JPS6118569B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a process for producing high molecular weight polyethers or polyesters with terminal moisture-curable silicification. A method for producing polyethers having olefin groups at the ends using polyethers having hydroxyl groups at the ends as a starting material has already been developed by General Electric Company
36319, Special Publick Showa 46-12154), Dow Corning
It was proposed by the Corporation (Special Publication 1977-36960). 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. A method in which a hydroxyl group and a polyfunctional isocyanate compound such as toluene diisocyanate are reacted to form a polyether having an isocyanate group at the end, and an allyl urethane group is introduced at the end by reacting the isocyanate group with allyl alcohol. be. The manufacturing method proposed by Dow 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 pyridine. This is the way to do it. In this production method, since a low molecular weight hydroxyl-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 a 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. This poses a major problem. The present inventors conducted various studies to solve these problems, and as a result, produced a high molecular weight polyether or polyester having an olefin group at the end,
Thereafter, the polyether or polyester is reacted with a silicon hydride compound to obtain a polyether or polyester having a moisture-curable siliconized terminal,
The present invention was achieved by discovering that a rubber elastic body with high elongation can be obtained by curing. That is, the present invention provides contains on average at least one bonding unit selected from the group consisting of Polyether or polyester containing 70% or more of the terminal groups shown in It is characterized by reacting a silicon hydride compound represented by The present invention provides a method for producing a polyether or polyester having at least one end siliconized as represented by the formula: In the present invention, the polyether or polyester having at least one bonding unit represented by formula (1) in the main chain is produced, for example, by the following method. (i) Polyoxyalkylene polyols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene triol, polyoxypropylene tetraol, polyoxybutylene glycol, polytetramethylene glycol, polyoxyethylene oxypropylene glycol, etc. with hydroxyl groups less than 1/2 mole An acid anhydride represented by, or (wherein Z is a group selected from a halogen atom, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms) It is reacted with a carboxylic acid derivative represented by the following formula. (ii) Monoallyl monohydroxy polyalkylene oxide is reacted with 1/2 mole or less of the acid anhydride represented by formula (8) or the carboxylic acid derivative represented by (9). (iii) Polycarboxylic acids such as maleic acid, adipic acid, phthalic acid, etc., their anhydrides, their esters, or their halides in a stoichiometric excess of ethylene glycol, propylene glycol, glycerin, etc. A polyester polyol obtained by reacting with a polyol is reacted with an acid anhydride represented by formula (8) or a carboxylic acid derivative represented by formula (9) in an amount of 1/2 mole or less based on the hydroxyl group. (iv) Reacting a lactone polyol obtained by ring-opening polymerization of lactones with an acid anhydride represented by formula (8) or a carboxylic acid derivative represented by formula (9) in an amount of 1/2 mole or less per hydroxyl group. . (v) Use a mixture of two or more polyhydroxy compounds selected from polyoxyalkylene polyols, monoallyl monohydroxy polyalkylene oxides, polyester polyols, and lactone polyols shown in (i) to (iv), and It is reacted with 1/2 mole or less of the acid anhydride represented by formula (8) or the carboxylic acid derivative represented by formula (9). In the present invention, the polyether or polyester having at least one bonding unit represented by formula (2) in the main chain is polyoxyalkylene polyol, monoallyl monohydroxy polyalkylene oxide,
An isocyanate compound represented by the formula οCN-R ¹ -NCO (10) in which polyhydroxy compounds selected from polyester polyols, lactone polyols, etc. are used alone or in combination of two or more, and 1/2 mole or less of the polyhydroxyl group is used. It can be obtained by reacting with In the present invention, polyethers or polyesters having at least one bonding unit represented by formula (3) in the main chain include polyoxyalkylene polyols, monohydroxymonoallyl polyalkylene oxides,
It can be obtained by using polyhydroxy compounds selected from polyester polyols, lactone polyols, etc. singly or in combination of two or more, and reacting 1/2 mole or less of COCl ₂ with the hydroxyl group of the polyhydroxy compound. In the present invention, a polyether or polyester having a terminal group represented by formula (4) at the end of the molecule is used. or bonded with polyester. For example, specific methods include the following. (i) converting the terminal hydroxy groups of the polyether or polyester into alkoxy groups by reacting with an alkali metal compound selected from alkali metals, alkali metal hydroxides, and alkali metal hydrides; (In the formula, Q is a halogen atom selected from chlorine, bromine, and iodine.) It is reacted with an unsaturated halogen compound represented by the following formula. The terminal group of formula (4) is introduced via an ether bond, ester bond or carbonate bond. (ii) When the terminal hydroxy group of polyether or polyester is reacted with an unsaturated isocyanate compound such as allyl isocyanate, an unsaturated group is introduced at the terminal via a urethane bond. (iii) Terminal hydroxy groups of polyether or polyester or (In the formula, V is a halogen atom selected from chlorine, bromine, and iodine, an alkoxy group, or a hydroxy group; R ⁵ is a divalent atom with a carbon number of 1 to 20 combined with hydrogen, oxygen, or carbon. (organic group)) is reacted with an unsaturated ester compound, unsaturated active halogen compound, or unsaturated carboxylic acid. An unsaturated group is introduced at the end via an ester bond or a carbonate bond. (iv) By reacting the terminal hydroxyl group of the polyether or polyester with a polyvalent isocyanate compound represented by formula (10), a polyether or polyester having an isocyanate group at the end is obtained, and then the isocyanate group and an unsaturated alcohol such as allyl alcohol, an unsaturated amine (primary or secondary) such as allylamine, or an unsaturated carboxylic acid such as acrylic acid. An unsaturated group is introduced at the end via a urethane bond. (v) By reacting the terminal hydroxy groups of polyether or polyester with phosgene,

[Formula] Polyether or polyester having a group Tell, followed by

React with an unsaturated alcohol, unsaturated amine or unsaturated carboxylic acid that can react with the [Formula] group. An unsaturated group is introduced at the end via a carbonate bond. (vi) By reacting the terminal hydroxy group of polyether or polyester with a compound represented by formula (8) or formula (9),

[Formula] Polyether or polyester having a group, followed by

React with an unsaturated alcohol, unsaturated amine, or unsaturated carboxylic acid that can react with the [Formula] group.
An unsaturated group is introduced at the end via a carbonate bond or an ester bond. (vii) Using a polyether or polyester having an unsaturated group represented by the formula (4) and a hydroxy group at the end, such as monoallyl monohydroxy polyalkylene oxide, and having a stoichiometrically equivalent amount of the hydroxy group. A polyvalent isocyanate compound, a polyvalent carboxylic acid, a carboxylic acid anhydride, a polyvalent carboxylic acid ester, a polyvalent carboxylic acid halide, or phosgene are reacted. At this time, polyethers or polyesters such as polyoxyalkylene polyols, polyester polyols, and lactone polyols may be used in combination. In the present invention, polyethers or polyesters containing on average at least one bonding unit selected from formulas (1), (2), and (3) in the main chain are used, where R ¹ is It is a divalent organic group having 1 to 20 carbon atoms. Especially preferred as R ¹ are alkylene groups having 1 to 20 carbon atoms, cycloalkylene groups, arylene groups, and aralkylene groups. In the present invention, a polyether or polyester having a terminal group represented by the formula (4) is used, where R ² is hydrogen or has 1 to 20 carbon atoms.
is a monovalent organic group. The monovalent organic group is preferably an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. More particularly, hydrogen is preferred as R ² . In the formula, R ³ is a divalent organic group having 1 to 20 carbon atoms. R ³ is particularly a carbonyl group, a divalent hydrocarbon group having 1 to 20 carbon atoms, an ether bond,
A divalent organic group having 1 to 20 carbon atoms containing an ester bond, a carbonate bond, a urethane bond, a urea bond, or an amide bond is preferred. In the present invention, the terminal group

[Formula] Based on By reacting the silicon hydride compound shown by A polyether or polyester having a silyl group at at least one terminal is produced. Specific examples of silicon hydride compounds include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, methyldiethoxysilane, and methyldimethoxysilane. and alkoxysilanes such as phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; ketoxylsilanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane Examples include matesilanes. Particularly preferred are halogenated silanes and alkoxysilanes. When reacting the silicon hydride compound of formula (5), it is necessary to use a platinum-based catalyst. Particularly favorable results are obtained using catalysts such as chloroplatinic acid, platinum metal, platinized activated carbon, platinum chloride, and platinum olefin complexes. Any temperature from 30 to 150°C can be used to carry out this reaction, but it is particularly preferably carried out at a temperature in the range from 50 to 120°C. 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. Furthermore, in the present invention, the hydrolyzable group in the terminal silyl group obtained by formula (6) is converted to another hydrolyzable group Y, An alkylene oxide polymer having a silyl group shown at at least one end can be produced.
In particular, when the X group is a halogen, hydrogen halide with a strong pungent odor is generated upon curing with moisture, so it is preferable to convert it to another hydrolyzable group. Hydrolyzable functional groups that can be converted include alkoxy groups, acyloxy groups, ketoximate groups, amide groups, amide groups, acid amide groups, aminooxy groups,
and a methcapto group. Various methods can be used to convert halogen functional groups into these hydrolyzable functional groups. For example, methanol,
Alcohols and phenols such as ethanol, 2-methoxyethanol and phenol; alkoxides of alcohols and phenols such as sodium, potassium and lithium; orthoformate esters such as methyl orthoformate and ethyl orthoformate; ethylene oxide Specific examples include a method in which epoxy compounds such as , propylene oxide, allyl glycidyl ether, etc. are reacted with a halogen functional group. In particular, the reaction can be easily carried out by using a reaction system consisting of alcohols and phenols in combination with orthoformic acid esters, and a reaction system consisting of alcohols and phenols in combination with epoxy compounds. You can get favorable results. Similarly, carboxylic acids such as acetic acid and propylene acid; hydroxylamines such as NN-dimethylhydroxylamine, NN-diethylhydroxylamine; primary and secondary amines such as NN-dimethylamine, NN-diethylamine, pyrrolidine; acetamide, Acid amides having at least one hydrogen atom on the nitrogen atom such as formamide; Ketoximes such as acetoxime and methyl ethyl ketoxime; n-
If a reaction system is used in which methylcaptans such as octyltylcaptan and t-butylmercaptan are combined with orthoformate esters or epoxy compounds, acyloxy groups, aminooxy groups, amide groups, acid amide groups, and ketoximate groups can be used, respectively. , and a mercapto group, and the other part can be converted into an alkoxide group derived from an orthoformate or an epoxy compound. As mentioned above, it is not only possible to convert halogen functional groups to other hydrolyzable functional groups, but also to convert various hydrolyzable functional groups into other hydrolyzable functional groups for use. . When exposed to the atmosphere, the silicon-terminated polyether used in the present invention 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 the atmospheric temperature, relative humidity, and type of hydrolyzable group, the type of hydrolyzable group must be carefully considered when using the resin. As the hydrolyzable groups X and Y, various groups can be used as described above, but alkoxy groups are particularly preferred. Among the alkoxy groups, a methoxy group is more preferred. or,
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. Alkyl titanates when using condensation catalysts; organosilicon titanates; metal salts of carboxylic acids such as tin octylate, dibutyltin laurate and dibutyltin maleate, dibutyltin phthalate; dibutylamine-2-ethylhexo 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 is 0 to 10% by weight based on the silicon-terminated polyether.
It is preferable to use it in When alkoxy groups are used as the hydrolyzable groups X and Y, the curing rate is slow if this polymer alone is used, so it is preferable to use a condensation catalyst. In this case, tin polyester salts are particularly preferred as condensation catalysts. The silicon-terminated polyethers of this invention can be modified by incorporating various fillers. Fillers include reinforcing fillers such as fume silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black, calcium carbonate, magnesium carbonate, 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, glass fibers and filaments can be used. If you want to obtain a cured composition with high strength using these fillers, mainly fume silica, precipitated silica,
1 to 100 parts by weight of a filler selected from anhydrous silicic acid, hydrated silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and activated zinc white per 100 parts by weight of silicon-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 carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon are used. Favorable results can be obtained if the amount of 5 to 200 parts by weight is used per 100 parts by weight of silicon-terminated polyether. Of course, these fillers may be used alone or in combination 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. For example, phthalate esters such as dioctyl phthalate, dibutyl phthalate, butylbenzyl phthalate; aliphatic dibasic acid esters such as dioctyl adipate, isodecyl succinate, dibutyl sebacate; and diethylene glycol dibenzoate, pentaerythritol ester, etc. Glycol esters; Aliphatic esters such as butyl oleate, methyl acetyl ricinoleate, etc.; Phosphate esters such as tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, etc.; Epoxidized soybean oil, benzyl epoxy stearate Epoxy plasticizers such as epoxy plasticizers; chlorinated paraffin and other plasticizers can be optionally used alone or in the form of a mixture of two or more types. The amount of plasticizer is silicon-terminated polyether 100
Preferable results can be obtained when the amount is used in the range of 0 to 100 parts by weight. 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. In the composition containing silicon-terminated polyether as an active ingredient in the present invention, a one-component composition and a two-component composition are used.
Any liquid composition is possible. When used as a two-component composition, for example, a component consisting of a silicon-terminated polyether, a filler and a plasticizer;
Good results can be obtained by separating the components into a plasticizer and a condensation catalyst and mixing the two components immediately before use. When used as a one-component composition,
If the silicon-terminated polyether, filler, plasticizer, and condensation catalyst are sufficiently dehydrated and dried, then mixed in the absence of moisture and stored in a cartridge, it can be used as a one-component composition with good storage safety. be. 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. Example 1 800 g of polypropylene oxide having a molecular weight of 8,000 is placed in a pressure-resistant reaction vessel equipped with a stirrer and purged with nitrogen. The polypropylene oxide contains in one molecule as a bonding unit for increasing the molecular weight,

【formula】

[Formula] It has two groups in total, and the terminal of the molecule is CH ₂ = CHCH ₂ O- group 85%, CH ₃ CH = CHO-
It consists of 5% base and 10% HO base. 23g of methyldichlorosilane was added under a nitrogen stream, followed by a catalyst solution of chloroplatinic acid (2g of H ₂ PtCl _{6.6H 2} O).
9 ml of iso-propanol, tetrahydrofuran
Add 0.52w (dissolved solution) to 82ml and heat at 80℃ for 6
Allow time to react. Lower the temperature of the reaction system to 30℃, add 23g of propylene oxide, and then add methanol.
After adding 12.8g and reacting at 30℃ for 2 hours with stirring,
The temperature was raised to ℃ and allowed to react for 4 hours. After the reaction is complete, volatile components are removed under reduced pressure, and 80% of the end groups are removed.

[Formula] A polymer is obtained. 1 part by weight of dibutyltin dilaurate and 1.5 parts by weight of activated zinc white were added to 100 parts by weight of the polymer, mixed well, and when left in the air at room temperature.
It cures in ~2 days, yielding a rubber elastic body with high elongation. Example 2 Molecular weight was added to a pressure-resistant reaction vessel equipped with a stirrer and replaced with nitrogen.
Add 700g of 7000 polypropylene oxide.
The polypropylene oxide contains a bonding unit in one molecule to increase the molecular weight.

[Formula] average the groups It has two molecules, and the end of the molecule is

[Formula] Group 50%, CH ₂ = CHCH ₂ O- group 40%, CH ₃ CH
= Consists of 5% CHO- group and 5% HO- group. 21 g of methyldimethoxysilane was added under a nitrogen stream, and then 2 g of a catalyst solution of chloroplatinic acid (H ₂ PtCl ₆ .6H ₂ O was added to iso-propanol 9
ml, solution dissolved in 82 ml of tetrahydrofuran)
Add 0.52 ml and react at 90°C for 8 hours. After the reaction is complete, volatile components are removed under reduced pressure, resulting in terminal groups.

[Formula] Group

A polymer is obtained in which the sum of the radicals is 82%. For 100 parts by weight of the polymer, 25 parts by weight of dioctyl phthalate, 50 parts by weight of fatty acid-treated calcium carbonate, 30 parts by weight of light calcium carbonate, 25 parts by weight of titanium oxide, 2 parts by weight of organic bentonite, 5 parts by weight of silicic acid anhydride, and carbon. 0.5 parts by weight of black, 2 parts by weight of activated zinc white, 1 part by weight of dibutyltin dilaurate, 0.5 parts by weight of nickel dibutyldithiocarbamate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol)
1 part by weight, 2(2'-hydroxy-3',5'-di-ter
A blended composition was prepared by adding 0.5 parts by weight of (butylphenol)-5-chlorobenzotriazole and mixing with three paint rolls. The composition is heated to 23°C,
When left in an atmosphere with 60% humidity, it hardens in 1 to 2 days and becomes a highly elongated rubber elastic body. Example 3 Molecular weight was added to a pressure-resistant reaction vessel equipped with a stirrer and replaced with nitrogen.
7000 block copolymer of polycaprolactone and polypropylene oxide [polycaprolactone/
Polypropylene oxide = 1/6 (weight ratio)] to 700
Take g. The block copolymer contains in one molecule as a bonding unit to increase the molecular weight.

[Formula] It has two groups on average, and the molecular terminal is

[Formula] Group 70%, CH ₂ = CHCH ₂ O- group 20%, HO- group 10%
It is made up of 32g methyldiacetoxysilane
was added under a nitrogen stream, and then a catalyst solution of chloroplatinic acid (H ₂ PtCl _{6.6H 2} O2g was added to iso-propanol).
9wl, solution dissolved in 82ml of tetrahydrofuran)
Add 0.52 ml and react at 85°C for 10 hours. After the reaction is complete, volatile components are removed under reduced pressure, resulting in terminal groups.

[Formula] group, A polymer with a total group content of 75% is obtained. To 100 parts by weight of the polymer, add 1 part by weight of dibutyltin dilaurate and 1 part by weight of activated zinc white, mix well, and when left in the air at room temperature, it will harden in 1 to 2 days to form a rubber-facilitating material with high elongation. can get. Example 4 The reaction conditions were the same as in Example 2, except that 42.7 g of methyldi(methylethylketoxime)silane was used instead of 21 g of methyldimethoxysilane, and a bonding unit for increasing the molecular weight was added in the main chain.

[Formula] Has two groups on average and serves as a terminal group base and 25 parts by weight of dioctyl phthalate, 50 parts by weight of fatty acid-treated calcium carbonate, 30 parts by weight of light calcium carbonate, and 25 parts by weight of titanium oxide were added to 100 parts by weight of the polymer in which a total of 78% of the polymer was obtained. ,
2 parts by weight of organic bentonite, 5 parts by weight of silicic acid, 0.5 parts by weight of carbon black, 2 parts by weight of activated zinc white
parts by weight, 1 part by weight of dibutyltin dilaurate, 0.5 parts by weight of nickel dibutyldithiocarbamate,
1 part by weight of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 0.5 part by weight of 2(2'-hydroxy-3',5'-di-tert-butylphenol)-5-chlorobenzotriazole. A blended composition is prepared by adding and mixing with three paint rolls.
When the composition is left in the atmosphere at 23 DEG C. and 60% humidity, it hardens in 1 to 2 days and becomes a highly elongated rubber elastic body. Example 5 The reaction conditions were the same as in Example 3, except that 43.5 g of methyldi(diethylaminooxy)silane was used instead of 32 g of methyldiacetoxysilane, and a bonding unit for increasing the molecular weight was added in the main chain.

[Formula] Has two groups on average and serves as a terminal group base and

A polymer was obtained in which the sum of the groups was 68%. The polymer 100
When 1 part by weight of dibutyltin dilaurate and 1 part by weight of activated zinc white are added to each part by weight and mixed well, and the mixture is left in the air at room temperature, it hardens in 1 to 2 days, and a rubber elastic body with high elongation is obtained.

Claims (1)

[Claims] 1. In the main chain (In the formula, R ¹ is a divalent organic group having 1 to 20 carbon atoms) containing on average at least one bonding unit selected from the group consisting of (In the formula, R ² is hydrogen or a monovalent organic group having 1 to 20 carbon atoms; R ³ is a divalent organic group having 1 to 20 carbon atoms; b
is an integer of 0 or 1) to polyether or polyester containing 70% or more of all terminal groups. (In the formula, R ⁴ is a monovalent hydrocarbon group having 1 to 12 carbon atoms; X is a group or atom selected from halogen, alkoxy group, acyloxy group, ketoximate group, and aminooxy group; a is 0, 1, or 2 is characterized by reacting a silicon hydride compound represented by A method for producing a polyether or polyester having at least one end silicided as represented by: