JPH0431432A - Production of polyetherester polyol - Google Patents

Abstract

PURPOSE:To obtain a polymer having a graft side chain by reacting a monool, a polycarboxylic anhydride having at least three functionalities, and a monoepoxide compd. in a specified manner in the presence of a composite metal cyanide complex as a catalyst. CONSTITUTION:In producing a polyetherester polyol by reacting a monool with a polycarboxylic anhydride having at least three functionalities and then with a monoepoxide compd. or by reacting the three reactants simultaneously, a composite metal cyanide complex is used as a catalyst at least at the reaction step of the monoepoxide compd. The resulting polyol is useful as a raw material of a synthetic resin, e.g. a polyester resin, as a resin modifier, a compatibilizer, an antioxidant, a surfactant, a fiber-treating agent, an adhesive, and a binder, and as a raw material in these uses, not to mention as a raw material of a polyurethane.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a polyether ester polyol, and particularly to a method for producing a polyether ester polyol having a graft type side chain.

[Prior art] [Problems to be solved by the invention] Grafted polymers are polymers that have a microscopic multiphase structure, and the diversity of their combinations and the ability to develop higher-order structures give the polymer unique performance. It is possible to do so. Conventional graft-type polymers are mainly vinyl polymer-based polymers, and this graft-type polymer is not well known among polymers such as polyether and polyester.

The object of the present invention is to provide a method for producing a novel graft-type polyetherester polymer.

[Means for Solving the Problems] The present invention provides the following method for producing a polyether ester polyol.

A method of producing a polyether ester polyol by reacting a monool, an anhydride of a trifunctional or more functional polycarboxylic acid, and a monoepoxide, by reacting the former two and then reacting the monoepoxide, or by reacting the three at the same time. A method for producing a polyetherester polyol, characterized in that a multimetal cyanide complex is used as a catalyst in the step of reacting a small amount of a monoepoxide.

It is known to use double metal cyanide complexes such as cobalt zinc cyanide-glyme as catalysts for producing polyethers and polyesters. As the double metal cyanide complex catalyst, for example, the following US patent and EP2
g3148 etc.

USP 3278457. , USP 327845g,
USP 3278459°USP 3427256. U
SP 3427334. USP 3427335゜US
P 3538043. USP 3829505. USP
3941849゜USP 435518g, USP
4472560. USP 4721818 As the double metal cyanide complex catalyst in the present invention, a double metal cyanide complex catalyst as shown in the above-mentioned known examples is used. This catalyst is considered to have the structure shown below - Shipura (1).

M-[M'-(CN)y]b(HtO)c(R)d++
(1) However, M is Zn(II), Fe(II)
, Fe(nl), Co(II), N1(II), AI
(III), 5r(II), Mn(II), Cr(II)
I), Cu(II), 5n(n), Pb(II), Mo
(IV), Mo(Vl), W(IV), etc. W(V
l) With Te, M' is Fe(II), Fe(III), C
o(II), Co(III), Cr(II), Cr(I
TI), Mn(II), Mn(III), N1(II)
, V(IV), V(V), etc., R is an organic ligand, and 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.

- M in shipyard (1) is preferably Zn(II) M'
are Fe(II), Fe(III), Co(II), Co
Preferred organic ligands such as (III) include ketones, ethers, aldehydes, esters, alcohols, amides, and the like.

The monoepoxide in the present invention is a compound having one epoxy ring, such as alkylene oxide, glycidyl ether, and glycidyl ester. Preferred monoepoxides are ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide,
Other alkylene oxides, particularly propylene oxide and butylene oxide, are preferred. As the polycarboxylic acid anhydride, anhydrides of trifunctional or higher functional polycarboxylic acids such as aliphatic, alicyclic and aromatic, particularly tricarboxylic acid anhydrides or tetracarboxylic acid anhydrides are preferred. Among these, aromatic polycarboxylic acid anhydrides are preferred. Apart from these trifunctional or higher functional polycarboxylic acid anhydrides, dicarboxylic acid anhydrides may be used in the present invention as described below. Specific examples of these polycarboxylic anhydrides include trimellitic anhydride, 1,2,3-butanetricarboxylic anhydride, 6-methyl-4-cyclohexene-1,2,3-tricarboxylic acid-1 , 2-anhydride, pyromellitic dianhydride, 3.3
', 4.4-benzophenonetetracarboxylic dianhydride, 3.3'', 4.4-diphenyltetracarboxylic dianhydride, 3,3.4.4-diphenyl ethertetracarboxylic dianhydride, 1,2 , 4.5-cyclohexanetetracarboxylic dianhydride, 1..2,3.4-butanetetracarboxylic dianhydride, norbornenetetracarboxylic dianhydride, etc.As the dicarboxylic acid anhydride, Examples include phthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, maleic anhydride, etc. Particularly preferred are trimellitic anhydride and pyromellitic dianhydride. Two or more of these monoepoxides, polycarboxylic acids, etc. can be used in combination.

A monol is a compound having one alcoholic hydroxyl group, and a wide variety of monols can be used in the present invention. This monol is a part that becomes a side chain of the graft type polymer, and preferably has a relatively long chain. For example, in the case of hydrocarbon monools such as alkanols, those with relatively high molecular weight (so-called higher alcohols) are preferable.
Preferred are hydrocarbon monools, halogenated hydrocarbon monools, monools having a polyether chain, polyester chain, or polyetherester chain, or monools having an organosilyl group or an organopolysiloxane chain.

As the hydrocarbon monool, lower monools such as methanol and ethanol can be used. However, as mentioned above, higher monools are preferable, especially those having 6 to 30 carbon atoms.
, preferably 8 to 25 monols are used. The hydrocarbon group is preferably an alkyl group, but may also be an unsaturated hydrocarbon group such as an akenyl group. As the halogenated hydrocarbon monool, an alkyl group or an akenyl group containing a fluorine atom is preferable, and a polyfluoroalkyl group is particularly preferable. Note that the hydroxyl group of the polyfluoroalkyl monool is bonded to a carbon atom to which a fluorine atom is not bonded. The number of carbon atoms in the polyfluoroalkyl group is 2 or more, especially 4
~20 is preferred. A monool having a polyether chain, a polyester chain, or a polyether ester chain has a hydroxyl group at one end, an alkoxy group at the other end,
Compounds having acyloxy groups, fluoroalkoxy groups, and other inert terminal groups are preferred. Such compounds can be produced by, for example, changing all but one terminal end group of polyether polyol, polyester polyol, polyether ester polyol, etc. into inert terminal groups, or ring-opening polymerization of cyclic ether or cyclic ester using a monofunctional initiator. It is manufactured by a method such as Examples of monofunctional initiators include monools, monocarboxylic acids,
There are monothiols. Examples of the cyclic ether include the above-mentioned monoepoxide, and examples of the cyclic ester include caprolactone. Further, polyether monools and polyether ester monools can also be produced by reacting monoepoxides with dicarboxylic acid anhydrides using l-functional initiators. The above-mentioned multimetal cyanide complex catalyst can be used as a catalyst for these ring-opening polymerizations. For example, in the presence of a composite metal cyanide mirror catalyst, a monool is reacted with an alkylene oxide to produce a polyether monool, and a monool, an alkylene oxide, and a dicarboxylic acid anhydride are reacted to produce a polyether ester monool. can do. Therefore, it is possible to produce a monol in the presence of a multi-metal cyanide complex catalyst and then carry out the present invention in the presence of the same catalyst. In addition, highly hydrophobic monools that are difficult to polymerize with alkali catalysts, which are conventionally widely used monoepoxide ring-opening polymerization catalysts, such as the above-mentioned higher alcohols, polyfluoroalkyl alcohols, organosilyl groups, or organopolysiloxane chains, can be used. When carrying out ring-opening polymerization of a monoepoxide to a monool having the following, it is suitable to use a multimetal cyanide complex catalyst.

In the present invention, the amounts of monol and monoepoxide relative to the polycarboxylic anhydride are not particularly limited. However, usually one equivalent of monool is used per equivalent of dicarboxylic anhydride group in the polycarboxylic anhydride, and at least the same equivalent amount of monoepoxide is used relative to the remaining carboxyl group. In addition, it is also possible to react with less than 1 equivalent of monool per 1 equivalent of dicarboxylic anhydride group, and then ring-open the remaining dicarboxylic acid anhydride group by hydrolysis, or to open the ring by reacting with a low molecular weight polyol or the like. In addition, the presence of unreacted monool is undesirable, and in practice, the presence of unreacted monool is 0.6 to 1
．． Preference is given to using 1 equivalent, especially 0.9 to 1.05 equivalents of monool.

Specifically, for example, when one molecule of tricarboxylic anhydride reacts with one molecule of monool, an ester having two carboxyl groups is produced, and when two molecules of monool react with one molecule of tetracarboxylic dianhydride, two molecules of carboxyl group are produced. A unique diester is produced. When one molecule of these esters is reacted with two molecules of monoepoxide, it reacts with the carboxyl group to produce a compound having a hydroxyl group at the end, and then the monoepoxide reacts with this hydroxyl group in sequence to extend the polyether chain.

When dicarboxylic acid anhydride is used in the latter stage together with monoepoxide in an amount equal to or less than the same amount as the monoepoxide, the polyester chain or polyetherester chain will be elongated. Furthermore, in some cases, a tricarboxylic anhydride or a tetracarboxylic anhydride may be used together with a monoepoxide to introduce a branch point. Thus, the polyether ester polyol of the present invention contains at least one trifunctional or higher functional polycarboxylic acid residue, at least two monool residues, and at least two monoepoxide ring-opening units. The upper limit of each unit is determined by the requirements such as the molecular weight of the target polyether ester polyol, the number of hydroxyl groups, and the ratio of ether bond to ester.Preferably, the hydroxyl value of the target polyether ester polyol is 200 or less, especially 5 to 120
, and the number of hydroxyl groups is 2 to 6, particularly about 2.

The reaction between the polycarboxylic anhydride and the monool can be carried out without a catalyst, but a multimetal cyanide complex catalyst may be present. Both reactions occur upon heating.

At this time, it is preferable to carry out the reaction in a suitable solvent. As the solvent, an aprotic solvent is suitable, and for example, tetrahydrofuran, dioxane, toluene, etc. are used. In order to prevent thermal oxidation and side reactions due to water in this reaction, it is preferable to carry out the reaction in a dry inert gas atmosphere.Also, an antioxidant etc. may be used. Performed at ~180°C. After that, if a multimetal cyanide complex catalyst is not present, add it, and as described above, add monoepoxide or dicarboxylic acid anhydride, etc. and react with it under an inert gas atmosphere. It is preferable to carry out the reaction at 160° C., and a solvent may be used if necessary. The amount of the multimetal cyanide complex catalyst used is not particularly limited, but is 10 ppm to 5 wt%, especially 1100 ppm to 5 wt% based on the finished amount of polyether ester polyol.
pp to 1 wt% is preferable.

The above reaction in the present invention has been made possible by using a multimetal cyanide complex catalyst that is non-aqueous and active in a substantially neutral atmosphere. Since the ester bonds in the chains and graft chains are cut and rearranged, there is the problem of broadening the molecular weight distribution due to disproportionation, and it is also difficult to maintain the graft structure.

The polyether ester polyol obtained by the present invention can be used not only as a raw material for polyurethane, but also as a raw material for polyester and other synthetic resins, resin modifiers, compatibilizers, anti-aging agents, surfactants, fiber processing agents, and adhesives. It is useful as an agent, binder, etc., or as a raw material thereof.

The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples. Note that "parts" indicating amounts refer to parts by weight.Example 1 108 parts of stearyl alcohol and trimellitic anhydride 7
7 parts and 1 part of zinc hexacyanocobalti-1 complex catalyst for 130'CX 1 h in a pressurized reactor in N2 atmosphere.
r reacted. The reactor was cooled to 110° C., and 550 parts of propylene oxide was gradually added over 5 hours to cause a reaction, thereby obtaining an ester-modified polyoxypropylene glycol having a stearyl group as a graft group. The viscosity of this product is 1050 cp (25°C), and the hydroxyl value is 63. l, weight average molecular weight (by gelvermation chromatography)
is approximately 1870, and the ratio of weight average molecular weight/number average molecular weight is 1
．． It was 21.

Example 2 54 parts of stearyl alcohol and 1 part of zinc hexacyanocopartate complex catalyst were placed in a pressurized reactor in an N2 atmosphere, 70 parts of propylene oxide was added, and the mixture was reacted at 110°C for 1 hour. Furthermore, 37 parts of phthalic anhydride was added, and 13
After reacting for 1 hour at 0°C, propylene oxide 70
The mixture was reacted at 110°C for 2 hours to obtain monool. The hydroxyl value of this monol was 47.3. 200 parts of this senol, 1 part of zinc hexazinocopaltate complex catalyst, and 32 parts of trimethic anhydride were placed in a pressurized reactor, and after reacting at 139°C for 1 hour, the reactor was heated to 110°C.
After cooling to ℃, 100 parts of propylene oxide was gradually added over 1 hour to react, and the grafted chains were reacted with phthalic acid/
An ester-modified polyoxypropylene glycol having a polyoxypropylene copolymer was obtained. The viscosity of this product was 2600 ep (25° C.), the hydroxyl value was 51.6, the weight average molecular weight was about 2100, and the ratio of weight average molecular weight/number average molecular weight was 1.46.

Example 3 Two stearyl groups were grafted in the same manner as in Example 1 except that 43 parts of pyromellitic anhydride was used instead of trimellitic anhydride and the amount of propylene oxide was 250 parts. Ester-modified oxypolypropylene glycol was obtained. The viscosity of this material is 1800 cp (2
5℃), hydroxyl value is 62.3, weight average molecular weight is approximately 19
30, and the ratio of weight average molecular weight/number average molecular weight was 1.31.

Example 4 Ester-modified polyoxypropylene glycol grafted with trimethylsilylpropyl groups was obtained in the same manner as in Example 1 except that 53 parts of 3-(trimethylsilyl)propyl alcohol was used instead of stearyl alcohol. The viscosity of this product is 900 ep (25°C), the hydroxyl value is 71, and the O1 weight average molecular weight is approximately 1600. The weight average molecular weight/number average molecular weight ratio was 1.18.

Example 5 Perfluoroalkyl alcohol with an average molecular weight of 522 (
C,,Fn-IC)lac)IJH, the average value of n was 8), and the process was carried out in exactly the same manner as in Example 1, except that 208 parts of propylene oxide were used and the amount of propylene oxide added was 313 parts. An ester-modified polyoxypropylene glycol having a perfluoroalkyl group as a graft chain was obtained. Hydroxyl value is 69.6, weight average molecular weight is approximately 14
50. The ratio of weight average 9 molecular weight/number average molecular weight was 1.58.

[Effects of the Invention] According to the present invention, it has become possible to easily produce a polyetherester polyol having a polycarboxylic acid residue by using a specific catalyst.

The obtained polyether ester polyol can have a graft structure, and the structure, length, number, etc. of the main chain and graft chains can be widely controlled, and the present invention can be used in various ways depending on the purpose. It is characterized by being able to produce polyether ester polyols having the following properties.

Claims (1)

[Claims] 1. A monool, an anhydride of a trifunctional or higher functional polycarboxylic acid, and a monoepoxide can be prepared by reacting the former two and then reacting the monoepoxide, or by reacting the three at the same time. 1. A method for producing an ether ester polyol, the method comprising using a multimetal cyanide complex as a catalyst at least in the step of reacting a monoepoxide. 2. The method according to claim 1, wherein an equivalent amount of monool is reacted with the anhydride dicarboxylic acid group of the polycarboxylic acid anhydride, and an equivalent or more equivalent amount of monoepoxide is reacted with the remaining carboxyl group. 3. A claim in which the monool is a hydrocarbon monool, a halogenated hydrocarbon monool, a monool having a polyether chain or a polyetherester chain, or a monool having an organosilyl group or an organopolysiloxane chain. The method described in paragraph 1. 4. The polycarboxylic acid anhydride is a tri- or tetracarboxylic acid anhydride, and the monoepoxide has 2 to 4 carbon atoms.
The method according to claim 1, wherein the alkylene oxide is at least one alkylene oxide. 5. The method according to claim 1, wherein the obtained polyether ester polyol has a hydroxyl value of 5 to 120.