JP2013241581A - Method of manufacturing polyether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing polyether that can manufacture the polyether in which a primary ratio of a terminal hydroxy group is high and an unsaturation degree is low, that can give excellent moldability to a modified resin using the same, and that can give excellent physical properties in strength, elongation and water resistance or the like to a molding obtained from the resin.SOLUTION: An initiator having at least one hydroxyl group in a molecule is made to perform ring-opening addition of propylene oxide in the existence of a composite metal cyanide catalyst, continuously ethylene oxide is performed by ring-opening addition in the existence of a non-nucleophilic basic catalyst, or the initiator having at least one hydroxyl group in a molecule is made to perform ring-opening addition of the propylene oxide in the existence of the composite metal cyanide catalyst, continuously the propylene oxide and the ethylene oxide are performed by random ring-opening addition in the existence of the composite metal cyanide catalyst and the non-nucleophilic basic catalyst, and further continuously the ethylene oxide is performed by ring-opening addition in the existence of the non-nucleophilic basic catalyst.

Description

  The present invention relates to a method for producing a polyether. Polyethers obtained by ring-opening addition of alkylene oxide to active hydrogen compounds are widely used for resin raw materials such as polyurethane and polyester, surfactants, lubricants and the like. In particular, to impart properties such as flexibility, flexibility, and low temperature rubber elasticity to aromatic polyester resins, unsaturated polyester resins, thermoplastic polyester elastomers, thermosetting urethane resins, thermoplastic polyurethane elastomers, and acrylic resins Thus, the use of polyethers has attracted attention. The present invention relates to an improvement in a method for producing such a polyether, and more particularly to a method for producing a polyether having a high degree of primary hydroxyl group terminalization and a low degree of unsaturation.

  In general, polyethers are obtained by ring-opening addition of an alkylene oxide such as propylene oxide to an initiator such as a polyhydric alcohol in the presence of a sodium catalyst such as sodium hydroxide or a potassium catalyst such as potassium hydroxide. It is manufactured. However, this conventional production method has a problem that unsaturated monool is produced as a by-product, and the production amount increases with an increase in the molecular weight of the polyether, and only propylene oxide is added as an alkylene oxide by ring-opening addition. In such a case, most of the terminal hydroxyl groups of the obtained polyether are secondary hydroxyl groups, and there is a problem that the reactivity of the polyether is low.

  Therefore, conventionally, a mixture of ethylene oxide and another alkylene oxide is subjected to ring-opening addition in the presence of a double metal cyanide catalyst (also referred to as double metal cyanide complex catalyst). There has been proposed a method for producing a polyether having a high primary ratio of terminal hydroxyl groups by introducing a random addition structure with an alkylene oxide (see Patent Documents 1 and 2). However, even in these conventional methods, there is actually a problem that the primary hydroxyl group conversion rate of the obtained polyether is still low.

  Conventionally, as a method for producing a polyether having a high primary hydroxyl group-termination rate, in the first step, the initiator is subjected to ring-opening addition of propylene oxide in the presence of a double metal cyanide catalyst, and then the second step. In the second step, ethylene oxide and propylene oxide are randomly ring-opened and added, and finally in the third step, ethylene oxide is ring-opened and added in the presence of an alkali metal catalyst (for example, Patent Document 3). And 4). However, in these conventional methods, water is generated by a side reaction in the presence of an alkali metal catalyst, and this water produces high molecular weight polyethylene glycol, and the physical properties of the resin molded product from which this high molecular weight polyethylene glycol is obtained. There is a problem of remarkably worsening.

JP-A-3-244632 JP-T-2002-543228 JP 2003-301041 A Special table 2007-533809 gazette

  The problem to be solved by the present invention is to provide a method capable of producing a polyether having a high terminal hydroxyl group primary ratio and a low degree of unsaturation, and practically using it. An object of the present invention is to provide an improved method for producing a polyether, which imparts good moldability to the modified resin, and gives good properties such as strength, elongation and water resistance to a molded product obtained from such resin.

  The present invention that solves the above-mentioned problems involves the ring-opening addition of propylene oxide to an initiator having at least one hydroxyl group in the molecule in the presence of a double metal cyanide catalyst, followed by the presence of a non-nucleophilic basic catalyst. Under the condition of ring-opening addition of ethylene oxide, a polyether having a terminal hydroxyl group primary ratio of 60 to 100%, a polystyrene-equivalent number average molecular weight of 2000 to 20000 and an unsaturation degree of 0.10 or less is obtained. The present invention relates to a method for producing a featured polyether.

  The present invention also provides propylene oxide ring-opening addition to an initiator having at least one hydroxyl group in the molecule in the presence of a double metal cyanide catalyst, followed by double metal cyanide catalyst and / or non-nucleophilic basicity. Propylene oxide and ethylene oxide are randomly subjected to ring-opening addition in the presence of a catalyst, and further ethylene oxide is subjected to ring-opening addition in the presence of a non-nucleophilic basic catalyst so that the terminal hydroxyl group primary ratio is 60 to 100. %, A polyether having a polystyrene-equivalent number average molecular weight of 2000 to 20000 and an unsaturation degree of 0.10 or less.

  In the method for producing a polyether according to the present invention (hereinafter simply referred to as the production method of the present invention), a double metal cyanide catalyst (hereinafter abbreviated as DMC catalyst) is added to an initiator having at least one hydroxyl group in the molecule. In the presence of propylene oxide (hereinafter abbreviated as PO).

  As the DMC catalyst, for example, a coordinated tert-butanol can be used. Examples of the organic complexing ligand of the DMC catalyst include water-soluble organic compounds having a hetero atom (for example, oxygen, nitrogen, phosphorus, or sulfur) that can form a complex with a double metal cyanide. Preferred as organic complexing ligands are alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides and mixtures thereof. More preferred organic complexing ligands are water-soluble fatty alcohols such as ethanol, isopropanol, n-butanol, iso-butanol, sec-butanol, tert-butanol and mixtures thereof, with tert-butanol being most preferred.

  When PO is ring-opened and added to an initiator having at least one hydroxyl group in the molecule in the presence of the DMC catalyst as described above, the DMC catalyst is unlikely to be unsaturated due to side reactions. A polyether having a low degree of unsaturation can be obtained as compared with the case of using an alkali metal catalyst such as potassium. However, at this stage, the obtained polyether has a high degree of secondaryization of terminal hydroxyl groups.

  Therefore, in the production method of the present invention, ring-opening addition of ethylene oxide (hereinafter abbreviated as EO) is continued in the presence of a non-nucleophilic basic catalyst, or a DMC catalyst and / or a non-nucleophilic basic catalyst is subsequently added. After the addition of PO and EO in the presence, EO is ring-opened in the presence of a non-nucleophilic basic catalyst. In any case, in the production method of the present invention, at least 1 in the molecule, with or without the ring-opening addition of PO and EO in the presence of a DMC catalyst and / or a non-nucleophilic basic catalyst in the middle. To an initiator having one hydroxyl group, PO is first subjected to ring-opening addition in the presence of a DMC catalyst, and then EO is subjected to ring-opening addition in the presence of a non-nucleophilic basic catalyst.

  As the non-nucleophilic basic catalyst, an alkali metal non-nucleophilic basic catalyst having a bulky alkyl group can be used. Specifically, alkali metal isopropoxide, alkali metal tert-butoxide, alkali metal 1-adamantoxide, One or more selected from alkali metal 2,4, α-triphenylbenzyl oxide and alkali metal triphenylmethoxide can be used.

  As other non-nucleophilic basic catalysts, one or more selected from triethylamine, N, N-diisopropylethylamine and diazabicycloundecene can be used.

  Among non-nucleophilic basic catalysts, N, N-diisopropylethylamine, diazabicycloundecene and the like are exemplified as those having a pKa of the conjugate acid around 10 to 13, but these are weakly basic. It is preferable to add a polar substance such as hexamethylphosphoric triamide and / or dimethyl sulfoxide.

  Among the non-nucleophilic basic catalysts, those having a pKa of the conjugate acid around 35-40 include lithium diisopropylamide, sodium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, lithium tetramethylpiperidide. These are not preferred because they are extremely basic and difficult to control the reaction. However, only lithium diisopropylamide can be used.

  Further, as a non-nucleophilic basic catalyst having a pKa of conjugate acid of around 17, potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium 1-adamantoxide, sodium 1-adamantoxide, sodium 2,4 , Α-triphenylbenzyl oxide, potassium 2,4, α-triphenylbenzyl oxide, lithium 2,4, α-triphenylbenzyl oxide, sodium triphenyl methoxide, potassium triphenyl methoxide, lithium triphenyl methoxide, etc. These are preferable as non-nucleophilic basic catalysts because of their favorable basic and strong basicity.

  Among non-nucleophilic basic catalysts in which the pKa of the conjugate acid is around 17, potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium 1-adamantoxide, sodium 1-adamantoxide and lithium 1-adamant One or two or more selected from xoxides are more preferable in terms of cost.

  An initiator having at least one hydroxyl group in the molecule is subjected to ring-opening addition of PO in the presence of a DMC catalyst, followed by PO and EO in the presence of a DMC catalyst and a non-nucleophilic basic catalyst as described above. If EO is further subjected to ring-opening addition in the presence of a non-nucleophilic basic catalyst with or without ring-opening addition, the terminal hydroxyl group primary ratio is 60 to 100% and the polystyrene-equivalent number average molecular weight is 2000. A polyether having ˜20000 and an unsaturation degree of 0.10 or less can be obtained. Among these, polyethers having a terminal hydroxyl group primary conversion ratio of 70 to 100%, polystyrene-equivalent number average molecular weight of 3000 to 15000 and unsaturation degree of 0.05 or less are preferred, and polystyrene-equivalent molecular weight distribution (mass average) A polyether having a ratio of molecular weight Mw / number average molecular weight Mn (hereinafter the same) is preferably 1.15 to 1.00. These polyethers can be arbitrarily obtained by setting reaction conditions.

  As in the conventional method described above, even if an initiator having at least one hydroxyl group in the molecule is subjected to ring-opening addition of PO in the presence of a DMC catalyst and subsequently ring-opening addition of EO, EO Almost no ring-opening addition is carried out, and the primary hydroxylation rate of the terminal polyether of the obtained polyether is hardly changed.

  Further, after ring-opening addition of PO to an initiator having at least one hydroxyl group in the molecule in the presence of a DMC catalyst, the DMC catalyst is removed using an adsorbent, and an alkali such as potassium hydroxide is newly added. Even when a metal catalyst is added and EO is subjected to ring-opening addition, only a cloudy polyether having a low primary hydroxyl group-termination rate can be obtained. The reason is that an alkali metal catalyst such as potassium hydroxide is a basic catalyst with strong nucleophilicity, and as a result, a nucleophilic attack on the cationic terminal carbon is carried out to pull out water molecules. It appears that ring-opening addition of EO to the compound cannot be performed.

  In the production method of the present invention, a non-nucleophilic basic catalyst having a correspondingly strong basicity is used, so that a nucleophilic attack on the cationic terminal carbon does not occur, and the above side reaction of drawing water is suppressed. It is considered that the production of high molecular weight polyethylene glycol by water can be suppressed, and as a result, only the terminal oxygen atom is activated and EO ring-opening addition occurs as in the initial stage.

  In the production method of the present invention, as described above, PO can be ring-opened and added in the presence of a DMC catalyst, and a non-nucleophilic basic catalyst can be added as it is, and EO can be ring-opened and added in the presence thereof. After the ring-opening addition of PO, the DMC catalyst can be removed by, for example, adsorbent treatment, and then a non-nucleophilic basic catalyst can be added to ring-add the EO in the presence thereof.

  In the production method of the present invention, as described above, PO is subjected to ring-opening addition in the presence of a DMC catalyst, PO and EO are subsequently subjected to random ring-opening addition, and a non-nucleophilic basic catalyst is further added as it is. In the presence of EO, ring-opening addition can also be carried out. However, after ring-opening addition of PO, the DMC catalyst is removed by, for example, adsorbent treatment, and then a non-nucleophilic basic catalyst is added to the presence of the EO. PO and EO can be randomly ring-opened and added, and EO can be further ring-opened and added as it is.

  The polyether obtained by the production method of the present invention obtains a polyurethane resin by reacting a polyol component, a polyisocyanate component such as diphenylmethane diisocyanate polyisocyanate or tolylene diisocyanate polyisocyanate, and a crosslinking agent in the presence of a catalyst. It is useful as a polyol component.

  When a polyurethane resin is obtained using the polyether obtained by the production method of the present invention, a non-vegetable oil-based (that is, petrochemical-derived) polyol such as polyether, polyester, polyacetal, polycarbonate, polyester ether is optionally used. , Polyester carbonate, polythioether, polyamide, polyester amide, polysiloxane, polybutadiene, and polyacetone can be used in combination.

  According to the production method of the present invention, it is possible to produce a polyether having a high terminal hydroxyl group primary ratio and a low degree of unsaturation, and give good moldability to a resin modified using such a polyether. The molded product obtained from the above has an effect of giving good physical properties in strength, elongation, water resistance and the like.

  Examples of the present invention will be described below in order to clarify the structure and effects of the production method of the present invention, but the present invention is not limited to these examples. In the following examples and the like, unless otherwise indicated, parts represent parts by mass and% represents mass%.

Test Category 1 (Manufacturing DMC catalyst)
In a 500 ml flask, potassium hexacyanocobaltate (K ₃ Co (CN)) was added to a first aqueous solution consisting of 10.2 g of zinc chloride, 10 g of distilled water and 10 g of tert-butyl alcohol and kept at 50 ° C. ₆ ) A second aqueous solution consisting of 4.2 g, 70 g of distilled water and 10 g of tert-butyl alcohol was added dropwise over 30 minutes. After completion of dropping, a mixture of 80 g of tert-butyl alcohol and 80 g of distilled water was added to obtain a reaction solution containing 38.5% by mass of tert-butyl alcohol. The reaction solution was heated to 70 ° C., stirred for 90 minutes and aged, and then filtered under pressure (196 kPa) under pressure. To the obtained cake, 40 g of tert-butyl alcohol and 70 g of distilled water were added and redispersed. After washing at room temperature (20 ° C., hereinafter the same) for 30 minutes, washing was performed, followed by pressure filtration as described above. . Further, 100 g of tert-butyl alcohol was added to the obtained cake for redispersion, and the mixture was stirred at room temperature for 30 minutes, and then pressure filtered as described above. The obtained cake was dried under reduced pressure at 50 ° C. for 3 hours and pulverized to obtain a DMC catalyst.

Test category 2 (polyether synthesis)
Example 1 (Synthesis of polyether (P-1))
As an initiator, 2040 g (2.0 mol, hydroxyl value 165, molecular weight 1000) of glycerin PO ring-opening adduct was charged into an autoclave together with 0.51 g of the DMC catalyst produced in Test Category 1, and after nitrogen substitution, the temperature was raised to 120 ° C. Then, 152 g (2.62 mol, molecular weight 58.1) of PO was added to activate the DMC catalyst. Thereafter, PO was gradually added while maintaining the inside of the autoclave at 130 ° C., and 2642.6 g (45.5 mol) of PO was added in total to obtain glycerin polyether polyol (hydroxyl value 70.3 mg KOH / g). It was. After aging while maintaining the temperature in the autoclave at 120 ° C., the same temperature was maintained, and the pressure in the autoclave was reduced for 2 hours to completely remove volatiles. Next, the temperature in the autoclave is cooled to 80 ° C., and 34.7 g (0.31 mol, molecular weight 112.2) of potassium tert-butoxide is charged as a non-nucleophilic basic catalyst while maintaining the temperature in the autoclave at 120 ° C. Gradually, 793.8 g (18 mol, molecular weight 44.1) of EO was added and aged at 130 ° C. for 2 hours. The obtained polyether had a hydroxyl value of 55.8 mgKOH / g, a molecular weight distribution (Mw / Mn) of 1.05, an unsaturation degree of 0.005 meq / g, and a terminal hydroxyl group primary conversion of 87%. .

Examples 2 to 5 (Synthesis of polyethers (P-2) to (P-5))
Polyethers (P-2) to (P-5) of Examples 2 to 5 were synthesized in the same manner as the polyether (P-1) of Example 1. The contents of the polyethers synthesized in the above examples are summarized in Tables 1 and 4.

Example 6 (Synthesis of Polyether (P-6))
As an initiator, 2040 g (2.0 mol, hydroxyl value 165, molecular weight 1000) of glycerin PO ring-opening adduct was charged into an autoclave together with 0.48 g of the DMC catalyst produced in Test Category 1, and after nitrogen substitution, the temperature was raised to 120 ° C. Then, 152 g (2.6 mol, molecular weight 58.1) of PO was added to activate the DMC catalyst. Thereafter, PO was gradually added while maintaining the inside of the autoclave at 130 ° C., and 9841.2 g (169.4 mol) of PO was added in total to obtain a glycerin polyether polyol (hydroxyl value 28.0 mgKOH / g). It was. After aging while maintaining the temperature in the autoclave at 120 ° C., the DMC catalyst was adsorbed and removed by adsorbent treatment. After removing the adsorbent, the glycerol polyether polyol was charged again into the autoclave, and 61.0 g (0.35 mol, molecular weight 174.2) of sodium 1-adamantoxide was added as a non-nucleophilic basic catalyst, and the inside of the autoclave was added. While maintaining the temperature at 120 ° C., 2000 g (45.4 mol, molecular weight 44.1) of EO was gradually added, followed by aging at 130 ° C. for 2 hours. The polyether obtained had a hydroxyl value of 24.1 mgKOH / g, a polystyrene-equivalent number average molecular weight of 7000, a molecular weight distribution (Mw / Mn) of 1.04, an unsaturation of 0.010 meq / g, and a terminal hydroxyl group. The primary conversion rate was 91%.

Examples 7 to 11 (Synthesis of polyethers (P-7) to (P-11))
Polyethers (P-7) to (P-11) of Examples 7 to 11 were synthesized in the same manner as the polyether (P-6) of Example 6. The contents of the polyethers synthesized in the above examples are summarized in Tables 1 and 4.

Example 12 (Synthesis of Polyether (P-12))
As an initiator, 900 g (0.90 mol, hydroxyl value 165, molecular weight 1000) of glycerin PO ring-opening adduct was charged into an autoclave together with 0.60 g of the DMC catalyst produced in Test Category 1, and after nitrogen substitution, the temperature was raised to 120 ° C. Then, 152 g (2.62 mol, molecular weight 58.1) of PO was added to activate the DMC catalyst. Thereafter, PO was gradually added while maintaining the inside of the autoclave at 130 ° C., 3517 g (60.5 mol) of PO was added in total, and the mixture was aged at 130 ° C. for 2 hours. After completion of the aging, 207 g (4.7 mol, molecular weight 44.1) of EO and 830 g (14.3 mol) of PO and 830 g (14.3 mol) of PO were gradually added while maintaining the inside of the autoclave at 130 ° C., and glycerin polyether polyol ( A hydroxyl value of 26.7 mgKOH / g) was obtained. After aging while maintaining the temperature in the autoclave at 120 ° C., the same temperature was maintained, and the pressure in the autoclave was reduced for 2 hours to completely remove volatiles. Next, the temperature in the autoclave is cooled to 80 ° C., 14 g (0.12 mol, molecular weight 112.2) of potassium tert-butoxide is charged as a non-nucleophilic basic catalyst, and the autoclave is gradually kept at 120 ° C. 828 g (18.8 mol) of EO was added and aged at 130 ° C. for 2 hours. The obtained polyether had a hydroxyl value of 23.2 mgKOH / g, a molecular weight distribution (Mw / Mn) of 1.11, an unsaturation of 0.012 meq / g, and a terminal hydroxyl group primary conversion of 77%. .

Example 13 (Synthesis of Polyether (P-13))
As an initiator, 900 g (0.90 mol, hydroxyl value 165, molecular weight 1000) of glycerin PO ring-opening adduct was charged into an autoclave together with 0.60 g of the DMC catalyst produced in Test Category 1, and after nitrogen substitution, the temperature was raised to 120 ° C. Then, 152 g (2.62 mol, molecular weight 58.1) of PO was added to activate the DMC catalyst. Thereafter, PO was gradually added while maintaining the inside of the autoclave at 130 ° C., and 3932 g (67.7 mol) of PO was added in total to obtain a glycerin polyether polyol (hydroxyl value: 30.0 mgKOH / g). After aging while maintaining the temperature in the autoclave at 120 ° C., the same temperature was maintained, and the pressure in the autoclave was reduced for 2 hours to completely remove volatiles. Next, the temperature in the autoclave is cooled to 80 ° C., 14 g (0.12 mol, molecular weight 112.2) of potassium tert-butoxide is charged as a non-nucleophilic basic catalyst, and the autoclave is gradually kept at 120 ° C. 630 g (14.3 mol, molecular weight 44.1) of EO and 415 g (7.1 mol) of PO were randomly added and aged at 130 ° C. for 2 hours. Next, 405 g (9.2 mol) of EO was gradually added while maintaining the inside of the autoclave at 120 ° C., and aged at 130 ° C. for 2 hours. The obtained polyether had a hydroxyl value of 25.0 mgKOH / g, a molecular weight distribution (Mw / Mn) of 1.06, an unsaturation of 0.014 meq / g, and a terminal hydroxyl group primary conversion of 62%. .

Examples 14 and 15 (Synthesis of polyethers (P-14) and (P-15))
The polyethers (P-14) and (P-15) of Examples 14 and 15 were synthesized in the same manner as the polyether (P-13) of Example 13. The contents of the polyethers synthesized in the above examples are summarized in Tables 2 to 4.

In Tables 1 to 4,
Hydroxyl value: measured by a method based on JIS-K1557-1.
Number average molecular weight (Mn): number average molecular weight in terms of polystyrene by GPC Molecular weight distribution (Mw / Mn): ratio of mass average molecular weight in terms of polystyrene by GPC / number average molecular weight in terms of polystyrene by GPC Unsaturation degree: JIS-K1557- It was measured by the method based on 3.
Primary hydroxyl ratio of terminal hydroxyl group: Calculated from the amount of terminal hydroxyl group lost by esterification with trifluoroacetic acid.

A-1: Ring-opening addition of PO to glycerin (manufactured by Takemoto Yushi Co., Ltd., number average molecular weight (Mn) 1000, hydroxyl value 168)
A-2: Trimethylolpropane with ring-opening addition of PO (manufactured by Takemoto Yushi Co., Ltd., number average molecular weight (Mn) 1000, hydroxyl value 169)
A-3: PO and EO randomly added at a ratio of PO / EO = 50/50 (mass ratio) to glycerin (manufactured by Takemoto Yushi Co., Ltd., number average molecular weight (Mn) 800, hydroxyl value 210)
A-4: Ring-opening addition of PO to propylene glycol (manufactured by Takemoto Yushi Co., Ltd., number average molecular weight (Mn) 1200, hydroxyl value 93)
A-5: EO ring-opening addition to ethylene glycol (manufactured by Takemoto Yushi Co., Ltd., number average molecular weight (Mn) 1000, hydroxyl value 112)
A-6: Ring-opening addition of PO to lauryl alcohol (manufactured by Takemoto Yushi Co., Ltd., number average molecular weight (Mn) 800, hydroxyl value 70)

B-1: Potassium tert-butoxide (Wako Pure Chemical Industries, Ltd.)
B-2: Dispersion in which N, N-diisopropylethylamine (manufactured by Tokyo Chemical Industry Co., Ltd., primary product) is dispersed in dimethyl sulfoxide (reagent grade) (effective concentration 20%)
B-3: 1-adamantanol (manufactured by Hychem) reacted with sodium metal B-4: tert-butyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., primary product) reacted with sodium hydride B- 5: 1-adamantanol (manufactured by Hichem) reacted with metal potassium * 1: The DMC catalyst at the time of PO ring-opening addition was used as it was.
* 2: Non-nucleophilic basic catalyst B-1 at the time of PO and EO ring-opening addition was used as it was.

Test category 3 (Evaluation of polyether)
Evaluation Example 1
Production and Evaluation of Polyurethane Resin for Synthetic Leather A urethane solution mixed according to the formulation described in Table 5 was put in a cup and polymerized while removing the solvent in a vacuum dryer. The obtained polyurethane resin was cut into a predetermined size, its tensile strength and elongation were measured with a universal testing machine, and the results are summarized in Table 5.

In Table 5,
P-8, P-11 to P-15: Polyethers described in Tables 1 to 4 G-1: EO and PO in ethylene glycol in the presence of a potassium hydroxide catalyst EO / PO = 30/70 (mass ratio) ) And a number average obtained by randomly opening and adding EO and PO at a ratio of EO / PO = 30/70 (mass ratio) in the presence of a DMC catalyst. Polyether having a molecular weight of 4000 and a terminal hydroxyl group primary conversion of 26%.
G-2: A polyether obtained by ring-opening addition of PO to propylene glycol in the presence of a potassium hydroxide catalyst having a number average molecular weight of 4000, a terminal hydroxyl group primary conversion of 2%, and an unsaturation degree of 0.17.

  As is clear from the results in Table 5, with respect to Test Examples 7 and 8 using the polyether (G-1, G-2) obtained by the conventional method, the terminal obtained by the production method of the present invention was used. In Test Examples 1 to 6 using polyethers (P-8 and P-11 to P-15) having a high hydroxyl primary ratio and a low degree of unsaturation, polyurethane resins having excellent tensile strength and elongation are obtained. It has been.

Evaluation example 2
Manufacture and evaluation of polyether for sealant The urethane solution mixed by the formulation described in Table 6 is put in a cup, cured at room temperature described in Table 6, and the polyurethane resin obtained is cut into a predetermined size, Tensile strength was measured with a universal testing machine. On the other hand, after the same polyurethane resin was allowed to stand at a temperature of 150 ° C. and a humidity of 95% for 7 days, its tensile strength was measured in the same manner. The tensile strength retention rate (%) indicating how much the tensile strength is retained was determined as compared with the tensile strength immediately after. The results are summarized in Table 6. The curing time of the urethane solution was measured by a method according to JIS-K6401.

In Table 6,
P-1, P-5, P-12 to P-15: Polyethers described in Tables 1 to 4 G-3: Number average molecular weight obtained by ring-opening addition of PO to ethylene glycol in the presence of a potassium hydroxide catalyst 1000 is used as an initiator, and PO is subjected to ring-opening addition in the presence of a DMC catalyst, and EO is further subjected to ring-opening addition in the presence of a potassium hydroxide catalyst. The number average molecular weight is 2800, and terminal hydroxyl groups are primaryized. Polyether with a rate of 38%.
G-4: Number average molecular weight obtained by ring-opening addition of PO to ethylene glycol in the presence of a potassium hydroxide catalyst having a number average molecular weight of 1000, and PO by ring-opening addition in the presence of a DMC catalyst Is a polyether having a terminal hydroxyl group primary ratio of 1% or less.

  As is apparent from the results in Table 6, terminal hydroxyl groups obtained by the production method of the present invention were compared with Test Examples 15 and 16 using polyethers (G-3, G-4) obtained by the conventional method. In Test Examples 9 to 14 using polyethers (P-1, P-5 and P-12 to P-15) having a high degree of primary conversion and low unsaturation, the curing time was short and the water resistance was high. An excellent polyurethane resin is obtained.

Claims (8)

  Propylene oxide is subjected to ring-opening addition in the presence of a double metal cyanide catalyst to an initiator having at least one hydroxyl group in the molecule, followed by ring-opening addition of ethylene oxide in the presence of a non-nucleophilic basic catalyst. A method for producing a polyether comprising obtaining a polyether having a terminal hydroxyl group primary ratio of 60 to 100%, a polystyrene-equivalent number average molecular weight of 2000 to 20000, and an unsaturation degree of 0.10 or less.   Propylene oxide is subjected to ring-opening addition to an initiator having at least one hydroxyl group in the molecule in the presence of a double metal cyanide catalyst, and subsequently in the presence of a double metal cyanide catalyst and / or a non-nucleophilic basic catalyst. Propylene oxide and ethylene oxide are randomly subjected to ring-opening addition, and then ethylene oxide is further subjected to ring-opening addition in the presence of a non-nucleophilic basic catalyst, so that the terminal hydroxyl group primary ratio is 60 to 100% in terms of polystyrene. A method for producing a polyether, comprising obtaining a polyether having a number average molecular weight of 2,000 to 20,000 and an unsaturation degree of 0.10 or less.   The non-nucleophilic basic catalyst is one or more selected from alkali metal tert-butoxide, alkali metal 1-adamantoxide, alkali metal 2,4, α-triphenylbenzyl oxide and alkali metal triphenylmethoxide. A method for producing a polyether according to claim 1 or 2.   The non-nucleophilic basic catalyst is one or more selected from potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium 1-adamantoxide, sodium 1-adamantoxide and lithium 1-adamantoxide A method for producing a polyether according to claim 1 or 2.   The method for producing a polyether according to claim 1 or 2, wherein the non-nucleophilic basic catalyst is one or more selected from triethylamine, N, N-diisopropylethylamine and diazabicycloundecene.   The polyether according to claim 1 or 2, wherein the non-nucleophilic basic catalyst is a product obtained by adding hexamethylphosphoric triamide and / or dimethyl sulfoxide to N, N-diisopropylethylamine and / or diazabicycloundecene. Method.   The method for producing a polyether according to any one of claims 1 to 6, wherein a polyether having a polystyrene-equivalent molecular weight distribution (Mw / Mn) of 1.15 to 1.00 is obtained.   8. The polyether according to claim 1, wherein a polyether having a terminal hydroxyl group primary ratio of 70 to 100%, a polystyrene-equivalent number average molecular weight of 3000 to 15000 and an unsaturation degree of 0.05 or less is obtained. A method for producing a polyether.