JPS5925809B2 - Method for producing high molecular weight alkylene oxide polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing high molecular weight polyethers having terminal olefin groups.

A method for producing a polyether having an olefin group at the end using a polyether having a hydroxyl group at the end as a starting material has already been proposed by General Electric Company (Japanese Patent Publication No. 4536319, Japanese Patent Publication No. 46-121).
54), proposed by Tau Corning Corporation (Special Publication No. 4836960).

The production method proposed by General Electric Company uses polyether having hydroxyl groups at all ends as a raw material, and introduces allyl urethane groups at the ends by reacting the hydroxyl groups with allyl isocyanate, or A method of reacting the hydroxyl group with a polyfunctional isocyanate compound such as toluene diisocyanate to obtain a polyether having an isocyanate group at the end, and further reacting the isocyanate group with allyl alcohol to introduce an allyl urethane group at the end. It is. The production method proposed by Tau Corning Corporation uses polyether having hydroxyl groups as a raw material, and introduces allyl carbonate groups at the ends by reacting the hydroxyl groups with allyl chloroformate in the presence of pyrrolidine. This is the way to do it. All of the above-mentioned production methods use expensive reaction reagents (isocyanate compounds, pyridine, allyl chloroformate), so the polyether having an olefin group at the end also has to be expensive. are doing. Further, in the existing production method, since a low molecular weight hydroxy-terminated polyether is used as a raw material, there is a problem that the obtained olefin group-terminated polyether must also have a low molecular weight. If the molecular weight is low, when reactive silicon-terminated polyether is produced by reacting a silicon compound with the terminal olefin group, the cured product of the reactive silicon-terminated polyether has extremely low elongation as a rubber elastic body. It has a big problem of becoming a thing. Taking the above points into consideration, some of the present inventors have already reported that -0H of polyether whose molecular terminal group is mainly -0H group or -0M group (M is Na or K) is -0H. 0M group, and the -0M
By reacting the group with a polyvalent halogen compound, the molecular weight of the polyether is increased, and then by reacting with an organic halogen compound represented by the formula CH2-CH-R-X, all terminals of the polyether are increased. More than 70% of the groups are C
H2-CH-R-0- group and has an average molecular weight of 40
A method for producing polyether having a molecular weight of 00 to 15,000 was discovered and proposed in Japanese Patent Application No. 5249174.

The above production method has the advantage that a high molecular weight polyether having an olefin group at the end can be obtained at low cost, and if the polyether is used to produce a reactive silicon-terminated polyether and a cured product is made, it can be It has the excellent feature of producing a rubber elastic body with a large

On the other hand, the above method has disadvantages in that it takes a relatively long time for the molecular weight increasing reaction and the reaction for converting the terminal into an olefin group is carried out in a high viscosity system after increasing the molecular weight.

In addition, when removing the basic alkali metal compound used after the reaction, it is necessary to dilute it with a large amount of solvent due to its high viscosity, which is a disadvantage in terms of purification.

The inventors of the present invention have conducted various studies in consideration of these problems, and as a result, have discovered a method for more advantageously obtaining a high molecular weight polyether having an olefin group at its terminal, and have arrived at the present invention.

That is, the present invention provides a structure in which the main chain essentially includes chemically bonded repeating units represented by the formula R1-0 (1) (wherein R1 is a divalent alkylene group having 2 to 4 carbon atoms). ,
and at the end of the molecule, a formula (in the formula, R2 is hydrogen or a monovalent organic group having 1 to 20 carbon atoms; R3 is a divalent organic group having 1 to 20 carbon atoms; a is O or 1
The polyether contains 70% or more of the total terminal groups (an integer of
(N is an integer of 2 to 6) and a silicon hydride compound having 2 to 20 silicon atoms is reacted with a mole of 1/N times or less with respect to the number of moles of the polyether end group represented by the formula (2). The present invention provides a method for producing a polyether in which 50% or more of all terminal groups are CH2-C-R3eO+8 groups and the average molecular weight is 1000 to 30000, which is characterized by increasing the molecular weight. .

According to the present invention, it is possible to perform the molecular weight increasing reaction quantitatively in a short time, and since there are no alkali metal compounds or by-product salts in the high viscosity system after increasing the molecular weight, purification is possible. There is no need to carry out a reaction, and it is possible to react a reactive silicon compound subsequent to the molecular weight increasing reaction, which is a great advantage in terms of the process.

In the present invention, the main chain essentially contains chemically bonded repeating units represented by the formula R1-0 (1), and 70% of all end groups have terminal groups represented by the formula at the molecular ends. The polyether containing the above is used as a starting material.

Specific examples of the chemically bonded structural unit represented by formula (1) include the following.

In the polyether main chain, not only one type of these structural units may be bonded, but also two or more types of structural units may be bonded in a mixed form, but in particular, polyethers manufactured using propylene oxide as a raw material may be bonded together. Polyether is good. Polyethers having such structural units are produced using cationic polymerization or anionic polymerization using ethylene oxide, propylene oxide, butene oxide, tetrahydrofuran, or the like as raw materials. Specifically, as a method for obtaining a polyether having an olefin group at the end, which is a starting material, an alkylene oxide is mixed with caustic potash and allyl alcohol or an aliphatic Examples include a method of producing a polyether having an allyl-type olefin group at the end by polymerizing with a polyhydric alcohol or the like and then reacting with an allyl halogen compound.

In addition, the terminal group of polyether whose molecular terminal group is mainly a hydroxyl group proposed in Japanese Patent Application No. 52-49174 is -0
M (M is Na or K), then CH2-C
A method for producing a polyether having an olefin group at the end by reacting with an organic halogen compound represented by H-R-X is mentioned. Various other methods are possible, but
In the present invention, a poly-1-noether having a terminal olefin group obtained by any method can be used as a starting material. In the present invention, the molecular weight of the polyether is increased by adding a polyvalent hydrogenated siloxane compound to the O+8 group at the end group H2C-C-R3.

N hydrogen monosilicon bonds in one molecule (N is an integer from 2 to 6)
A polyvalent silicon hydride compound having 2 to 20 silicon atoms is used, and it is preferable that the polyvalent silicon hydride compound is an organopolysiloxane compound.

The organopolysiloxane compound is a linear, branched, reticulated 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 hydrogenated siloxane compounds having N hydrogen-monosilicon bonds can be used alone or in the form of a mixture, dihydrogenated siloxane compounds having two hydrogen-silicon bonds are particularly preferred. Specific examples include the following.

In the present invention, it is necessary to use a platinum-based catalyst when reacting a polyvalent hydrogenated siloxane compound or when reacting a silicon hydride compound afterwards.

Particularly favorable results are obtained using catalysts such as chloroplatinic acid, platinum metal, platinized activated carbon, platinum chloride, and platinum olefin complexes. In carrying out this reaction, any temperature between 30.degree. A solvent may or may not be used, but if used, inert solvents without active hydrogen such as ethers, aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons are suitable. be. The amount of polyvalent hydrogenated siloxane compound used is
(2) 1/ of the number of moles of end groups of the polyether represented by the formula
The amount can be freely selected as long as it is N times the mole or less, and the amount used can be selected depending on the molecular weight of the raw material polyether used and the molecular weight design of the target polyether.

When exposed to the atmosphere, the silicon-terminated polyether used in the present invention forms a three-dimensional mesh structure 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 temperature, and the type of hydrolyzable group, it is necessary to carefully consider the type of hydrolyzable group when using the resin. Further, preferable results can be obtained if the silicon-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 silicon-terminated polyether of the present invention and the composition containing the polyether as an active ingredient, a silanol condensation catalyst may or may not be used.

When using a condensation catalyst, alkyl titanates; organosilicon titanates; metal salts of carboxylic acids such as tin octylate, dibutyltin laurate and dibutyltin maleate, dibutyltin phthalate; dibutylamine-2-ethylhexoester; Known silanol condensation catalysts such as amine salts such as ates; 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 silicon-terminated polyether. The silicon-terminated polyethers of this invention can be modified by incorporating various fillers.

Fillers include fume silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and reinforcing fillers such as carbon black: calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite. , organic bentonite, ferric oxide, zinc oxide,
Fillers such as activated zinc white and shirasu balloons;
Fibrous fillers such as asbestos, glass fibers and filaments can be used. If you want to obtain a hardened composition with high strength using these fillers, use mainly fume silica, precipitated silica, anhydrous silicic acid, hydrated silicic acid, carpon plaque, surface-treated fine calcium carbonate, calcined resin, clay, and Favorable results can be obtained if the filler selected from activated zinc white is used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the silicon-terminated polyether. 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 carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon, etc. 5 to 2 parts by weight of silicon-terminated polyether
Favorable results can be obtained if the amount is used within the range of 0.00 parts by weight. Of course, these fillers may be used alone or in a mixture of two or more. In the present invention, it is more effective to use a plasticizer in combination with a filler because the elongation of the cured product can be increased and a large amount of filler can be mixed.

The plasticizer is one that is commonly used. Phthalate esters such as dioctyl phthalate, dibutyl phthalate, butylbenzyl phthalate, etc.: dioctyl adipate, isodecyl succinate,
Aliphatic dibasic acid esters such as dibutyl sebacate; glycol esters such as diethylene glycol dibenzoate and pentaerythritol ester; aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; tricresyl phosphate, phosphorus; Phosphate esters such as trioctyl acid and octyl diphenyl phosphate; Epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate; Plasticizers such as chlorinated paraffin alone or in a mixture of two or more Can be used in any shape. Preferable results are obtained when the amount of plasticizer is used in the range of 0 to 100 parts by weight based on 100 parts by weight of the silicon-terminated polyether. Fillers, plasticizers, and condensation catalysts are mainly used in the compounded composition containing silicon-terminated polyether as an active ingredient in the present invention, but adhesion promoters such as phenolic resins and epoxy resins, pigments, anti-aging agents, The optional use of additives such as ultraviolet absorbers is also included.

The composition of the present invention containing silicon-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 silicon-terminated polyether, a filler and a plasticizer, and a component consisting of a filler, IZ plasticizer and condensation catalyst, and the two components are mixed immediately before use. Use it with good results.

When used as a one-component composition, the silicon-terminated polyether, filler, plasticizer, and condensation catalyst can be thoroughly dehydrated and dried, then mixed in the absence of moisture, and stored in a cartridge to ensure storage safety. It can also be used as a good one-component composition.

The compositions containing the silicon-terminated polyether as an active ingredient obtained in the present invention are particularly useful as one-component and two-component elastic sealants, and can be used as sealants for buildings, ships, automobiles, roads, etc. 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., and therefore can be used in various types of sealing and adhesive compositions. . Furthermore, it is also useful as a food packaging material, a casting rubber material, a molding material, and a paint. Examples will be specifically described below.

Reference Example (4) Polyoxypropylene having an allyl olefin group at the end is synthesized according to the method disclosed in JP-A-50-149797.

Polyether was synthesized by polymerizing propylene oxide with caustic potash and allyl alcohol, and then reacting the terminal with allyl chloride to convert the terminal to allyl ether.
This was treated with aluminum silicate to synthesize purified end-allyl etherified polyoxypropylene (polyether A). (B) Polyoxypropylene having an allyl olefin group at the end is synthesized according to the method disclosed in Japanese Patent Application No. 52-49174.

Polyoxypropylene glycol having an average molecular weight of 3200 and powdered caustic soda are stirred at 60°C, and allyl chloride is added and reacted at 110°C to convert the terminals into allyl ether. This is treated with aluminum silicate,
Purified, terminally etherified polyoxypropylene (polyether B) was synthesized. 0 Patent application 1974-49174
Polyoxypropylene having an allylic olefin group at the end is synthesized according to the method disclosed in .

Polyoxypropylene glycol having an average molecular weight of 3200 and powdered caustic soda are stirred at 60°C, and bromochloromethane is added to carry out the reaction to increase the molecular weight.

Next, allyl chloride is added to convert the terminal to allyl ether at 110°C. This was treated with aluminum silicate to synthesize purified end-allyl etherified polyoxypropylene (polyether C). Example 1 11? Polyether A of Reference Example 2007 was placed in a pressure-resistant reaction vessel equipped with a stirrer.

Catalyst solution of chloroplatinic acid (H2PtCl2.6H203.
97 dissolved in 18 ml of isopropyl alcohol and 160 ml of tetrahydrofuran) 0.33 ml (1 x 10-4 times the mole of the polymer end) 1.1.1.3.5.
9.17 g of 7,7,7-octamethyltetrasiloxane was added and reacted at 80° C. for 2 hours. The remaining hydrosilyl groups were quantified from IR spectrum, and the reaction rate was 98%. The average molecular weight is 6100, and 94% of the terminals are olefin groups based on the iodine value and OH value determination.
6% were hydroxyl groups.

Example 2 The reaction was carried out using the same apparatus and method as in Example 1.

Polyether B2OO7 of the reference example and 0.32 ml of a catalyst solution of chloroplatinic acid (12.97 ml of 111.1.1.3.5.7.7.7-octamethyltetrasiloxane) were reacted at 80'C for 6 hours. The results are shown in the table below.

After 6 hours, 93% of the terminals of the reaction product were olefin groups and 7%
was a hydroxyl group.

Example 3 The reaction was carried out using the same apparatus and method as in Example 1.

A catalyst solution of polyether C5OOy chloroplatinic acid (0.32ml) of Reference Example 111.1.1.3.5.7.7.7-octamethyltetrasiloxane 8.707 was reacted at 80° C. for 3 hours. The reaction rate of the hydrosilyl group was 100%, and the average molecular weight was 17,100.

Further, 94% of the terminal groups were olefin groups and 6% were hydroxyl groups.

Example 4 Polyether B2OO7 of the reference example, 0.32 ml of a catalyst solution of chloroplatinic acid, 9.87 silicon dihydride having an average of two silicon hydride groups per molecule according to the following formula, and a temperature of 80° C.
Allowed time to react.

It has an average of 2 Si-H groups per n of 5 to 6.

The reaction rate after 2 hours was 100%, and the average molecular weight was 56.
It was 00.

Furthermore, 97% of the terminals were olefin groups and 3% were hydroxyl groups. Example 5 A polyether synthesized under the same conditions as Reference Example 1 was used except that allyl chloride and methallyl chloride were used in a 1:1 (molar ratio) instead of allyl chloride, and the reaction time was 5 hours. The reaction was carried out under the same conditions as in Example 1 except for this.

As a result of quantifying the remaining hydrocinole groups from IR spectrum, the reaction rate was 85%. Average molecular weight is 5600
According to the quantitative determination of the iodine value and the OH value, 90% of the terminals were olefin groups and 10% were hydroxyl groups. Kouki Example 6 Polyether synthesized under the same conditions as Reference Example 2 was used, except that various organic halides shown in the table below were used instead of allyl chloride, and the same conditions as Example 2 were used. The reaction was carried out.

The results are shown in the table below.

Claims (1)

[Scope of Claims] 1 [A] The main chain essentially has the formula (1) -R^1-O-(1) (wherein R is a divalent alkylene group having 2 to 4 carbon atoms) ) contains a chemically bonded repeating unit represented by
And at the end of the molecule, there is a formula (2) ▲ a mathematical formula, a chemical formula, a table, etc. ▼ (2) (in the formula, R^2 is hydrogen or has 1 to 2 carbon atoms
0 monovalent organic group; R^3 is a divalent organic group having 1 to 20 carbon atoms; a is an integer of 0 or 1) A polyether containing 70% or more of all terminal groups. . [B] Polyvalent hydrogenated siloxane compound having N hydrogen-silicon bonds (N is an integer of 2 to 6) in one molecule and having 2 to 20 silicon atoms (A) represented by formula (2) The molecular weight is increased by reacting the polyvalent hydrogenated siloxane compound (B) to 1/N times or less of the number of moles of the polyether end groups in ▲ or more of the total end groups have the following formula:
There are chemical formulas, tables, etc. A method for producing high molecular weight polyether which is a ▼ group and has an average molecular weight of 1000 to 30000. 2. The manufacturing method according to claim 1, wherein the polyvalent hydrogenated siloxane compound is a dihydrogenated siloxane compound. 3 The polyvalent hydrogenated siloxane compound has the formula (3)▲mathematical formula,
There are chemical formulas, tables, etc. ▼ The manufacturing method according to claim 1, which is a dihydrogenated siloxane compound having a structural unit shown in (3) in the molecule. 4. The manufacturing method according to claim 1, wherein the polyvalent hydrogenated siloxane compound is 1,1,3,3-tetramethyldisiloxane. 5 Polyvalent hydrogenated siloxane compound is 1, 1, 1, 3, 5
- The manufacturing method according to claim 1, which is 7,7,7-octamethyltetrasiloxane.