JPH0676484B2 - Method for producing sulfur-containing polyalkylene ether polyol - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a polyalkylene ether polyol having a sulfur atom in its molecule.

(Prior Art) Polyalkylene ether polyols are used in various fields as raw materials for various polyurethanes used in spandex, synthetic leather, etc., or as raw materials for polyester elastomers, nylon elastomers, etc. It is an industrially useful polymer.

Among them, polyoxytetramethylene glycol (hereinafter abbreviated as PTMG), which is a homopolymer of tetrahydrofuran (hereinafter abbreviated as THF), is an important polymer most often used for the above applications. These polyalkylene ether polyols usually undergo ring-opening polymerization of cyclic ethers, and then
It is obtained by hydrolyzing the terminal and converting it into a hydroxyl group.

(Problems to be solved by the invention) However, polyalkylene ether polyols such as PTMG and polyurethane elastomers and polyester elastomers synthesized using these as raw materials are yellowed or have a high strength when exposed to oxygen, light or heat. It is known that deterioration such as deterioration occurs. As a method of preventing such deterioration, it has been generally practiced to add a stabilizer such as a phenol compound, an amine compound or a sulfur compound to a polymer. However, this method has a drawback that the amount of the stabilizer used is limited due to the compatibility with the polymer and the added stabilizer is separated from the polymer surface, so that the effect of the stabilizer is reduced.

(Method for Solving Problems) Under the circumstances, the present inventors have diligently studied a polyalkylene ether polyol having a structure corresponding to a stabilizer in the molecule. As a result, using a heteropolyacid and or a salt thereof as a catalyst, by reacting a cyclic ether such as THF and a polyhydric alcohol having a sulfur atom in the molecule, a polyalkylene ether polyol having a sulfur atom in the molecule is obtained. The present invention has been accomplished and the present invention has been accomplished.

That is, the present invention uses, as a catalyst, a heteropoly acid and / or a salt thereof in which 15 molecules or less of water are coordinated or present per molecule, and (1) one kind containing at least one cyclic ether having 5 or more ring members or A method for producing a sulfur-containing polyalkylene ether polyol, which comprises copolymerizing two or more kinds of cyclic ether (2) a polyhydric alcohol having a sulfur atom in the molecule.

According to the method of the present invention, even with a 5-membered or higher cyclic ether having a low ring-opening polymerizability such as THF, the copolymerization with a polyhydric alcohol having a sulfur atom proceeds, and in the obtained polymer, Thus, the sulfur-containing moiety is not limited to the molecular end and is introduced into the chain. Further, the method of the present invention is characterized in that after the reaction, it is not necessary to add water to hydrolyze, and the terminal is directly made into an OH group.

Such a surprising polymerization was achieved only when a heteropoly acid or a salt thereof in which one molecule or less of 15 molecules or less of water was coordinated or present was used as a catalyst.

The heteropoly acids and salts thereof according to the present invention are Mo, W, V
Among them, at least one kind of oxide and another element, for example, heteropoly acid, which is a general term for oxyacids formed by condensation of oxyacids such as P, Si, As, Ge, B, Ti, Ce and Co, and its It is salt.

Specific examples of these heteropolyacids and salts thereof, phosphomolybdate, phosphotungstic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid, phosphomolybdotungstovanadic acid, phosphotungstovanadic acid, phosphomolybdniobic acid, Tungstosilicic acid, silicomolybdic acid, silicomolybdotungstic acid, silicomolybdotungstovanadic acid, germanium tungstic acid, borotungstic acid, boromolybdic acid, homolybdotungstic acid, homolybdovanadic acid, homolybdotungsto Examples thereof include vanadic acid, cobalt molybdic acid, cobalt tungstic acid, arsenic molybdic acid, arsenic tungstic acid, titanium molybdic acid, cerium molybdic acid and salts thereof.

The type of salt is not particularly limited, but for example, Li, Na, K,
Rb, Cs, Cu, Ag, Au, etc., Periodic Table Group I, Mg, Ca, Sr, B
Group II of a, Zn, Cd, Hg, etc., III of Sc, La, Ce, Al, In, etc.
Group VIII such as Fe, Co, Ni, Ru, Pd, Pt, and Sn, P
Examples thereof include metal salts such as d, Mn and Bi, ammonium salts, amine salts and the like.

Examples of these salts include 12-tungstophosphoric acid-1-
Lithium (LiH ₂ PW ₁₂ O ₄₀ ), 12-tungstophosphoric acid-2
-Sodium (Na ₂ HPW ₁₂ O ₄₀ ), 12-Tungstophosphate 2-potassium (K ₂ HPW ₁₂ O ₄₀ ), 12-Tungstophosphate 2-cesium Cs ₂ HPW ₁₂ O ₄₀ ), 12-Tungstoline Acid-1-silver (AgHPW ₁₂ O ₄₀ ), 12-tungstophosphoric acid-1-
Magnesium (MgHPW ₁₂ O ₄₀ ), 12-Tungstophosphoric acid-
1-calcium (CaHPW ₁₂ O ₄₀ ), 12-tungstophosphoric acid-1-zinc (ZnHPW ₁₂ O ₄₀ ), 12-tungstophosphoric acid-1
-Aluminum (AlPW ₁₂ O ₄₀ ), 12-tungstophosphoric acid-1-gallium (GaPW ₁₂ O ₄₀ ), 12-tungstophosphoric acid-1-indium (InPW ₁₂ O ₄₀ ), 12-tungstophosphoric acid-1-chromium (CrPW ₁₂ O ₄₀ ), 12-tungstophosphoric acid-1-bismuth (BiPW ₁₂ O ₄₀ ), 12-tungstophosphoric acid-1-iron (FePW ₁₂ O ₄₀ ), 12-tungstosilicic acid-1-
Nickel (NiHSiW ₁₂ O ₄₀ ), 12-Tungstosilicic acid-2
- Lithium _{(Li 2 H 2 SiW 12 O} 40), 12- tungstosilicic acid-2 silver _{(Ag 2 H 2 SiW 12 O} 40), 12- tungstosilicic acid -
1- aluminum _{(MgH 2 SiW 12 O 40)} , 12- tungstosilicic acid-1- aluminum (AlHSiW ₁₂ O _40), 12- tungstosilicic acid-1-indium (InHSW ₁₂ O _40), 12- tungstosilicic acid-1-gallium (GaHSiW ₁₂ O ₄₀ ), 12-molybdophosphoric acid-1-lithium (LiH ₂ PMo ₁₂ O ₄₀ ), 12-molybdophosphoric acid-1-magnesium (MgHPMo ₁₂ O ₄₀ ), 12
-Tungstophosphoric acid 2-ammonium [(NH ₄ ) ₂ HPW
₁₂ O ₄₀ ], 12-tungstosilicic acid-1-tetramethylamine [N (CH ₃ ) ₄ H ₃ SiW ₁₂ O ₄₀ ] and the like. Also, a mixture of heteropolyacid and heteropolyacid salt may be used. The heteropolyacid salt is prepared by titrating an aqueous solution of heteropolyacid with a carbonate or nitrate of each metal, ammonia, or amine, and evaporating to dryness.

Further, a reduced form of these heteropolyacids or salts thereof may be used as a catalyst.

Heteropoly acids and their salts usually have 20 to 40 coordinated water, but they do not have polymerization activity as they are, but when the hydration number is 15 or less, they start to exhibit polymerization activity, and especially 8 or less have rapid activity. . The polymerization activity and the molecular weight of the obtained polymer change depending on the number of coordinated waters, and the relationship changes slightly depending on the type of catalyst.Therefore, the reaction should be performed at the optimum number of coordinated waters that can be easily determined according to each condition and purpose. It is preferable to carry out.

The number of coordinated waters can be adjusted by heating the heteropolyacid or a salt thereof to a high temperature or keeping it under a reduced pressure at a relatively low temperature. It can also be adjusted by mixing a predetermined amount of water with a polymerization raw material such as a cyclic ether and supplying it from a state where the number of coordinating water is smaller than the required number.

Water is formed when the sulfur-containing polyhydric alcohol is incorporated into the polymer chain by an ether bond. Therefore, in the case of the copolymerization reaction of polyhydric alcohol and cyclic ether, the amount of sulfur-containing polyhydric alcohol used should be adjusted or water should be removed from the system so that the number of coordination water does not exceed 15 due to the generated water. It is better to carry out the reaction while removing. Conversely, when the amount of the sulfur-containing polyhydric alcohol used is small, water is consumed for the terminal OH formation, the amount of water coordinated to the catalyst decreases, and the resulting polymer becomes a high molecular weight over time. , It is better to carry out the reaction while adding water to control the amount of water in the system to be constant.

Depending on the type of the heteropolyacid or its salt and the type and amount of the cyclic ether or sulfur-containing polyhydric alcohol used, the amount of water is 1 to 1 for each heteropolyanion.
When present in a ratio of 15 molecules, the polymerization system forms two liquid phases, a catalyst liquid phase and a raw material organic phase. When the amount of water is less than the above amount, the heteropolyacid and / or its salt becomes a solid phase in the reaction system, and when the amount is more, the catalyst is uniformly dissolved. In a two-liquid system, the catalyst liquid phase is preferably 10% or more of the total liquid phase volume in the reactor,
More preferably, when the reaction is carried out using 30% or more, a sharp polymer having a very high molecular weight distribution is obtained from the raw material organic phase. Although the detailed mechanism by which the molecular weight distribution becomes sharp is unknown, the two-liquid phase system has a selective extraction function of selectively transferring a polymer having a certain molecular weight or more to the raw material organic phase. It is estimated to be. Therefore, when the ratio of the catalyst liquid phase to the total liquid phase is low, the molecular weight selective extraction function by the two liquid phases is impaired and the molecular weight distribution does not become sharp.

The catalyst may be supported on activated carbon, silica alumina or the like and used as a fixed bed or a fluidized bed.

The polyhydric alcohol having a sulfur atom in the molecule as used in the present invention is not particularly limited as long as it has a sulfur atom and two or more hydroxyl groups in the molecule. When a dihydroxyalkyl sulfide having one hydroxyl group is used, a polyalkylene ether glycol having a sulfur atom in the main chain is obtained, and these polyalkylene ether glycols are preferable as an elastomer raw material. Examples of sulfur-containing polyhydric _{alcohol, HO-CH 2 CH 2 -S} -CH 2 CH 2 -OH (2,2 '
- _{thiodiethanol), HO-CH 2 CH 2} CH 2 -S-CH 2 CH 2 CH 2
-OH _{(3,3'-thio-di-propanol), CH 3 CH (OH)} CH 2
_{-S-CH 2 -CH (OH)} -CH 3, HO-CH 2 CH 2 CH 2 -S-CH 2 CH
(OH) CH ₃ , HOOH ₄ SCH _{2 4} OH, HO-CH ₂ CH ₂ -SC
_{H 2 CH 2 CH 2 -OH,} HO-CH 2 CH 2 -S-CH 2 CH 2 -O-CH 2 CH 2 -
_{OH, HO-CH 2 CH 2} -S-CH 2 CH 2 -S-CH 2 CH 2 OH, HO-CH 2 C
_{H 2 -S-CH 2 CH (} CH 3) -OH, HO-CH 2 CH 2 -S-CH 2 CH (C
_{H 3) CH 2 OH, HO} -CH 2 CH (OH) -CH 2 -S-CH 2 CH 2 -OH and the like.

Further, in this reaction, a polyhydric alcohol containing no sulfur or a monohydric alcohol can be added and reacted. When a monohydric alcohol is added, a polyether having an alkyl group at a terminal is obtained.

The copolymerization composition of the sulfur-containing polyhydric alcohol and the 5- or more-membered cyclic ether is not particularly limited, but when the sulfur-containing polyhydric alcohol is present in the reaction system in an amount of 4 times or more moles of the heteropolyanion, the polymerization activity is reduced. In addition, the sulfur-containing polyhydric alcohol in the reaction system is a heteropolyanion of 4
It is preferable to use a double molar end.

Examples of the cyclic ether used in the method of the present invention include three-membered cyclic ethers such as ethylene oxide, propylene oxide, isobutylene oxide, and epichlorohydrin, oxetane, 3,3-dimethyloxetane, 3-methyloxetane, and 3,3-bis (chloromethyl) oxetane. 4-membered ring ethers such as tetrahydrofuran, methyltetrahydrofuran, 1,3-dioxolane and the like, 6-membered ring ethers such as trioxane and its derivatives, 7-membered ring ethers such as oxepane and its derivatives, 1,4- Bicyclic 5-membered ring ethers such as epoxycyclohexane and macrocyclic ethers such as 15-crown-3 and 20-crown-4 can be mentioned. The term "5- or more-membered cyclic ether" as used in the method of the present invention means the above cyclic ethers excluding 3-membered cyclic ethers and 4-membered cyclic ethers.

The cyclic ether copolymer composition and the copolymer composition of the cyclic ether and the sulfur-containing polyhydric alcohol are not particularly limited.

The compound used for the polymerization preferably does not contain impurities such as peroxide.

When the reaction temperature is increased, the degree of polymerization tends to decrease, and in view of the polymerization yield, it is preferably -10 to 150 ° C, particularly preferably 30 to 100 ° C. 150
If it exceeds ℃, the yield will decrease, and if it is below -10 ℃, the reactivity will be low.

The amount of the heteropolyacid and / or its salt to be used is not particularly limited, but the polymerization rate is slow when the amount of the catalyst in the reactor is small, 0.001 to 20 times the raw material, and more preferably 0.1.
~ 3 times weight used. In order to obtain a polymer having a sharp molecular weight distribution, it is preferable to carry out the reaction using 10% by volume or more of the total liquid phase in the reactor under the condition that the catalyst phase forms a liquid phase.

The time required for the reaction is 0.5 to 50 hours, depending on the amount of catalyst and the reaction temperature. The reaction pressure may be normal pressure, increased pressure, or reduced pressure.

After the reaction, if the catalyst is in the solid phase, it is filtered, if it is a two-phase liquid separation, it is phase separation, and if it is homogeneously dissolved, the catalyst is separated by extraction, etc., and the unreacted monomer is distilled. By removing, a sulfur-containing polyalkylene ether polyol is obtained. The polymer obtained is subjected to purification such as washing and treatment with an adsorbent to obtain a product. The separated catalyst phase can be used repeatedly as it is or after readjusting with the amount of water if necessary. The reaction can be carried out while stirring the polymerization raw material and the catalyst, so no particular solvent is required,
You may add the thing inactive to reaction.

As the reaction type, a generally used type such as a tank type or a tower type is used. Further, both batch type and continuous type can be carried out.

(Effect) A polyalkylene ether polyol containing sulfur can be synthesized in one step by the method of the present invention, and the obtained sulfur-containing polyalkylene ether polyol has better heat resistance than a polyalkylene ether polyol containing no sulfur. .

(Examples) Hereinafter, the present invention will be described with reference to Examples.

Example 1 A container equipped with a stirrer and a reflux condenser was charged with 200 g of THF and 2,2 '.
− Charge 8.2 g of thiodiethanol. Then 3 at 320 ℃
Phosphotungstic acid (H ₃
Add 100 g of PW ₁₂ O ₄₀ ). Fill the container with nitrogen and raise the temperature to 6
The temperature was set to 0 ° C. and stirring was continued for 6 hours. The reaction liquid is in the state of two liquid phases, and after the reaction, it is allowed to stand at room temperature to separate into two phases. By the reaction, 2,2'-thiodiethanol was almost consumed, and unreacted THF was distilled off from the upper phase to obtain 14 g of a transparent and viscous polymer. The results of elemental analysis and'H-NMR measurement of the obtained polymer by fluorescent X-ray,
The polymer is 2,2'-thiodiethanol / THF = 1/22 (mol
It was found to be a sulfur-containing polyalkylene ether glycol copolymerized by the ratio. As a result of gel permeation chromatography (GPC) measurement, the number average molecular weight is 2
It was 000.

Comparative Example 1 The same operation as in Example 1 was carried out except that phosphotungstic acid having coordinated water number of 16 (H ₃ PW ₁₂ O ₄₀ ) was used, but no polymer was obtained.

Example 2 The same operation as in Example 1 was performed using various thioglycols shown in Table 1 in place of 2,2′-thiodiethanol. The results are shown in Table-1.

Example 3 Example 1 using various catalysts shown in Table 2 in an anhydrous state
The reaction was carried out according to the method of 1. to obtain a polymer. The results are shown in Table-2.

Claims (3)

[Claims] 1. A heteropoly acid in which 15 molecules or less of water per molecule are coordinated or present, or a salt thereof is used as a catalyst,
(1) Sulfur-containing polyalkylene characterized by copolymerizing one or two or more cyclic ethers containing at least one 5-membered ring or more ether and (2) a polyhydric alcohol having a sulfur atom in the molecule. Method for producing ether polyol. 2. The method according to claim 1, wherein the polyhydric alcohol having sulfur in the molecule is a dihydroxyalkyl sulfide having one hydroxyl group in each of the two substituents on the sulfur atom. 3. The amount of water coordinated or present in the heteropolyacid and / or salt thereof is 15 molecules or less per one heteropolyanion, and the polymerization system is used in such an amount as to form two liquid phases of a raw material organic phase and a catalyst liquid phase. The method according to claim 1, wherein the reaction is carried out in a two-liquid phase system.