JPH04227925A - Production of polyoxyalkylene compound - Google Patents

Abstract

PURPOSE:To obtain the title compound excellent in abrasion resistance, impact resistance, lubricity, water repellency, low-temperature properties, etc., by polymerizing an alkylene oxide through ring opening with an initiator having an organopolysiloxane as a basic skeleton in the presence of a specified catalyst. CONSTITUTION:A process for producing a polyoxyalkylene compound by polymerizing through ring opening an alkylene oxide with an initiator in the presence of a catalyst, wherein the initiator comprises an organopolysiloxane compound having an active hydrogen functional group reactive with the alkylene oxide [e.g. a compound of formula I or II (wherein X is 3-10 C hydrocarbyl having a functional group such as OH, SH or COOH which may have an ether bond or the like, R<1>, R<2>, R<3>, R<4>, R<5>, R<6> and R<7> are each 1-6 C hydrocarbyl; R<5> is 1-18 C hydrocarbyl ; and (n) is 0 or 1-200), and the catalyst comprises a compound metal cyanide complex (particularly desirably hexacyanocobalt zinc complex). Thus, a polyoxyalkylene compound having an organopolysiloxane skeleton can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention is a method for producing polyoxyalkylene compounds having organopolysiloxane residues. [0002] A polyoxyalkylene compound is produced by ring-opening polymerization of an alkylene oxide such as propylene oxide or ethylene oxide with an initiator having at least one active hydrogen-containing functional group with which the alkylene oxide can react. It is industrially useful as a polyol component, a surfactant, and its raw material used in the polyurethane industry. Such polyoxyalkylene compounds are
Depending on the initiator used, it is possible to develop various characteristics. The most common initiator is a compound having a hydroxyl group. Alkali catalysts such as alkali metal hydroxides are widely used as catalysts for ring-opening polymerization of alkylene oxides. In the alkali catalyst, the hydroxyl group or alkylene oxide of the initiator reacts with the hydroxyl group newly generated to form an alkali metal alkoxide, and this alkali metal ion is thought to act as a catalyst. [0004] Polyoxyalkylene compounds obtained by ring-opening polymerization of alkylene oxide with an initiator having an organopolysiloxane as a basic skeleton can be used as various raw materials, modifiers, and additives, and have excellent weather resistance and water resistance in their uses. It is expected to have features such as improvement in hardness, reduced tack, and improved self-releasing properties. However, when a highly hydrophobic initiator such as an initiator with an organopolysiloxane as its basic skeleton is used, conventional alkaline catalysts exhibit a significant ring-opening addition reaction of alkylene oxide to the active hydrogen-containing functional group of the initiator. It will be disadvantageous. [0005] When an alkali catalyst is added to a highly hydrophobic initiator, the initiator and the alkali catalyst do not easily react. Therefore, the hydroxyl group of the initiator is difficult to convert into an alkali metal alkoxide, and the alkylene oxide is difficult to react with the hydroxyl group. For this reason, the alkali catalyst itself such as alkali metal hydroxide and the existing water tend to act as initiators, and polyoxyalkylene glycol that is not bonded to the highly hydrophobic initiator is produced as a by-product. happens. Another problem is that if the temperature inside the system is raised to a high temperature of 100° C. or higher in the presence of an alkali metal hydroxide, the decomposition reaction of the organopolysiloxane is likely to occur. SUMMARY OF THE INVENTION The object of the present invention is to produce a polyoxyalkylene compound by addition polymerizing an alkylene oxide to an initiator having an organopolysiloxane as its basic skeleton. [Means for Solving the Problems] The present invention provides a method for producing a polyoxyalkylene compound by ring-opening polymerization of an alkylene oxide using an initiator having an organopolysiloxane as a basic skeleton in the presence of a composite metal cyanide complex. The following invention relates to [0008] In a method for producing a polyoxyalkylene compound by ring-opening polymerization of an alkylene oxide to an initiator in the presence of a catalyst, an organopolysiloxane compound having an active hydrogen-containing functional group with which the alkylene oxide can react is used as an initiator. and a method for producing a polyoxyalkylene compound, characterized in that a double metal cyanide complex is used as a catalyst. [0009] The multimetal cyanide complex catalyst in the present invention refers to a complex containing two or more metals and having cyanide ions as part or all of the ligands, and is capable of controlling the ring-opening polymerization reaction of alkylene oxide. A substance that has the ability to catalyze. Specifically, for example, hexacyanocobalt zinc complexes such as the hexacyanocobalt zinc-glyme complex described in Japanese Patent Publication No. 59-15336, and other hexacyanocobalt zinc complexes described in U.S. Patent No. 3
No. 278457, No. 3278458, No. 3278
There are multimetal cyanide complex catalysts as described in No. 459 and the like. This catalyst is known to exhibit high catalytic activity for ring-opening polymerization of alkylene oxides. However, until now, this catalyst has not been known as a catalyst for polymerization of alkylene oxide using a highly hydrophobic initiator having an organopolysiloxane structure in the molecule. [0011] The multimetal cyanide complex in the present invention has the following general formula (1) as shown in the above-mentioned known examples.
It is thought to have the following structure. M1a[ M2x (CN)y]b (H2O)cR
d [0012] However, M1 is Zn(II), Fe
(II), Fe(III), Co(II), Ni(I
I), Al(III), Sr(II), Mn(II)
, Cr(III), Cu(II), Sn(II), P
b(II), Mo(IV), Mo(VI), W(IV)
, W(VI), etc., and M2 is Fe(
II), Fe(III), Co(II), Co(II
I), Cr(II), Cr(III), Mn(II
), Mn(III), Ni(II), V(IV), V
(V) is a metal ion such as, and R is an organic ligand. a, b, x and y are positive integers that vary depending on the valence and coordination number of the metal, and c and d are positive numbers that vary depending on the coordination number of the metal. In the multimetal cyanide complex represented by the above chemical formula, M1 is preferably Zn(II);
2 is Fe(II), Fe(III), Co(II)
, Co(III), etc. are preferred. Examples of organic ligands include ketones, ethers, aldehydes, esters,
These include alcohols, amides, nitriles, and sulfides. Particularly preferred as the multimetal cyanide complex is a zinc hexacyanocobalt complex. Further, a catalyst comprising a combination of a hexacyanocobalt zinc complex and another complex metal cyanide complex can also be used. The combination may be a combination of metal components or a mixture of two or more types of catalysts. The composite metal cyanide complex represented by the above chemical formula is composed of a metal salt M1 Ya (M1, a is the same as above, Y is an anion that forms a salt with M1) and a polycyanometalate (salt) Ze[M2x ( CN)y]f(M
2, x, y are the same as above. Z is hydrogen, alkali metal,
alkaline earth metals, etc. (e, f are positive integers determined by the valence and coordination number of Z and M2) or a solution of a mixed solvent of water and an organic solvent are mixed, and an organic ligand is added to the obtained composite metal cyanide. It is produced by contacting R and then removing excess solvent and organic ligand R. Polycyanometalate (salt) Ze[M2x
In (CN)y]f, various metals including hydrogen and alkali metals can be used for Z, but lithium salts, sodium salts, potassium salts, magnesium salts, and calcium salts are preferable. Particular preference is given to the customary alkali metal salts, ie the sodium and potassium salts. As the metal salt, metal halides are preferred, and zinc chloride and the like are suitable, for example. The organopolysiloxane compound having an active hydrogen-containing functional group with which the alkylene oxide can react, which is used as an initiator in the present invention, has at least one active hydrogen-containing functional group in the molecule that serves as a polymerization initiation point for the alkylene oxide. It is an organopolysiloxane compound with The active hydrogen-containing functional group is a functional group having 1 to 2 hydrogen atoms with which an alkylene oxide can react, such as a hydroxyl group, a mercapto group, a primary amino group, a secondary amino group, and a carboxyl group. The organopolysiloxane compound is a polymer of siloxane to which at least one organic group is bonded, and at least one of the organic groups is an organic group having an active hydrogen-containing functional group. The organic group having an active hydrogen-containing functional group may be present at at least one of both ends of the molecule, or may be present in the middle of the molecular chain. This organopolysiloxane compound may be a low polymer such as an organodisiloxane compound. There is no particular upper limit to the number of polymerized units, but 500, particularly 200, is preferred. It is preferable that two organic groups are bonded to silicon atoms other than both ends of the organopolysiloxane compound. This organic group other than the organic group having an active hydrogen-containing functional group is preferably a hydrocarbon group. Preferred examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group. Particularly preferred are alkyl groups having 4 or less carbon atoms (hereinafter also referred to as lower alkyl groups) and phenyl groups. It is preferable that three organic groups are bonded to the silicon atoms at both ends, and the above-mentioned hydrocarbon groups are preferable as the organic groups excluding the organic group having an active hydrogen-containing functional group. Furthermore, at least one of the three organic groups may be a long-chain hydrocarbon group. Examples of the organic group having an active hydrogen-containing functional group include -OH, -SH, -NH2, -NHR4, -CO2
A hydrocarbon group having 3 to 10 carbon atoms and containing one or more functional groups of one or more types selected from H is preferred. Also,
Furthermore, it may contain a linking group such as an ether bond, a thioether bond, or an amino bond. In particular, it is preferable that the organic group has 1 to 4 active hydrogen-containing functional groups. Moreover, it is preferable that the organopolysiloxane compound has 1 to 10 active hydrogen-containing functional groups. As specific organopolysiloxane compounds, compounds represented by the following formulas (1) to (3) are preferred. [Formula 4] [Formula 4] [Formula 4] [Formula 6] [Formula X is -OH, -SH, -NH2,
It is a hydrocarbon group having 3 to 10 carbon atoms and containing one or more functional groups of one or more types selected from -NHR10 and -CO2H, and may include an ether bond, a thioether bond, and an amino bond. R1, R2, R3, R4, R6
, R7, R8 and R10 are each the same or different hydrocarbon groups having 1 to 6 carbon atoms. R5 and R9 have 1 carbon number
18 hydrocarbon groups. n is 0 or 1 to 20
0 is an integer, m is an integer from 1 to 10. ) R1 and R2 are each preferably a lower alkyl group, particularly a methyl group. Each of R3 to R10 is preferably a lower alkyl group. As X, for example, a hydroxyalkyl group, a dihydroxyalkyl group, a hydroxyalkoxy-substituted alkyl group, a mercaptoalkyl group, an aminoalkyl group, an N-aminoalkyl-substituted aminoalkyl group, a carboxyalkyl group, etc. are preferable. The alkylene oxides that can be used in the ring-opening polymerization reaction of the present invention include all alkylene oxides that can be polymerized using a multimetal cyanide complex catalyst. Specific examples include ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, isobutene oxide, 1-hexene oxide, cyclohexene oxide, phenyl glycidyl ether, allyl glycidyl ether, and styrene oxide. Particularly preferred alkylene oxides are those having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, and isobutene oxide. Two or more alkylene oxides can be used in combination, and in that case, the two or more alkylene oxides can be mixed and reacted, or can be reacted separately and sequentially. In the actual polymerization reaction, a mixture of an initiator, a multimetal cyanide complex, and an alkylene oxide may be heated under nitrogen atmosphere to the polymerization reaction temperature conditions. At this time, the alkylene oxide may be added all at once, or may be added little by little while checking the progress of the reaction. Furthermore, when two or more alkylene oxides are polymerized as described above, block copolymers and random copolymers can also be freely produced depending on the method of addition. In other words, a random copolymer can be obtained by adding a mixture of two or more alkylene oxides, or a random copolymer can be produced by adding a mixture of two or more alkylene oxides, one by one, after the polymerization reaction of each type is completed. block copolymers can be produced. The polymerization reaction temperature is suitably 20 to 180°C, preferably 60 to 130°C. This polymerization reaction can be carried out with or without a solvent. When a solvent is used, the solvent can be recovered by distilling it off from the reaction mixture after the reaction is complete. Solvents that can be used in the present invention include ether, hydrocarbon, halogenated hydrocarbon, ketone, amide, and ester solvents, with ether and ketone solvents being particularly preferred. Specifically, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, 1,2-dimethoxypropane, diethylene glycol dimethyl ether, methyltetrahydrofuran,
Examples include dioxane, acetone, and methyl ethyl ketone. In the present invention, since the multimetal cyanide complex catalyst easily coordinates with active hydrogen-containing functional groups, it is possible to achieve high It is believed that alkylene oxide can be easily polymerized even when an initiator having a hydrophobic organopolysiloxane structure in the molecule is used. Moreover, the decomposition reaction of organopolysiloxane does not occur in the multimetal cyanide complex catalyst of the present invention. [Examples] The present invention will be explained in detail with reference to Examples below, but the present invention is not limited to these Examples. [Example 1] α,ω-bis[3-(2-hydroxyethoxy)propyl]polydimethylsiloxane having a molecular weight of about 1800 and represented by the following formula (4) 500
g and hexacyanocobalt zinc-glyme complex 0.1 g
was placed in an autoclave under a nitrogen atmosphere, and the internal temperature was increased to 10
The reactor was heated to 0°C and reacted while introducing 1.5 kg of propylene oxide so that the internal temperature did not exceed 120°C. After the introduction of propylene oxide was completed, the mixture was further stirred at the same temperature for 1 hour, and unreacted monomers were distilled off under reduced pressure to obtain 2.5 kg of a slightly cloudy oil. The product showed a single peak different from that of the raw material polydimethylsiloxane in GPC analysis, and its hydroxyl value was 12.9 mgKOH/g. The resulting oil did not separate even after storage at 25°C for 3 months. [Example 2] 25 g of 1-(3-mercaptopropyl)-1,1,3,3,3-pentamethyldisiloxane was dissolved in 25 g of tetrahydrofurne, and zinc hexacyanocobalt- 0.05 g of glyme complex was added and placed in an autoclave. Furthermore, when 50 g of propylene oxide was added and heated to 100° C. under a nitrogen atmosphere, an exothermic reaction occurred. After the exotherm had ended, the mixture was further heated to 100° C. for 30 minutes, and unreacted monomers were degassed under reduced pressure to obtain 74.8 g of an oily substance. The product showed a single peak in GPC analysis. [Example 3] α, ω of average molecular weight 876
-0.0 g of hexacyanocobalt zinc-glyme complex in a mixture of 100 g of -bis(3-meltocaptopropyl)-polydimethylsiloxane and 100 g of tetrahydrofuran.
2g was added and heated in an autoclave under a nitrogen atmosphere for 10 minutes.
Heated to 0°C. A mixture of 300 g of propylene oxide and 100 g of ethylene oxide was gradually introduced into the autoclave so that the internal temperature did not exceed 120°C. After the monomer introduction was completed, the mixture was further heated for 1 hour, and then the solvent was distilled off under reduced pressure to obtain 498 g of an oily substance. GPC analysis of the product showed a single peak;
The hydroxyl value was 26.5 mgKOH/g. The resulting oil did not separate even after storage at 25°C for 3 months. [Example 4] α, ω of average molecular weight 800
A mixture of 25 g of -bis(3-aminopropyl)-polydimethylsiloxane and 5 g of propylene oxide was heated in an autoclave at 120 DEG C. for 2 hours. After degassing unreacted monomers and cooling to room temperature, 0.01 g of hexacyanocobalt zinc-glyme complex and 50 g of tetrahydrofuran were added, and 50 g of propylene oxide was heated under a nitrogen atmosphere until the internal temperature was reached.
The mixture was introduced little by little so as not to exceed 120°C. After the monomer introduction was completed, the mixture was further heated for 1 hour, and then the solvent and unreacted monomers were distilled off under reduced pressure to obtain 75.1 g of an oily substance. GPC analysis of the product showed a single peak, and the hydroxyl value was 95.
It was 0mgKOH/g. [Example 5] 50 g of α-methyl-ω-3-(2,2-bis(hydroxymethyl)butoxy)propyl polydimethylsiloxane having an average molecular weight of 2000 and represented by the following formula (5) and hexacyanocobalt zinc- 0.02 g of glyme complex was placed in an autoclave and heated to 100°C under a nitrogen atmosphere. Propylene oxide 1
A mixture of 00 g and 30 g of 1-butene oxide was introduced little by little and reacted so that the internal temperature did not exceed 120°C. After the alkylene oxide was introduced, the mixture was further heated at the same temperature for 1 hour to remove unreacted monomers and obtain 180 g of an oily substance. GPC analysis of the product showed a single peak;
The hydroxyl value was 14.5 mgKOH/g. The resulting oil did not separate even after storage at 25°C for 3 months. [Example 6] Represented by the following formula (6),
α of molecular weight 5000, hydroxyl value 27mgKOH/g,
50 g of ω-bismethylpolydimethylsilyloxy-polymethyl-3-(2-hydroxyethoxy)propylsiloxane and 0.0 g of hexacyanocobalt zinc-glyme complex.
02g into an autoclave and under nitrogen atmosphere 10
Heated to 0°C. 150 g of propylene oxide was gradually introduced and reacted so that the internal temperature did not exceed 120°C. After the introduction of propylene oxide was completed, the mixture was further heated at the same temperature for 1 hour to remove unreacted monomers and obtain 200 g of an oily substance. GPC analysis of the product showed a single peak;
The hydroxyl value was 7.0 mgKOH/g. The resulting oil did not separate even after storage at 25° C. for 3 months. EFFECT OF THE INVENTION The present invention has made it possible to produce a polyoxyalkylene compound having an organopolysiloxane skeleton, which has been difficult to produce using conventional alkali catalysts. In particular, the interfacial properties such as wear resistance, lubricity, and water repellency,
It is expected to have excellent mechanical properties such as impact resistance and low-temperature properties, and can be used as a raw material for elastomers, sealants, foams, etc.
It can be considered to be used as a modifier for resins.

Claims (6)

[Claims] Claim 1: An organopolysiloxane compound having an active hydrogen-containing functional group with which an alkylene oxide can react as an initiator in a method for producing a polyoxyalkylene compound by ring-opening polymerization of an alkylene oxide to an initiator in the presence of a catalyst. and a double metal cyanide complex as a catalyst. 2. The method according to claim 1, wherein the active hydrogen-containing functional group is a functional group selected from a hydroxyl group, a mercapto group, a primary amino group, a secondary amino group, and a carboxyl group. 3. The manufacturing method according to claim 1, wherein the organopolysiloxane compound is at least one compound represented by the following chemical formulas (1) to (3). [Chemical 1] [Chemical 2] [Chemical 3] (In the formula, X is -OH, -SH, -NH2, -NHR10
, -CO2H, and may contain an ether bond, a thioether bond, or an amino bond. R1, R2, R3, R4, R6, R7, R8,
R10's are each the same or different hydrocarbon group having 1 to 6 carbon atoms. R5 and R9 are hydrocarbon groups having 1 to 18 carbon atoms. n is 0 or an integer from 1 to 200, m
is an integer from 1 to 10. ) 4. The organopolysiloxane compound comprises R1,
4. The manufacturing method according to claim 3, wherein the polydimethylsiloxane compound is a polydimethylsiloxane compound in which each R2 is a methyl group. 5. X is a hydroxyalkyl group, a dihydroxyalkyl group, a hydroxyalkoxy-substituted alkyl group,
4. The production method according to claim 3, which is a mercaptoalkyl group, an aminoalkyl group, an N-aminoalkyl-substituted alkyl group, or a carboxyalkyl group. 6. The manufacturing method according to claim 1, wherein the alkylene oxide is an alkylene oxide having 2 to 4 carbon atoms.