JPH0350230A - Polyether - Google Patents

Abstract

PURPOSE:To obtain a polyether useful as a machine oil or a starting material for urethane by specifying the relationship between the number-average mol.wt. and the viscosity and the hydroxyl value. CONSTITUTION:At least two members selected from among polypropylene oxide, butylene oxide and propylene oxide are copolymerized in the presence of a catalyst, desirably a double metal cyanide complex (e.g. iron hexacyanocobaltate) to obtain a polyether satisfying the relationship of the formula (wherein M is the number-average mol.wt. and V is the viscosity (cp/25 deg.C)) and having a hydroxyl value of 5-56, a mol.wt. distribution <=1.3, a total degree of unsaturation <=0.07 and an SP value (according to the Hoy method) >=7.0.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to polyethers, and particularly to polyether polyols.

[Prior art] Polyethers obtained by ring-opening reaction of monoepoxides such as alkylene oxides as initiators are widely used as raw materials for synthetic resins such as polyurethane, surfactants, lubricants, and other uses. . The inishek is a hydroxyl group-containing compound represented by A (H), l (A: a residue obtained by removing the hydrogen atom of the hydroxyl group of the hydroxyl group-containing compound, n: an integer of 1 or more). Examples of initiators include monohydric alcohols, polyhydric alcohols, monohydric phenols, and polyhydric phenols. Compounds having a hydroxyalkylamino group (alkanolamines, amines-alkylene oxide adducts, etc.) are also used as initiators. Furthermore, polyethers obtained by reacting the above initiator with a monoepoxide can also be used as an initiator.

Polyethers are the following compounds obtained by subjecting the above initiator to a ring-opening reaction with monoepoxide.

A-HR-0)h H]n R: Ring-opened unit of monoepoxide n, m: An integer of 1 or more Conventionally, as a method for producing polyethers, a method of reacting monoepoxide in the presence of an alkali catalyst has been widely used. It is used. Alkali metal compounds such as potassium hydroxide and sodium hydroxide have been used as alkali catalysts.

However, polyethers obtained using an alkali catalyst have the following problems. That is, an unsaturated monool produced by isomerization of monoepoxide, particularly propylene oxide, serves as an initiator, and an unsaturated monoether to which monoepoxide is added is produced.

As the molecular weight of polyethers increases, the rate of isomerization increases, and this tendency becomes noticeable when the molecular weight is 5000 or higher (in the case of trifunctional).As a result of the formation of this unsaturated monol, propylene oxide is added to monoepoxide. When using polyethers, it is virtually impossible to synthesize polyethers with a molecular weight of 6,000 or more, and even if the molecular weight is 3,000 or more, the ratio of viscosity to number average molecular weight decreases as the molecular weight increases.

Therefore, for polyethers with a molecular weight of 3000 or more, we control the viscosity and solubility parameters of the product,
It has not been possible to synthesize polyethers whose viscosity index and solubility parameters meet product specifications as machine oils, and polyethers whose compatibility with isocyanate is controlled as raw materials for polyurethane.

[Problem to be solved by the invention] Polypropylene oxide, which is a raw material for polyurethane foam, elastomers, and machine oil, has a number average It is difficult to obtain polyethers having a viscosity in a constant ratio to the molecular weight, especially for polyethers having a hydroxyl value of 56 or less.

For this reason, conventionally, even if one or two of the property values, hydroxyl value, viscosity, and solubility parameters of polyethers deviated from the target values, they could not be used as machine oil or urethane raw materials. We have used items that fall within the target values for the following items.

However, with these existing methods, it is difficult to obtain high-performance products as raw materials for machine oil and urethane, and there is a problem in that polyethers are used with low performance.

[Means for Solving the Problems] The present invention aims to reduce by-products and reduce the molecular weight of polyethers in order to improve their properties as machine oil and urethane raw materials, their viscosity index, their compatibility with incyanate, etc. Considering that it would be effective to use controlled polyethers, we investigated the use of polyethers with controlled molecular weight, viscosity, and solubility parameters, which were previously impossible, as raw materials for machine oil and urethane.

The present invention provides the following invention to solve the above-mentioned problems.

In the method of using polyethers as machine oil and urethane raw materials, the polyethers have a hydroxyl value of 5 to 56, a viscosity, and a number average molecular weight that satisfy the relationship of logV ≧ 1.28 ・1ogM −1,8. It is something. The correlation between molecular weight and viscosity is as shown in Figure 1, and a comparison was made between the range that satisfies this item and conventional polyols.

The polyethers used in the present invention have fewer by-products and have controlled viscosity and compatibility parameters than conventional polyether machine oils, polyurethane elastomers, polyurethane foams, etc. Problems observed, especially when using high molecular weight polyether polyols with a hydroxyl value of 56 or less (relative decrease in viscosity, deterioration of viscosity index, and deterioration of isocyanate compatibility in the low hydroxyl value region) It suppresses the deterioration of the curing properties of urethane elastomer foam, and exhibits excellent properties as the above raw material.

Such polyether polyols are generally obtained by using diethylzinc, iron chloride, metal porphyrin, double metal cyanide complex, etc. as a catalyst other than an alkali catalyst. In particular, good polyether polyols are obtained by using double metal cyanide complexes.

In the present invention, as the polyol, one or more of the above-mentioned polyether polyols having a low degree of unsaturation and a low hydroxyl group can be used. In addition to polyether polyols, polyols having 2 to 8, especially 2 to 4 hydroxyl groups such as polyester polyols and hydroxyl group-containing polydiene polymers can be used in combination. In particular, it is preferable to use only one or more types of polyether polyols, or to use polyether polyols as the main component in combination with a small amount (usually 30% or less) of polyester or hydroxyl group-containing polydiene polymers. As the polyether polyol, a polyether polyol obtained by adding a cyclic ether, particularly propylene oxide alone or ethylene oxide to a polyhydric alcohol, saccharide, alkanolamine, polyhydric phenol or other initiator, is preferable. These high molecular weight polyether polyols or high molecular weight polyol mixtures need to have a hydroxyl value of 5 to 56 and a total unsaturation degree of 0.07 or less, and a total unsaturation degree of 0.05 or less is particularly preferred.

Furthermore, so-called polymer polyols in which fine particles of addition polymerization polymers or condensation polymerization polymers are dispersed can also be used as high molecular weight polyols. This polymer polyol can also be used in combination with the above-mentioned high molecular weight polyol. As the polymer polyol, a polyether polyol containing 3 to 40% by weight of fine particles of acrylonitrile, styrene, or the like alone or as a copolymer is preferred. The hydroxyl value of this polymer polyol or a mixture of it and other high molecular weight polyols must also be from 5 to 56, and the total degree of unsaturation must be 0.07 or less, preferably 0.05 or less.

The hydroxyl value is expressed in r mgKOH/gJ, and the total unsaturation degree is expressed in milliequivalents/gJ.

When these polyethers are used as urethane raw materials, compatibility with isocyanates becomes a problem, and in order to improve compatibility, conventionally they have been used as compatibilizers such as silicone surfactants.

The compatibility between polyethers and isocyanates is expressed by a solubility parameter (SP value).

The SP value is related to the energy required to mix two components, and researchers have developed a method for calculating it.
dors, Hildebrand, TeasBagl
Although there is a method by Hay et al., Hoy's method was used for calculation here. According to Hoy's method, the SP value and δ are expressed by the following formula. G: Molecular structural constant Calculate the value of G as follows (example) -CHs 147.3 CH* -131,5 -CH- 85,99 10 -114,98 -OH225,84 The sp value of polyethers is:

G -3000-0 (glycerin initiator, booxypropylene ether polyol with molecular weight 3000) ΣG=131.5 X85.99 + (114
,98+131.5 +85.99 +147.3)
+50.14+ 225.84 As such a high molecular weight polyether polyol, a polyether polyol having a block chain of oxyethylene group at the terminal is preferable. The content of the terminal oxyethylene group is preferably 2 to 20% by weight, particularly 5 to 15% by weight, based on the molecular weight of the polyether polyol.

In the present invention, only the above-mentioned polyol with a low hydroxyl value (i.e., high molecular weight) can be reacted with an isocyanate compound (excluding water). Can be used with molecular weight polyols. This polyfunctional compound is a compound having two or more incyanate-reactive groups such as a hydroxyl group, a primary amino group, or a secondary amino group, and a molecular weight per inocyanate-reactive group of 600 or less, particularly 300 or less. is appropriate. Such compounds include compounds commonly referred to as crosslinkers or chain extenders, such as polyhydric alcohols, alkanolamines, polyamines; There are low molecular weight polyether polyols obtained by adding a small amount of alkylene oxide to monoamines, polyhydric phenols, etc. Furthermore, low molecular weight polyester polyols can also be used. Preferably, polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, and glycerin, alkanolamines such as jetanolamine and triethanolamine, and polyether polyols having a hydroxyl value of 200 or more are used. The amount of this polyfunctional compound used is about 10 parts by weight per 100 parts by weight of high molecular weight polyol.
It is preferably at most 5 parts by weight, particularly at most 5 parts by weight. Although there is no particular lower limit to the amount used, when used, about 0.2 parts by weight is sufficiently effective.

Examples of the polyisocyanate compound include aromatic, alicyclic, or aliphatic polyisocyanates having two or more isocyanate groups, mixtures of two or more thereof, and modified polyisocyanates obtained by modifying them. Specifically, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylisocyanate (commonly known as crude MDI)
) Polyisocyanates such as xylylene diisocyanate, inphorone diisocyanate, and hexamethylene diisocyanate, as well as prepolymer-type modified products, nurate-modified products, urea-modified products, and carbodiimide-modified products thereof.

When reacting polyols and polyisocyanate compounds, the use of catalysts is usually required.

As the catalyst, a metal compound catalyst such as an organic tin compound or a tertiary amine catalyst such as triethylenediamine is used, which promotes the reaction between an active hydrogen-containing group and an isocyanate group. Further, a polymerization catalyst that causes incyanate groups to react with each other, such as a carboxylic acid metal salt, is used depending on the purpose.

When polyethers are used as machine oil or lubricating oil, stabilizers such as antioxidants are added to improve storage stability. As the stabilizer, amino-based and quaternary ammonium-based stabilizers are usually used.

Hydroxyl value 5 to 56, molecular weight distribution M shown in the present invention
The molecular weight distribution M w / M n of polyethers in which w / M n is 1.3 or less and the number average molecular weight and viscosity satisfy the relationship shown in claim 1 is determined by GPC.

[Example] The following polypropylene ether polyol was synthesized, its viscosity and molecular weight distribution were analyzed, and comparisons were made with conventional polyethers.

Polyol A: polyoxybrobylene diol with a molecular weight of 5000 using a complex metal cyanide complex (iron hexacyanocopaltate) as a catalyst Polyol B: using a complex metal cyanide complex (zinc hexacyanocopaltate) as a catalyst Polyoxypropylene diol polyol C with a molecular weight of 3000: A polyoxypropylene triol with a molecular weight of 9000 using a composite metal cyanide complex (zinc hexacyanocopaltate) as a catalyst is reacted with ethylene oxide in the presence of an alkali catalyst (potassium alcoholade). , the molecular weight where the oxyethylene group content accounts for 10% by weight of the whole, to, oo
o polyether polyol Example 1 The viscosity of polyol A is 1150 (cp/25°C)
, molecular weight distribution M w / M n = 1.10 (G
(Calculated from PC) The sp value was calculated taking into account 3 wt% of unsaturated monool contained as a by-product.

Sp value of polyether polyol main chain δ = 8.323 Sp value of by-product monool δ = 8.180 Sp value of polyol A of these mixtures δ = 8.319 Therefore, isocyanate (P-MDI) δ = 10.4
00 and shows good miscibility.

Comparative Example 1 The properties of polyoxypropylene triol with a molecular weight of 5000 synthesized as a conventional KOH catalyst were as follows.

Viscosity 900 (cp/25℃), molecular weight distribution Mw/M
n −1,35, sp value was calculated considering 25 wt % of by-product unsaturated monol.

δ=8.287, and the state of mixing with isocyanate (MDI) is poor.

Example 2 Polyol B had a viscosity of 590 (cp/25°C), a molecular weight distribution Mw/Mn=1.08, and an unsaturated monool contained as a by-product of 2 wt%.

sp value of polyether polyol main chain = 8.361, sp value of by-product monol = 7.570, sp value of polyol B of these mixtures = 8.345, incyanato (MDI) δ = 10.600, which is good. It shows a good mixability.

Comparative Example 2 The property values of polyoxypropylene diol with a molecular weight of 3000 synthesized using conventional KOH as a catalyst were as follows.

Viscosity 520 (cp/25℃), molecular weight distribution = 1.2
8-1.35, sp value is 4.5wt% unsaturated monol
Including 8.325, cell stability during slab foam foaming is poor due to low miscibility with TDI and low viscosity.

Example 3 Viscosity of polyol C: 2700 (cp/25°C), molecular weight distribution M w / M n = 1.08 (GPC
(calculated from), and the sp value was 6 wt% of unsaturated monool contained as a by-product.

The sp value of the polyol main chain = near, 796, the sp value of the by-product monol = 7.630, and the sp value of these mixtures =
7.786, showing relatively good compatibility with isocyanate (MDI).

Comparative Example 3 When using the conventional method KOH, it was impossible to synthesize polyoxypropylene triol having a molecular weight of 7000 or more.

[Effects of the Invention] As described above, it has been found that polyethers having the same molecular weight and controlled viscosity have controlled solubility parameters and molecular weight distribution.

[Brief explanation of drawings]

FIG. 1 is a graph showing the correlation between molecular weight and viscosity.

Claims (1)

[Claims] 1. Polyethers having a hydroxyl value in the range of 5 to 56, where the number average molecular weight and viscosity have the relationship shown in the following formula. logV≧1.28・logM−1.8 V: Viscosity (cp/25°C) M: Number average molecular weight 2, the polyether is polypropylene omoxide or a copolymer of at least two types of butylene oxide and propylene oxide. A polyether polyol according to claim 1. 3. The polyethers according to claim 1, which have a molecular weight distribution Mw/Mn of 1.3 or less. 4. The polyethers according to claim 1, which have a total degree of unsaturation of 0.07 or less. 5. The polyether according to claim 1, which has an SP value (according to Hoy's method) of 7.0 or more.