs 'h was added and reacted at 80°C for 6 hours. After the reaction, the residual >5i-H groups were quantified by IR spectroscopy, and it was found that most of them had reacted, and a liquid polymer having approximately 70% of the CHs width at the ends was obtained.

To 100 parts by weight of the polymer, 1 part by weight of diptyltin dilaurate and 2 parts by weight of activated zinc white were added and mixed well, and when left in the air at room temperature, it cured in 1 to 2 days to obtain a rubber elastic body.

Example 2 Oh.

The reaction was carried out in the same manner as in Example 1 except that 62 g of a silicon hydride compound having the structure was used for the reaction. After the reaction, the remaining 31-H group was quantified by IR spectrum.
It was found that almost all of the polymers were reacted, and a liquid polymer having ON (skin), CH, and CH3 at the terminals with a proportion of about 70% of the total terminal group width was obtained. The polymer is stable without curing in a moisture-free atmosphere, but when taken out and exposed to air, it hardens and becomes a rubber elastic body.

Example 6 CHs　　CH.

In Example 1, H-Si -0-S”r, (0(H
s h CHs CHs CH3 c) (m ci Example 1 except that the reaction was performed using 26 g of a silicon compound.
The reaction was carried out in the same manner. After the reaction, 8-E-3i-
As a result of quantifying the H group by IR spectrum, it is found that most of the H groups are reacted. Subsequently, the reaction vessel was cooled to 30'C, 80 g of propylene oxide was added and stirred well, and a mixed solution of 35 g of methanol and 40 f of propylene oxide was added dropwise over a period of 60 minutes with stirring. After reacting for 5 hours at 60"C, the temperature is raised to 60°C and the reaction is continued for a further 8 hours.Then, the temperature is raised to 80°C and volatile substances are devolatilized under reduced pressure, resulting in a CH3 base width ratio of approximately 65%. A liquid polymer having terminals is obtained.To 100 parts by weight of the liquid polymer, 20 parts by weight of dioctyl phthalate, 50 parts by weight of fatty acid-treated calcium oxide, 30 parts by weight of titanium oxide, 11 parts by weight of 2.2'-methylene-
Bis-(4-methyl-6-tθr-butylphenol)
1 part by weight of tin octylate, 2 parts by weight of tin octylate, and 1 part by weight of laurylamine were processed and thoroughly mixed using three paint rolls to obtain a blend. The compound was left in the atmosphere at 25'C and 60% humidity (and cured into a rubber elastic body in one day.
-H-shaped test piece was prepared according to A575B, and 7-
After curing for 7 days +50'C, the tensile properties were a breaking strength of 7.8 kQ/cd and an elongation at break of 500%.

Example 4 810 g of the polymer obtained in Reference Example 1 was placed in a pressure-resistant reaction vessel equipped with a stirrer and purged with nitrogen. Subsequently, 27 g of a silicon hydride compound and 1 ml of a catalyst solution of chloroplatinic acid (see Example 1) were added, and the mixture was reacted at 80"C for 6 hours. As a result of molecular weight measurement, the average molecular weight was approximately 8!+00. .Subsequently, hydrogenated OH having the structure H-8i-0-31(OC=CH*)2.

Add 69 g of silicon compound and react at 80"C for 6 hours.

I let it happen. After the reaction, the remaining ≧5i-H groups were quantified by IR spectroscopy, and it was found that most of them had reacted.

A liquid polymer containing at the end is obtained. The polymer is stable without curing in a moisture-free atmosphere, but when taken out and exposed to air, a curing reaction occurs and it becomes a rubber elastic body.

Patent applicant Kanebuchi Chemical Industry Co., Ltd. Representative Patent Attorney Makoto Asano

Claims (1)

[Scope of Claims] 1 Contains at least one siloxane bonding unit on average in the main chain, and has a compound having the formula (wherein RII is hydrogen or a monovalent organic group having 1 to 20 radicals) at the molecular end. ;- is degree prime number 1 ~
20 divalent organic groups; I is the same or different monovalent hydrocarbon group or triorganosiloxy group; a is 0,1°2
, or 3. b and b' are 0, 1 or 2. However, 1≦a
10b+b'≦4iY is a 5y-ynol group, or a different or similar hydrolyzable group; m is an integer selected from 0 to 18) A polyether having at least one silicon group. 2. [A] A polyether containing a terminal group represented by the formula % at the end of the molecule [B] One molecule has N hydrogen-silicon bonds (N is an integer from 2 to B), and silicon Silicon hydride compound consisting of 2 to 20 atoms [Silicon hydride compound [A], [B] and [C] represented by formula 03 (in the formula, X is a hydrolyzable group) are reacted. A polyether otga having a silicon group represented by the formula at at least one end thereof and containing on average at least one siloxane bonding unit in the main chain. 6. In claim 2, [A], (
A method for producing a polyether having a silicon group represented by the formula at least one end thereof, which comprises reacting Bl and [C) and then converting an X group into a Y group. 4. In claim 2, [A] and CB)
A method for producing a polyether having a silicon group represented by the formula at least at one end, the method comprising first reacting (C) and then reacting (C). 5. A method for producing a polyether having a silicon group at at least one end, as set forth in claim 2, wherein the silicon hydride compound [B] is an engineered silicon hydride compound. 6. A method for producing a polyether om having a silicon group represented by the formula at least at one end, wherein the silicon hydride compound CB) in claim 4 is an engineered silicon hydride compound.