JPH0699554B2 - Method for producing nitrogen-containing polyalkylene ether polyol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a nitrogen-containing polyalkylene ether polyol having a moiety composed of a secondary and / or a tertiary amine in the molecule.

(Prior Art) Polyalkylene ether polyols are widely used as raw materials for various polyurethanes used in spandex, synthetic leather, etc., or as raw materials for polyesters, nylon elastomers, etc. Is a 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.

(Problems to be Solved by the Invention) However, polyalkylene ether polyols such as PTMG and polyurethane elastomers and polyester elastomers synthesized from these as raw materials are
It is known that exposure to heat, chlorine, NOx, etc. causes deterioration such as yellowing and strength reduction. As a method for 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. But this method
There are drawbacks such that the amount of the stabilizer used is limited due to its compatibility with the polymer and the added stabilizer is separated from the polymer surface, so that the effect of the stabilizer is reduced.

(Means for Solving Problems) Under the circumstances, the present inventors have earnestly studied a method for producing a polyalkylene ether polyol having a structure corresponding to a stabilizer in the molecule. As a result, it is generally considered that the acid catalyst forms a salt with amines and the activity as an acid decreases, but a heteropolyacid and / or a salt thereof is used as an acid catalyst, and as an amine, 2 per molecule is used. When a secondary or tertiary amine having at least one hydroxyl group is used, it is unexpectedly possible to copolymerize the cyclic ether and the amine through the reaction of the hydroxyl group portion, and further to use the same catalyst. It was found that the copolymerization of cyclic ethers with cyclic nitrogen compounds is also possible. The nitrogen-containing polyalkylene ether polyol thus obtained was found to be excellent in yellowing resistance to NOx gas, and the present invention was completed.

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 Alternatively, two or more kinds of cyclic ethers, and (2) a cyclic nitrogen compound and a secondary amine or tertiary amine having two or more hydroxyl groups in one molecule (hereinafter, these amines may be referred to as nitrogen-containing polyhydric alcohols. is there)
A method for producing a nitrogen-containing polyalkylene ether polyol, which comprises copolymerizing one or more compounds selected from the above.

Further, the elastomer obtained by using the polyalkylene ether polyol modified so as to have nitrogen in the chain, which is obtained by the method of the present invention, also has excellent dyeability.

According to the present invention, for example, as a polyhydric alcohol containing nitrogen, a structural formula [Wherein R ₁ and R ₂ are CH ₂ n (where n = 2-1
_{0), - CH 2 CH 2} -O-CH 2 CH 2 -, - CH 2 CH 2 CH 2 -O-CH 2 C
H ₂ CH ₂ — and the above CH ₂ n, —CH ₂ CH ₂ —O—CH ₂ CH _{2
-, - CH 2 CH 2 CH} 2 -O-CH 2 CH 2 CH 2 - at least one hydrogen on the methylene carbon represents any one of those substituted in the alkyl group having 1 to 5 carbon atoms, R ₃ Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ], And when tetrahydrofuran is used as the cyclic ether, both ends of the molecule are composed of a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II). A polyether glycol having a hydroxyl group is obtained.

[Wherein R ₁ and R ₂ are CH ₂ n (where n = 2-1
_{0), - CH 2 CH 2} -O-CH 2 CH 2 -, - CH 2 CH 2 CH 2 -O-CH 2 C
H ₂ CH ₂ — and the above CH ₂ n, —CH ₂ CH ₂ —O—CH ₂ CH _{2
-, - CH 2 CH 2 CH} 2 -O-CH 2 CH 2 CH 2 - at least one hydrogen on the methylene carbon represents any one of those substituted in the alkyl group having 1 to 5 carbon atoms, R ₃ Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ] Polyether glycol having a unit (II) / unit (I) (molar ratio) of 1/99 to 1/5 and a number average molecular weight of 500 to 10,000 is a soft segment of an elastomer such as polyurethane, polyester and polyamide. It is a polyether glycol that can be effectively used as. The polyurethane synthesized using the above-mentioned nitrogen-containing polyether glycol as a raw material is characterized by being less likely to turn yellow even when exposed to NO _X gas and being excellent in dyeability.

According to the present invention, even with a cyclic ether having a low ring-opening polymerizability, such as THF, having a 5-membered ring or more, copolymerization with a nitrogen-containing polyhydric alcohol and / or a cyclic ether having nitrogen in the ring proceeds. Also, the nitrogen-containing moiety in the obtained polymer is not limited to the molecular end and is introduced into the chain.
Furthermore, the method of the present invention does not require the addition of water after the reaction for hydrolysis, and has a feature that the terminal is directly an OH group.

Such a surprising polymerization was achieved only when one molecule of heteropolyacid or a salt thereof was coordinated or present with 15 molecules or less of water as a catalyst.

The heteropolyacid and salts thereof according to the present invention include Mo, W,
Heteropolyacid, which is a general term for oxyacids formed by condensation of at least one oxide of V and other elements, for example, oxyacids such as P, Si, As, Ge, B, Ti, Ce, and Co. And its salt.

Specific examples of these heteropolyacids and salts thereof include phosphomolybdic acid, phosphotungstic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid, phosphomolybdotungstovanadic acid, phosphotungtovanadic acid, and phosphomolybdniobic acid. , Silicotungstic acid, silicomolybdic acid, silicomolybdotungstic acid, silicomolybdotungstovanadic acid, germanium tungstic acid, borotungstic acid, boromolybdic acid, boromolybdotungstic acid, boromolybdovanadic 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., I of Sc, La, Ce, Al, Ga, In, etc.
Group II, Group VIII such as Fe, Co, Ni, Ru, Pd, Pt, and Sn,
Examples thereof include metal salts such as Pb, 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 ), 2-sodium 12-tungstophosphate (Na ₂ HPW
₁₂ O ₄₀ ), 12-potassium _2- tungstophosphate (K ₂ HPW ₁₂ O ₄₀ ), 2-cesium 12-tungstophosphate (Cs ₂ HPW)
₁₂ O ₄₀ ), 12-tungstophosphate-2-silver (Ag ₂ HPW ₁₂ O ₄₀ ), 12-tungstophosphate-1-magnesium (MgHPW
₁₂ O ₄₀ ), 12-Tungstophosphate-1-calcium (CaHPW
₁₂ O ₄₀ ), 12-tungstophosphate-1-zinc (ZnHPW ₁₂ O ₄₀ ), 12-tungstophosphate-1-aluminum (AlPW
₁₂ O ₄₀ ), 12-tungstophosphate-1-gallium (GaPW ₁₂ O ₄₀ ), 12-tungstophosphate-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-magnesium (MgH ₂ SiW ₁₂ O
₄₀ ), 12-tungstosilicic acid-1-aluminum (AlHSiW ₁₂ O
₄₀ ), 12-Tungstosilicic acid-1-indium (InHSiW
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-tungstophosphate-2-ammonium [(NH ₄ ) ₂ HP
W ₁₂ O _40], 12-tungstosilicic acid-1-tetramethyl amine _{[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, the reduced form of these heteropolyacids or salts thereof may be used as a catalyst.

Heteropoly acids and salts thereof usually have coordinated water of 20 to 40, but have no polymerization activity as they are, but have a hydration number of
Polymerization activity begins to be exhibited at 15 or less, and rapid activity is exhibited particularly at 8 or less. The polymerization activity and the molecular weight of the obtained polymer change depending on the number of coordinated waters, and the relationship also slightly changes depending on the type of catalyst.Therefore, the optimum number of coordinated waters that can be easily determined by each condition and purpose is used. It is preferable to carry out the reaction.

The number of coordinated waters can be adjusted by heating the heteropolyacid or a salt thereof to a high temperature or keeping it under 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 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 nitrogen-containing polyhydric alcohol is incorporated into the polymer chain by an ether bond. Therefore, in the case of a copolymerization reaction of a polyhydric alcohol and a cyclic ether, the amount of the nitrogen-containing polyhydric alcohol used is adjusted so that the number of coordinated waters does not exceed 15 due to the produced water, or water is added to the system. It is better to carry out the reaction while removing it to the outside. Conversely, when the amount of the nitrogen-containing polyhydric alcohol used is small, or in the copolymerization reaction of the cyclic ether and the cyclic ether having a nitrogen atom in the ring, water is consumed for the terminal OH formation and coordinates with the catalyst. The amount of water decreases,
Since the polymer obtained has a high molecular weight over time, it is preferable to carry out the reaction while adding water to control the amount of water in the system constant.

Depending on the type of the heteropolyacid or its salt and the type and amount of the cyclic ether or nitrogen-containing polyhydric alcohol used, the amount of water used is 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 preferably has a total liquid phase volume of 10 in the reactor.
%, And more preferably 30% or more, a polymer having a very sharp molecular weight distribution can be obtained from the raw material organic phase. Although the detailed mechanism for sharpening the molecular weight distribution is unknown, the two-liquid phase system has a selective extraction function of selectively migrating a polymer having a certain molecular weight or more to the raw material organic phase. It is estimated to be. Therefore, when the proportion of the catalyst liquid phase in 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 secondary and tertiary amines having two or more hydroxyl groups in one molecule referred to in the method of the present invention are not particularly limited, but aminoglycols each having one hydroxyl group in each of the two substituents on the nitrogen atom. When is used, a polyalkylene ether glycol having a nitrogen atom in its main chain is obtained, and these polyalkylene ether glycols are preferable as an elastomer raw material. Furthermore, the above-mentioned aminoglycol, which is a tertiary amine having a large substituent such as a t-butyl group, an n-butyl group or a t-amyl group on the nitrogen atom, is particularly preferable. Examples of these are bis-
(2-hydroxyethyl) -n-butylamine, bis-
(2-hydroxyethyl) -t-butylamine, bis-
(2-hydroxyethyl) -t-amylamine, diethanolamine (2-hydroxyethyl)-(4-hydroxy-n-butyl) -n-butylamine, bis- (4-
(Hydroxy-n-butyl) -n-butylamine, bis-
(4-hydroxy-n-butyl) -t-butylamine,
Bis- (3-hydroxy-n-propyl) -n-butylamine, bis- (5-hydroxy-n-pentyl) -t
-Butylamine, bis- (8-hydroxy-n-octyl) -n-butylamine, the following structural formulas, and the like can be given.

Further, the amines may be subjected to the reaction in the form of salt.

In this reaction, the reaction can be carried out by adding a polyhydric alcohol or a monohydric alcohol containing no nitrogen. When a monohydric alcohol is added, a polyether having an alkyl group at a terminal is obtained.

The copolymerization composition of the nitrogen-containing polyhydric alcohol and the 5- or more-membered cyclic ether is not particularly limited, but when the nitrogen-containing polyhydric alcohol is present in the reaction system in an amount of 4 times or more moles of the heteropolyanion, the polymerization activity decreases. Therefore, it is preferable that the nitrogen-containing polyhydric alcohol in the reaction system is less than 4 times the molar amount of the heteropolyanion.

The cyclic ether having nitrogen in the ring as used in the present invention is a cyclic ether having a nitrogen atom in the ring and having ring-opening polymerizability, and is not particularly limited. A preferable example thereof is the above-described compound in which aminoglycol having one hydroxyl group in each of the two substituents on the nitrogen atom is intramolecularly dehydrated and cyclized.

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, 3,3-bis (chloromethyl). ) 4-membered ring ethers such as oxetane, 5-membered ring ethers such as tetrahydrofuran, methyltetrahydrofuran, 1,3-dioxolane, 6-membered ring ethers such as trioxane and its derivatives, 7-membered ring ethers such as oxepane and its derivatives, 1, Bicyclic 5-membered ring ethers such as 4-epoxycyclohexane and macrocyclic ethers such as 15-crown-3 and 20-crown-4 can be mentioned. The 5- or more-membered cyclic ether referred to in the method of the present invention is the above-mentioned cyclic ether excluding 3-membered cyclic ethers and 4-membered cyclic ethers.

Copolymerization composition of various cyclic ethers, copolymerization composition of cyclic ethers and nitrogen-containing polyhydric alcohols, copolymerization composition of cyclic ethers and cyclic nitrogen compounds, is not particularly limited, with nitrogen-containing polyhydric alcohols or cyclic nitrogen compounds Polyether glycol having a molar ratio of 1/99 to 1/5 with cyclic ether can be effectively used as a soft segment of elastomer such as polyurethane, polyester and polyamide.

The compound used for the polymerization is preferably one that does not contain impurities such as peroxides.

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, and the amount is 0.001 to 20 times, more preferably 0.1 to 3 times the weight of the raw material. It In order to obtain a polymer having a sharp molecular weight distribution, it is preferable to carry out the reaction under the condition that the catalyst phase forms a liquid phase, using 10% by volume or more of the total liquid phase in the reactor.

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 a solid phase, it is filtered, if it is a liquid that is two-phase separated, it is phase-separated, if it is homogeneously dissolved, the catalyst is separated by extraction, etc., and the unreacted monomer is distilled, etc. The nitrogen-containing polyalkylene ether polyol can be obtained by removing with. 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 repeatedly used as it is or after re-adjusting the amount of water as necessary. Since the reaction can be carried out while stirring the polymerization raw material and the catalyst, a solvent is not particularly required, but an inert solvent for the reaction may be added.

When the catalyst supported on the carrier is used, the polymer and the catalyst can be easily separated, the amount of the catalyst dissolved in the polymer is extremely small, and the purification process can be greatly simplified.

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.

(Effects of the Invention) According to the method of the present invention, a nitrogen-containing polyalkylene ether polyol can be synthesized in one step, and the obtained polyurethane elastomer using the nitrogen-containing polyalkylene ether polyol as a raw material is exposed to NO _X gas. However, it is stable and has excellent dyeability.

(Example) Example 1 THF200g and bis- (2-hydroxyethyl) -n-butylamine 11.2g in a container equipped with a stirrer and a reflux condenser.
Charge. Then, 100 g of phosphotungstic acid (H ₃ PW ₁₂ O ₄₀ ) made anhydrous by heating at 300 ° C. for 3 hours is added. The mole number of bis- (2-hydroxyethyl) -n-butylamine is about twice that of phosphotungstic acid. The space was filled with nitrogen, the temperature was set to 60 ° C. and stirring was continued for 6 hours. The reaction solution is in a two-liquid phase state, and after the reaction, it is left standing at room temperature to separate into two layers. Unreacted THF was distilled off from the upper layer to obtain 60.3 g of a transparent and viscous polymer. As a result of elemental analysis and ¹ H-NMR (100 MHz) measurement of the obtained polymer, the polylimer was bis- (2-hydroxyethyl)-
It was found to be a polyether glycol copolymerized with n-butylamine / THF = 1/25. ¹ H-NMR of polymer
The spectrum is shown in FIG. Further, it was confirmed by gas chromatography that almost no unreacted bis- (2-hydroxyethyl) -n-butylamine was present in the obtained polymer. As a result of measuring the molecular weight of the polymer by gel permeation chromatography (GPC), the number average molecular weight was 1,700.

Comparative Example 1 Except that phosphotungstic acid having 16 coordinated waters was used,
The same operation as in Example 1 was carried out, but the solution was in a uniform liquid phase and no polymer was formed.

Example 2 In a container equipped with a stirrer and a reflux condenser, THF 200 g and Table 1 were added.
Charge the various amines shown in. Then, 100 g of phosphotungstic acid which has been made anhydrous by heating at 300 ° C. for 3 hours is added. The temperature is set to 60 ° C., stirring is continued for 6 hours, and the mixture is left standing at room temperature to separate into two phases. Unreacted THF was distilled off from the upper layer to obtain a polymer in which amine was copolymerized with THF. Table 1 shows the amine charged, the composition of the raw material liquid, the polymer yield after the reaction, and the nitrogen weight percentage in the obtained polymer.

Example 3 200 g of THF and 11.2 of bis- (2-hydroxyethyl) -n-butylamine were placed in a container equipped with a stirrer and a reflux condenser.
g charge. Next, 100 g of various heteropolyacids or salts thereof shown in Table 2 in an anhydrous state are added. The temperature is set to 60 ° C., stirring is continued for 6 hours, and the mixture is left standing at room temperature to separate into two phases. Unreacted THF was distilled off from the upper layer, and bis-
A polymer obtained by copolymerizing (2-hydroxyethyl) -n-butylamine was obtained. The yield of the obtained polymer is shown in Table 2.

Example 4 A container equipped with a stirrer and a reflux condenser was charged with 200 g of THF (2
-Hydroxyethyl)-(4-hydroxybutyl) -t
-Butylamine 13.3 g was charged. Then, the number of coordination water is 2
Add 100 g of phosphotungtenic acid prepared as above. Temperature 60
The temperature is set to 0 ° C., stirring is continued for 6 hours, and the mixture is left standing at room temperature to separate into two phases. Unreacted THF was distilled off from the upper layer,
A polymer was obtained. The number average molecular weight of the obtained polymer is 10
00, the result of elemental analysis and ¹ H-NMR measurement showed that amine / THF
It was found that the polyether glycol was copolymerized at a ratio of 1/33 (molar ratio). The polymer yield was 30 g.

Example 5 Table 3 shows the polymer yields when the charged amount of amine was changed according to the method of Example 4.

Example 6 The same operation as in Example 1 was performed using 13.7 g of bis- (2-hydroxyethyl) -n-butylamine hydrochloride instead of bis- (2-hydroxyethyl) -n-butylamine. The yield of the obtained polymer was 34 g, and the number average molecular weight was 1,000.

Example 7 200 g of THF and Nt-butyl-perhydro-1,4-oxazepine were added to the container used in Example 1. Charge 8.0g. Then, 100 g of phosphotungstic acid in the state of coordination water number 4 is added. After stirring at a temperature of 60 ° C. for 6 hours, the mixture is left standing at room temperature to separate into two phases. Unreacted from upper layers
THF was removed by distillation to obtain a polymer in which amine was copolymerized. The polymer yield was 38 g.

Example 8 In the method of Example 7, 100 g of anhydrous phosphotungstic acid and 8.5 g of ethylene glycol were charged in place of the phosphotungstic acid in the coordination water 4. The yield of the obtained polymer is 33.
It was g.

[Brief description of drawings]

The drawing shows the ¹ H-NMR spectrum of the copolymerized polyether glycol of THF and bis- (2-hydroxyethyl) -n-butylamine described in Example 1 at 200 MHz using a JEOL FX-200 nuclear magnetic resonance apparatus. Measurement). The horizontal axis is the chemical shift (ppm) when the standard substance is tetramethylsilane
Indicates.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-59-159824 (JP, A) JP-A-60-203633 (JP, A) JP-A-61-120830 (JP, A) JP-A-61- 123626 (JP, A) JP-A-61-123628 (JP, A)

Claims (4)

[Claims] 1. A heteropolyacid and / or a salt thereof in which 15 molecules or less of water are coordinated or present per molecule is used as a catalyst, and (1) one or more containing at least one cyclic ether having 5 or more ring members, or Two or more cyclic ethers, (2)
Nitrogen-containing, characterized by copolymerizing a cyclic ether having nitrogen in the ring and a secondary amine having two or more hydroxyl groups in one molecule, and one or more compounds selected from tertiary amine Process for producing polyalkylene ether polyol. 2. A structure in which the secondary amine and the tertiary amine have two hydroxyl groups, and each of the two substituents on the nitrogen atom has one hydroxyl group. The method according to item 1. 3. A cyclic ether having a nitrogen atom in the ring is a compound obtained by intramolecular dehydration cyclization of two hydroxyl groups of an amine according to claim 2.
Method described in section. 4. The amount of water coordinated or present in the heteropolyacid and / or its salt is one per heteropolyanion.
The method according to claim 1, wherein the reaction is carried out in a two-liquid phase system using 15 molecules or less and an amount in which the polymerization system forms two liquid phases of the raw material organic phase and the catalyst liquid phase.