KR20100062031A - Polyols catalyzed by double-metal cyanide or multi-metal cynide complexes in new organic complexing reagents via ring-opening polymerization of propylene oxide - Google Patents

Abstract

PURPOSE: A method for manufacturing polyols is provided to simplify a manufacturing process using double-metal cyanide catalysts or multi-metal cyanide catalyst and to obtain a short induction time and very high activity due to very fast polymerization activation when an epoxy monomer is ring-opened. CONSTITUTION: A method for manufacturing polyols comprises a step of manufacturing the polyol by heating epoxide under a catalyst including double-metal cyanide or multi-metal cyanide compound, a lactate-based compound, and a polyether compound. The lactate-based compound is shown as a chemical formula 1. The chemical formula 1 is R_1COOC(H)_n(OH)R_2R_3. In the chemical formula 1, R_1 is an aryl group, an alkyl group of C1-C20, or a group including R_4-NH-.

Description

Polyols catalyzed by double-metal cyanide or multi-metal cynide complexes in new organic complexing using a double metal cyanide catalyst or a multimetal cyanide catalyst synthesized using a new organic complexing agent reagents via ring-opening polymerization of propylene oxide}

The present invention relates to a highly active double metal cyan salt (DMC) catalyst or a multi-metal cyan salt (MMC) catalyst, and more particularly, to a double metal cyan salt (DMC) using a lactate-based compound as a complexing agent. A catalyst or a multimetal cyanide salt (MMC) catalyst and a polyol manufacturing process using the same.

Double metal cyanide salts ("DMC") or multimetal cyanide salts (hereinafter "MMC") complexes are well known as catalysts useful for ring-opening polymerization of epoxide monomers. These catalysts can be used to make many polymer products, such as polyethers, polyesters and polyetherester polyols having a low degree of unsaturation compared to polyols prepared using KOH catalysts. These polymer products can be used to make polyurethane coatings, elastomers, sealants, foaming agents and adhesives.

Conventional patented DMC catalysts are generally made by reacting a metal salt with a metal cyan salt in an aqueous solution to form a precipitate of the DMC compound. Generally low molecular weight complexing agents such as ethers, alcohols are used to prepare the catalyst. Ketones, esters, amides and ureas are also used as complexing agents.

See U. S. Pat. In No. 4,477,589, 3,821,505, 5,158,922, glyme (or dimethoxyethane) has traditionally been used as a complexing agent, which has a catalyst content of 0.1 ppm at 100 ppm based on the amount of polyether finally used at 105 ° C. It has an activity of about 0.5 kg-PO / g-Co min. More recently, water-soluble aliphatic alcohols such as tertiary butyl alcohol have been used as complexes to further increase the activity of the catalyst (U.S. Pat. No. 5,780,584). However, when these catalysts are used to polymerize epoxides such as propylene oxide, there is a drawback that the induction time for the catalyst to be activated is long, which takes 4 hours or more.

In addition, a DMC catalyst containing about 5 to 80 wt% of the catalyst using a polyether (US Pat. No. 5,482,908) having a number average molecular weight of 500 or more or a polyether (US Pat. No. 5,789,626) of 500 or less as a complexing agent It was invented to increase activity. The catalyst containing the organic complexing agent (tertiary butyl alcohol) and the polyether polyol is at a rate of at least 2 kg-PO / g-Co / min with a catalyst amount of 100 ppm based on the amount of polyether finally used at 105 ° C. Propylene oxide can be polymerized. In this case, the induction time is more than 3 hours. Induction time is the time at which the catalyst is activated so that no polymerization occurs at this time. Therefore, a long induction time has a disadvantage of low productivity. In addition, since the synthesis process is too cumbersome and takes a long time to show catalytic activity when synthesizing DMC or MMC catalyst, not only the efficiency is lowered, but also the organic complexing agent used is toxic and adversely affects the environment due to the excessive use in the preparation of the catalyst. It's crazy. In case of DMC or MMC catalyst using various organic complexing agents in the existing patent, it shows very long induction time of about 3 hours, and when ring-opening polymerization reaction occurs, it shows very high activity of catalyst during the reaction. Even higher risks are associated with commercial use.

It is an object of the present invention to provide a process for preparing polyols using solid double or multiple metal cyanide with new complexing agents.

Another object of the present invention is to provide a solid double or multiple metal cyanide catalyst using a novel complexing agent.

It is yet another object of the present invention to provide a process for preparing solid double or multiple metal cyanide catalysts using new complexing agents.

Another object of the present invention is to prepare polyols using new metal double or multi metal cyanide catalysts.

For the above purpose, the present invention

Double metal cyanide or multi metal cyanide compounds; Lactate compounds; Optionally in the presence of a catalyst comprising a polyether compound, the process comprises heating the epoxide to produce a polyol.

In the present invention, the DMC and MMC catalyst compounds are reaction products of metal salts soluble in water and metal cyan salts soluble in water. Metal salts soluble in water preferably have the general formula of M (X) _n .

Where M is Zn (II), Fe (II), Ni (II), Mn (II), Co (II), Sn (II), Pb (II), Fe (III), Mo (IV), Mo (VI), Al (II), V (V), V (IV), Sr (II), W (IV), W (VI), Cu (II), Cr (III). Among them, Zn (II), Fe (II), Co (II), Ni (II) and the like are more suitable. X is a halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate It is an anion selected from carboxylate and nitrate. The value of n is 1 to 3 and satisfies the valence of M. Examples of suitable metal salts are zinc chloride, zinc bromide, zinc acetate, zinc acetonylacetonate, zinc benzoate, zinc nitrate, iron bromide (II), cobalt chloride (II), cobalt thiocyanate (II), formic acid Compounds such as nickel (II), nickel nitrate (II) and the like.

Metal cyanide salts soluble in water used to prepare DMC cyanide compounds generally have the structural formula (Y) _a M '(CN) _b (A) _c . M 'is Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), Ir (III), Ni ( II), Rh (III), Ru (II), V (V), V (IV) and the like. Among these, Co (II), Co (III), Fe (II), Fe (III), Cr (III), Ir (III), and Ni (II) are more suitable. Metal cyanide salts that are soluble in water may contain one or more of these metals. Y is an alkali metal ion or an alkaline metal ion. A is an ion selected from halides, hydroxides, sulfates, carbonates, cyanates, oxalates, thiocyanates, isocyanates, isothiocyanates, carboxylates, nitrates and the like. a and b are integers greater than one. The sum of the charges a, b and c balances the M 'charge.

Suitable metal cyanide salts which are soluble in water are potassium hexacyanocobaltate (III), potassium hexacyanoperate (II), potassium hexacyanoperate (III), calcium hexacyanocobaltate (III), and lithium hexa Cyanoiridate (III) and the like, but are not limited thereto.

Examples of MMC catalyst compounds used in the present invention include zinc hexacyanocobaltate (III) hexacyanoperate (III) and zinc hexacyanocobaltate (III) hexacyanoperate composed of Zn, Co, Fe. And (II). In addition, examples of the DMC catalyst include zinc hexacyanocobaltate (III), zinc hexacyanoperate (III), nickel (II) hexacyanoperate (II), and cobalt (II) hexacyanocobaltate ( III), and examples of DMC catalysts are described in US Pat. No. 5,158,922 is shown well, among which zinc hexacyanocobaltate (III) is the most preferred DMC catalyst compound.

In the present invention, the lactate compound is an organic complexing agent, and means a lactate compound having both an ester and an alcohol group. In the present invention, the lactate compound may be represented by the following formula (I),

R ₁ COOC (H) n (OH) R ₂ R ₃ (I)

Wherein R ₁ represents H, an aryl group, a C ₁ -C ₂₀ alkyl group, or a group containing R ₄ -NH-,

In the case of R ₂ , R ₃ , H, C ₁ -C ₂₀ alkyl group, R ₄ -NH- group, -R ₆ -C (O) OR ₇ group, or cyanide Group,

Wherein R 4 comprises H, C ₁ -C ₂₀ alkyl groups, R 6 comprises C ₂ -C ₁₅ alkylene groups or substituted alkylene groups, and in the case of R ₇ Is H, a C ₁ -C ₂₀ alkyl group, or a substituted alkyl group, n is 0 or 1. Examples include a wide range of acetate (CH ₃ COO-) groups or propionate (CH ₃ CH ₂ COO-) groups, butyrate (CH ₃ CH ₂ CH ₂ COO-) groups, and the like. A few simple cases are methyl acetate, ethyl acetate, propyl acetate, propyl acetate, isopropyl acetate, amyl acetate, and isoamyl acetate. , Methylamyl acetate, 2-ethylbutyl acetate, 2-ethylbutyl acetate, ethyleneglycol monoacetate, ethyleneglycol diacetate, ethylenetriol acetate, ethylenetriol acetate Examples include methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, and butyl butyrate. Can be. In the present invention, a particularly preferred kind may be referred to as a lactate-based compound species having both ester and alcohol groups. Some simple compounds are methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, and isobutyl lactate. (Isobutyl lactate), amyl lactate, isoamyl lactate, hexyl lactate, 2-ethyl butyl lactate, 2-ethylhexyl lactate It can be called all kinds of lactate species such as (2-ethyl hexyl lactate).

In a preferred embodiment of the present invention, the lactate compound is ethyl lactate, which is advantageous in terms of price, performance, and environment. Lactate-based compounds include both lactate-based compounds and mixtures of all the lactate-based compounds and all organic complexing agents in the prior patents, including only one or more lactate-based compounds. Particularly preferred lactate compound species in the present invention is ethyl lactate, which is almost non-toxic and can be used as a food additive, which is harmless to the human body, and is also inexpensive, thus making it the most preferred tertiary butyl alcohol. It is a much more suitable organic solvent than.

The organic complexing agent of the prior patent is U.S. Pat. Nos. 3,278,457, 3,278,459, 3,289,505, 3,427,256, 4,477,589, 5,158,922, 5,470,813, 5,482,908, 5,545,601, 5,627,122, 6,423,662 WO 01/04180, WO 02/09875. The complexing agent that can be used in combination with the lactate compound is disclosed as an organic compound containing a hetero atom that is soluble in water that can be mixed with the DMC catalyst compound, for example. Suitable complexing agents include alcohols, aldehydes, ketones, ethers, esters, amides, urea, nitriles, sulfates and mixtures thereof. When synthesizing the existing DMC or MMC catalyst, ether complexes such as dimethoxy ethane and diglyme or water-soluble aliphatic alcohols were preferred as organic complexing agents. Among them, alcohols that are well soluble in water such as ethanol, isopropanol, normal butanol, isobutanol, sec-butanol, and tert-butanol are more suitable. In particular, tertiary alcohol is most suitable and widely used to make DMC or MMC catalyst compound.

In the present invention, the lactate compound is used in an amount in the range of 1 to 80% by weight, more preferably 1 to 60% by weight, most preferably 1 to 30% by weight based on the DMC catalyst or MMC catalyst. desirable. When the amount of the lactate compound is too small, there is a problem that the activity of the catalyst is lowered, and when the amount of the lactate compound is high, there may be a problem in drying during the catalyst preparation process.

In the present invention, the polyether compound is a compound selectively used to improve the reactivity of the catalyst, it contains about 5 to 80 wt% in the total catalyst, more preferably 10 to 70 wt%, most preferably Is contained 20 to 50 wt%. When the polyether compound is less than 5 wt%, the activity difference of the catalyst is not large compared to the catalyst made without polyether, and when the polyether content is 80 wt% or more, the effect of improving the activity of the catalyst is not large, and generally It is hard to store and use because it is not sticky solid but sticky dough.

The polyether may be those produced by ring-opening polymerization of a cyclic ether compound, low molecular weight epoxy polymers, oxetane polymers, and the like, and these polymers may be prepared by various methods. The terminal groups of these polymers may be hydroxyl groups, amine groups, ester groups, ether groups and the like.

In the present invention, it is preferable that the polyether compound uses a polyether polyol so as to induce the activation of polymerization at a rapid rate, so that the induction time is very short. Particularly suitable polyethers have a hydroxyl functionality. It is a polyether polyol which has about 1-8. Useful polyether polyols include poly (propylene glycol), poly (ethylene glycol), EO-capped poly (oxypropylene) polyols, EO-PO polyols, butylene oxide polymers and copolymers thereof. Although molecular weights are higher than those listed above, hyper-branched polyols (molecular weight of 500 or more) and their copolymers with hydroxyl groups are also available as complexing agents.

In the present invention, the polyether compound preferably has a number average molecular weight of 500 or more, it is best for the PEO- b -PPO- b -PEO as organic complexing agent used with the lactate-based compound.

The polyol preparation process according to the invention has a significantly shorter induction time than most conventional DMC or MMC catalysts. DMC catalyst that uses polyether complexing agent and lactate compound at the same time than DMC catalyst which does not use poly (ethylene glycol) -Block -polyether complexing agent but only lactate compound as organic complexing agent In the case of high polymerization activity was confirmed. In particular, there is an advantage that the induction time required to activate the polymerization is shortened from 3 hours to 30 minutes or less.

In the polyether polyol products produced at low catalyst concentrations, the presence of the catalyst does not significantly affect the quality of the product. In practice, the remaining amounts of Zn and Co in the polyols produced by the catalysts invented are less than 5 ppm each prior to the purification of the polyols.

When the purity of the product needs to be high, simple filtration can be used to remove trace catalyst from the polyol product. This is because the catalyst is present in the product in a heterogeneous state. In general, most commercial polyether polyols produced by conventional KOH catalysts require a catalyst removal step, so it is an important advantage to be able to omit this process in the polyols.

The present invention is, in one aspect, a method for producing a catalyst for polyol production using epoxide, characterized in that the aqueous solution of the metal salt and metal cyan salt is optionally mixed with a lactate compound containing a polyether compound to react.

In the practice of the present invention, the metal salt and the metal cyan salt are mixed with the lactate-based complexing agent and the polyether-based depositing agent in the catalyst manufacturing process. Metal salts are used in excess here. A catalyst slurry containing a reaction product of a metal salt and a metal cyan salt is obtained, the slurry containing excess metal salt, water and an organic complexing agent. The solid catalyst containing the lactate-based complexing agent and the polyether-based complexing agent is separated from the catalyst slurry by filtration or centrifugation.

The solid catalyst containing the separated primary and secondary organic complexing agents is washed with an aqueous solution containing the organic complexing agent. The catalyst is separated and immediately mixed and washed with an aqueous solution containing an organic complexing agent. Impurities are removed from the catalyst in the cleaning step. For example, the catalyst will not be active unless KCl is completely removed. The amount of organic complexing agent in the aqueous phase is preferably in the range of about 40-70 wt%. The addition of a small amount (0.1 ~ 0.8 wt%) of the polyether complexing agent in the washing solution can increase the amount of polyether complexing agent in the catalyst, generally increasing the activity of the catalyst.

The catalyst shows sufficient activity in one washing step, but washing the catalyst more than once can remove impurities completely. In the washing process, it is preferable not to use distilled water but only an organic complexing agent or a mixture of a lactate organic complexing agent and a polyether complexing agent.

The catalyst is washed and then dried under a vacuum of 26 in Hg to 30 in Hg at a temperature in the range 40 to 90 ° C. until the weight of the catalyst remains constant.

The present invention relates to a catalyst for producing a polyol using an epoxide, in one aspect, a double metal cyanide or a multimetal cyanide compound; Lactate compounds; And optionally a polyether compound.

In the present invention, the DMC or MMC cyanide catalyst using the complexing agent has a different structural tendency compared to the conventional DMC catalyst prepared using tertiary butyl alcohol and other co-complexing agents well known in the existing patent. Indicates. The DMC catalyst of the present invention shows narrow sharp lines at d-spacing of 3.76 angstroms (see Table 2 and Figure 4). On the other hand, lactate-based compounds show sharp lines at 3.76 angstroms d-spacing, but much sharper lines at 5.07 angstroms d-spacing. This diffraction trend is compared with zinc hexacyanocobaltate in the form of high crystallinity Prussian blue analogue with sharp peaks at 5.07, 3.59, 2.54 and 2.28 angstroms.

The present invention provides DMC or MMC catalysts using new complexing agents. The catalyst according to the invention is simple in the manufacturing process, low in the amount of organic complexing agent used, and environmentally friendly. In addition, when the ring-opening polymerization of the epoxy monomer using this catalyst, the polymerization activation is very fast, so the induction time or induction period is short and the activity is very high. In addition, the prepared polyol has a low viscosity, excellent transparency, significantly high molecular weight, narrow molecular weight distribution, and unsaturation level or monool content.

Hereinafter, the present invention will be described in detail through examples.

Example 1

Preparation of catalyst (DMC7G) containing ethyl lactate as main organic complexing agent and polytetramethylene ether glycol (PTMEG) [or Poly (THF)] as complexing agent

In a beaker, 16 g of zinc chloride, 69 mL of distilled water, 19.5 mL of ethyl lactate are mixed (mixed solution 1). In a second beaker 1.95 g of potassium hexacyanocobaltate is dissolved in 24 mL of distilled water (mixture 2). In a third beaker, 2.1 g of poly (THF) is dissolved in 18 mL of ethyl lactate (mixture 3). Mixing solution 2 is added dropwise to the mixing solution 1 at 50 ° C. for 1 hour while mixing using a mechanical stirrer. The mixed solution 3 is reacted for 3 minutes. After the reaction, the solid is separated using high-speed centrifugation. 30 mL of distilled water and 18 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After 1 hour of reaction, 1.05 g of Poly (THF) was dissolved in 9 mL of ethyl lactate, and the mixed solution was stirred for 3 minutes. After the reaction, the solid is separated by high-speed centrifugation. 30 mL of distilled water and 9 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After the reaction for 1 hour, 0.3 g of Poly (THF) was dissolved in 3 mL of ethyl lactate, and the mixed solution was stirred for 3 minutes. The catalyst cake thus obtained is subjected to three centrifugations using 30 mL of distilled water and 15 mL of ethyl lactate to remove remaining impurities. Finally, the catalyst cake is dried until it has a constant weight at 60 ° C. and 30 in. Hg vacuum.

Example 2

Preparation of catalyst (DMC7H) containing ethyl lactate as the main organic complexing agent and poly (propylene glycol) as the complexing agent

In a beaker, 16 g of zinc chloride, 69 mL of distilled water, 19.5 mL of ethyl lactate are mixed (mixed solution 1). In a second beaker 1.95 g of potassium hexacyanocobaltate is dissolved in 24 mL of distilled water (mixture 2). In a third beaker, 1.68 g of poly (propylene glycol) is dissolved in 18 mL of ethyl lactate (mixture 3). Mixing solution 2 is added dropwise to the mixing solution 1 at 50 ° C. for 1 hour while mixing using a mechanical stirrer. The mixed solution 3 is reacted for 3 minutes. After the reaction, the solid is separated using high-speed centrifugation. 30 mL of distilled water and 18 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After the reaction for 1 hour, 0.84 g of poly (propylene glycol) was dissolved in 9 mL of ethyl lactate, and then mixed for 3 minutes. After the reaction, the solid is separated by high-speed centrifugation. 30 mL of distilled water and 9 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After the reaction for 1 hour, 0.3 g of poly (propylene glycol) was dissolved in 3 mL of ethyl lactate, and then mixed for 3 minutes. The catalyst cake thus obtained is subjected to three centrifugations using 30 mL of distilled water and 15 mL of ethyl lactate to remove remaining impurities. Finally, the catalyst cake is dried until it has a constant weight at 60 ° C. and 30 in. Hg vacuum.

Example 3

Preparation of Catalyst (DMC7I) Containing Ethyl Lactate as Primary Organic Complexing Agent and Hyper-branched Glycerols as Secondary Organic Complexing Agent

In a beaker, 16 g of zinc chloride, 69 mL of distilled water, 19.5 mL of ethyl lactate are mixed (mixed solution 1). In a second beaker 1.95 g of potassium hexacyanocobaltate is dissolved in 24 mL of distilled water (mixture 2). In a third beaker, 1.5 g of Hyper branched glycerols are dissolved in 18 mL of ethyl lactate (mixture 3). Mixing solution 2 is added dropwise to the mixing solution 1 at 50 ° C. for 1 hour while mixing using a mechanical stirrer. The mixed solution 3 is reacted for 3 minutes. After the reaction, the solid is separated using high-speed centrifugation. 30 mL of distilled water and 18 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After 1 hour of reaction, 0.75 g of Hyper branched glycerols was dissolved in 9 mL of ethyl lactate, and stirred for 3 minutes. After the reaction, the solid is separated by high-speed centrifugation. 30 mL of distilled water and 9 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After 1 hour of reaction, 0.3 g of Hyper branched glycerols was dissolved in 3 mL of ethyl lactate, and the mixture was stirred for 3 minutes. The catalyst cake thus obtained is subjected to three centrifugations using 30 mL of distilled water and 15 mL of ethyl lactate to remove remaining impurities. Finally, the catalyst cake is dried until it has a constant weight at 60 ° C. and 30 in. Hg vacuum.

Example 4

Preparation of Block -poly catalyst (DMC7J-20a) containing (ethylene glycol) - the main organic complexing with ethyl lactate, part organic complexing agent agent (ethylene glycol) poly - Block -poly (propylene glycol)

In a beaker, 16 g of zinc chloride, 69 mL of distilled water, 19.5 mL of ethyl lactate are mixed (mixed solution 1). In a second beaker 1.95 g of potassium hexacyanocobaltate is dissolved in 24 mL of distilled water (mixture 2). In a third beaker, 1.5g of poly (ethylene glycol) - Block -Poly (propylene glycol) - Block -poly (ethylene glycol) is dissolved in the ethyl lactate in 18 mL (mixture 3). The mixed solution 2 is added dropwise to the mixed solution 1 at 50 ° C. for 1 hour while mixing using a mechanical stirrer. The mixed solution 3 is reacted for 3 minutes. After the reaction, the solid is separated using high-speed centrifugation. The catalyst cake thus obtained is subjected to three centrifugations using 30 mL of distilled water and 15 mL of ethyl lactate to remove remaining impurities. Finally, the catalyst cake is dried until it has a constant weight at 60 ° C. and 30 in. Hg vacuum.

Example 5

Preparation of Block -poly (ethylene glycol) catalyst (DMC7J-20b) comprising - a main organic complexing with ethyl lactate, part organic complexing agent agent (ethylene glycol) poly - Block -poly (propylene glycol)

In a beaker, 16 g of zinc chloride, 69 mL of distilled water, 19.5 mL of ethyl lactate are mixed (mixed solution 1). In a second beaker 1.95 g of potassium hexacyanocobaltate is dissolved in 24 mL of distilled water (mixture 2). In a third beaker, 1.5g of poly (ethylene glycol) - Block -Poly (propylene glycol) - Block -poly (ethylene glycol) is dissolved in the ethyl lactate in 18 mL (mixture 3). The mixed solution 2 is added dropwise to the mixed solution 1 at 50 ° C. for 1 hour while mixing using a mechanical stirrer. The mixed solution 3 is reacted for 3 minutes. After the reaction, the solid is separated using high-speed centrifugation. 30 mL of distilled water and 18 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After 1 hour the reaction 0.75 g of poly (ethylene glycol) - Block -Poly (propylene glycol) - Block - put a mixed solution of a poly (ethylene glycol) in 9 mL of ethyl lactate to give the mixture was stirred for 3 minutes. After the reaction, the solid is separated by high-speed centrifugation. The catalyst cake thus obtained is subjected to three centrifugations using 30 mL of distilled water and 15 mL of ethyl lactate to remove remaining impurities. Finally, the catalyst cake is dried until it has a constant weight at 60 ° C. and 30 in. Hg vacuum.

Example 6

Preparation of Block -poly (ethylene glycol) catalyst (DMC7J-20c) comprising - a main organic complexing with ethyl lactate, part organic complexing agent agent (ethylene glycol) poly - Block -poly (propylene glycol)

In a beaker, 16 g of zinc chloride, 69 mL of distilled water, 19.5 mL of ethyl lactate are mixed (mixed solution 1). In a second beaker 1.95 g of potassium hexacyanocobaltate is dissolved in 24 mL of distilled water (mixture 2). In a third beaker, 1.5g of poly (ethylene glycol) - Block -Poly (propylene glycol) - Block -poly (ethylene glycol) is dissolved in the ethyl lactate in 18 mL (mixture 3). The mixed solution 2 is added dropwise to the mixed solution 1 at 50 ° C. for 1 hour while mixing using a mechanical stirrer. The mixed solution 3 is reacted for 3 minutes. After the reaction, the solid is separated using high-speed centrifugation. 30 mL of distilled water and 18 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After 1 hour the reaction 0.75 g of poly (ethylene glycol) - Block -Poly (propylene glycol) - to put a mixed solution of the Block -poly (ethylene glycol) in 9 mL of ethyl lactate, thereby anti-T for 3 minutes. After the reaction, the solid is separated by high-speed centrifugation. 30 mL of distilled water and 9 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After 1 hour the reaction 0.3 g of poly (ethylene glycol) - Block -Poly (propylene glycol) - to put a mixed solution of the Block -poly (ethylene glycol) in 3 mL of ethyl lactate, and the mixture was stirred for 3 minutes. The catalyst cake thus obtained is subjected to three centrifugations using 30 mL of distilled water and 15 mL of ethyl lactate to remove remaining impurities. Finally, the catalyst cake is dried until it has a constant weight at 60 ° C. and 30 in. Hg vacuum.

Example 7

Preparation of Block -poly (ethylene glycol) catalyst (DMC7J-20d) comprising - a main organic complexing with ethyl lactate, part organic complexing agent agent (ethylene glycol) poly - Block -poly (propylene glycol)

In a beaker, 16 g of zinc chloride, 69 mL of distilled water, 19.5 mL of ethyl lactate are mixed (mixed solution 1). In a second beaker 1.95 g of potassium hexacyanocobaltate is dissolved in 24 mL of distilled water (mixture 2). In a third beaker, 1.5g of poly (ethylene glycol) - Block -Poly (propylene glycol) - Block -poly (ethylene glycol) is dissolved in the ethyl lactate in 18 mL (mixture 3). The mixed solution 2 is added dropwise to the mixed solution 1 at 50 ° C. for 3 hours while mixing using a mechanical stirrer. The mixed solution 3 is reacted for 3 minutes. The catalyst cake thus obtained is subjected to three centrifugations using 30 mL of distilled water and 15 mL of ethyl lactate to remove remaining impurities. Finally, the catalyst cake is dried until it has a constant weight at 60 ° C. and 30 in. Hg vacuum.

Example 8

Preparation of Block -poly (ethylene glycol) catalyst (DMC7J-10) containing - a primary organic complexing with ethyl lactate, part organic complexing agent agent (ethylene glycol) poly - Block -poly (propylene glycol)

In a beaker, 8 g of zinc chloride, 69 mL of distilled water, 19.5 mL of ethyl lactate are mixed (mixed solution 1). In a second beaker 1.95 g of potassium hexacyanocobaltate is dissolved in 24 mL of distilled water (mixture 2). In a third beaker, 1.5g of poly (ethylene glycol) - Block -Poly (propylene glycol) - Block -poly (ethylene glycol) is dissolved in the ethyl lactate in 18 mL (mixture 3). The mixed solution 2 is added dropwise to the mixed solution 1 at 50 ° C. for 1 hour while mixing using a mechanical stirrer. The mixed solution 3 is reacted for 3 minutes. After the reaction, the solid is separated using high-speed centrifugation. 30 mL of distilled water and 18 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After 1 hour the reaction 0.75 g of poly (ethylene glycol) - Block -Poly (propylene glycol) - to put a mixed solution of the Block -poly (ethylene glycol) in 9 mL of ethyl lactate, and the mixture was stirred for 3 minutes. After the reaction, the solid is separated by high-speed centrifugation. 30 mL of distilled water and 9 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After 1 hour the reaction 0.3 g of poly (ethylene glycol) - Block -Poly (propylene glycol) - to put a mixed solution of the Block -poly (ethylene glycol) in 3 mL of ethyl lactate, and the mixture was stirred for 3 minutes. The catalyst cake thus obtained is subjected to three centrifugations using 30 mL of distilled water and 15 mL of ethyl lactate to remove remaining impurities. Finally, the catalyst cake is dried until it has a constant weight at 60 ° C. and 30 in. Hg vacuum.

Example 9

Preparation of Block -poly (ethylene glycol) catalyst (DMC7J-7) comprising - a main organic complexing with ethyl lactate, part organic complexing agent agent (ethylene glycol) poly - Block -poly (propylene glycol)

In a beaker, 5.6 g of zinc chloride, 69 mL of distilled water, 19.5 mL of ethyl lactate are mixed (mixed solution 1). In a second beaker 1.95 g of potassium hexacyanocobaltate is dissolved in 24 mL of distilled water (mixture 2). In a third beaker, 1.5g of poly (ethylene glycol) - Block -Poly (propylene glycol) - Block -poly (ethylene glycol) is dissolved in the ethyl lactate in 18 mL (mixture 3). The mixed solution 2 is added dropwise to the mixed solution 1 at 50 ° C. for 1 hour while mixing using a mechanical stirrer. The mixed solution 3 is reacted for 3 minutes. After the reaction, the solid is separated using high-speed centrifugation. 30 mL of distilled water and 18 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After 1 hour the reaction 0.75 g of poly (ethylene glycol) - Block -Poly (propylene glycol) - to put a mixed solution of the Block -poly (ethylene glycol) in 9 mL of ethyl lactate, and the mixture was stirred for 3 minutes. After the reaction, the solid is separated by high-speed centrifugation. 30 mL of distilled water and 9 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After 1 hour the reaction 0.3 g of poly (ethylene glycol) - Block -Poly (propylene glycol) - to put a mixed solution of the Block -poly (ethylene glycol) in 3 mL of ethyl lactate, and the mixture was stirred for 3 minutes. The catalyst cake thus obtained is removed through 30 centrifugations and 15 mL of ethyl lactate, followed by three centrifugations to remove remaining impurities. Finally, the catalyst cake is dried until it has a constant weight at 60 ° C. and 30 in. Hg vacuum.

Example 10

Preparation of Block -poly (ethylene glycol) catalyst (DMC7J-5) comprising - a main organic complexing agent as ethyl lactate, part organic complexing agent (ethylene glycol) poly - Block -poly (propylene glycol)

In a beaker, 4 g of zinc chloride, 69 mL of distilled water, 19.5 mL of ethyl lactate are mixed (mixed solution 1). In a second beaker 1.95 g of potassium hexacyanocobaltate is dissolved in 24 mL of distilled water (mixture 2). In a third beaker, 1.5g of poly (ethylene glycol) - Block -Poly (propylene glycol) - Block -poly (ethylene glycol) is dissolved in the ethyl lactate in 18 mL (mixture 3). The mixed solution 2 is added dropwise to the mixed solution 1 at 50 ° C. for 1 hour while mixing using a mechanical stirrer. The mixed solution 3 is reacted for 3 minutes. After the reaction, the solid is separated using high-speed centrifugation. 30 mL of distilled water and 18 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After 1 hour the reaction 0.75 g of poly (ethylene glycol) - Block -Poly (propylene glycol) - to put a mixed solution of the Block -poly (ethylene glycol) in 9 mL of ethyl lactate, and the mixture was stirred for 3 minutes. After the reaction, the solid is separated by high-speed centrifugation. 30 mL of distilled water and 9 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After 1 hour the reaction 0.3 g of poly (ethylene glycol) - Block -Poly (propylene glycol) - to put a mixed solution of the Block -poly (ethylene glycol) in 3 mL of ethyl lactate, and the mixture was stirred for 3 minutes. The catalyst cake thus obtained is subjected to three centrifugations using 30 mL of distilled water and 15 mL of ethyl lactate to remove remaining impurities. Finally, the catalyst cake is dried until it has a constant weight at 60 ° C. and 30 in. Hg vacuum.

Example 11

Preparation of Catalyst (DMC8) Containing Ethyl Lactate as Primary Organic Complexing Agent and Poly (THF) as Secondary Organic Complexing Agent

In a beaker, 16 g of zinc chloride, 69 mL of distilled water, 21.8 mL of ethyl-2-hydroxy-isobutyrate are mixed (mixed solution 1). In a second beaker 1.95 g of potassium hexacyanocobaltate is dissolved in 24 mL of distilled water (mixture 2). In a third beaker 2.1 g of poly (THF) is dissolved in 18 mL of ethyl-2-hydroxy-isobutyrate (mixture 3). Mixed solution 2 is added dropwise to mixed solution 1 at 50 ° C. for 1 hour while mixing using a mechanical stirrer. The mixed solution 3 is reacted for 3 minutes. After the reaction, the solid is separated using high-speed centrifugation. 30 mL of distilled water and 20.16 mL of ethyl-2-hydroxy-isobutyrate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After 1 hour of reaction, 1.05 g of poly (THF) was dissolved in 10 mL of ethyl-2-hydroxy-isobutyrate, and the mixture was stirred for 3 minutes. After the reaction, the solid is separated by high-speed centrifugation. 30 mL of distilled water and 10 mL of ethyl-2-hydroxy-isobutyrate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After the reaction for 1 hour, 0.3 g of poly (THF) was dissolved in 3.36 mL of ethyl-2-hydroxy-isobutyrate, and the mixture was stirred for 3 minutes. The catalyst cake thus obtained is subjected to three centrifugations using 30 mL of distilled water and 16.8 mL of ethyl-2-hydroxy-isobutyrate to remove the remaining impurities. Finally, the catalyst cake is dried until it has a constant weight at 60 ° C. and 30 in. Hg vacuum.

Comparative Example 1

Preparation of catalyst (DMC-5) containing tertiary butyl alcohol as main organic complexing agent and poly (THF) as secondary organic complexing agent

In a beaker mix 30 g of zinc chloride, 69 mL of distilled water, 115.5 mL of tert-butanol (mixture solution 1). Dissolve 3.15 g of potassium hexacyanocobaltate in 42 mL distilled water in a second beaker (mixture 2). In a third beaker, 3.5 g of poly (THF) is dissolved in 20 mL of tertiary butyl alcohol and 20 mL of distilled water (mixture 3). The mixed solution 2 is added dropwise to the mixed solution 1 at 50 ° C. for 1 hour while mixing using a mechanical stirrer. The mixed solution 3 is reacted for 3 minutes. After the reaction, the solid is separated using high-speed centrifugation. 46 mL of distilled water and 104 mL of tertiary butyl alcohol were mixed with the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After the reaction for 1 hour, 0.85 g of poly (THF) was added to the reactor and stirred for 3 minutes. Solids are separated using high speed centrifugation. 77.75 mL of tertiary butyl alcohol was mixed with the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After the reaction for 1 hour, 0.45 g of poly (THF) was added to the reactor and stirred for 3 minutes. The catalyst cake thus obtained is subjected to three centrifugations using 100 mL of distilled water and 50 mL of tertiary butyl alcohol to remove remaining impurities. Finally, the catalyst cake is dried until it has a constant weight at 60 ° C. and 30 in. Hg vacuum.

Comparative Example 2

Preparation of Catalyst (DMC6) Containing Only Ethyllactate as Main Organic Complexing Agent

In a beaker, 16 g of zinc chloride, 69 mL of distilled water, 19.5 mL of ethyl lactate are mixed (mixed solution 1). In a second beaker 1.95 g of potassium hexacyanocobaltate is dissolved in 24 mL of distilled water (mixture 2). The mixed solution 2 is added dropwise to the mixed solution 1 at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After the reaction, the solid is separated using high-speed centrifugation. 30 mL of distilled water and 18 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. After the reaction, the solid is separated by high-speed centrifugation. 30 mL of distilled water and 9 mL of ethyl lactate were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ° C. for 1 hour while mixing using a mechanical stirrer. The catalyst cake thus obtained is subjected to three centrifugations using 30 mL of distilled water and 15 mL of ethyl lactate to remove remaining impurities. Finally, the catalyst cake is dried until it has a constant weight at 60 ° C. and 30 in. Hg vacuum.

Example 12

Preparation of Polyol Using DMC7G Catalyst (1): Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

Into a 1 L high pressure reactor is introduced 70 g of glycerol propoxylate with a molecular weight of 725 as starter polyol and 0.1 g of the prepared catalyst (638 ppm catalyst based on the last polyol product). The temperature is raised to 115 ° C. with good stirring of the mixture. Hold under vacuum for 2 hours to remove moisture remaining in the mixture. About 15 g of propylene oxide monomer (PO) is injected into the reactor. At this time, the pressure in the reactor increases from vacuum to 4 psig. After some time (induction time), a pressure drop appears in the reactor. This shows that the activity of the catalyst is shown. When the activity of the catalyst appears, propylene oxide (400 g total) is continuously injected into the reactor to maintain a pressure of about 10 psig.

The activity of the catalyst is measured at the steepest point in the graph of PO consumption versus time (see polymerization rates in Figure 1 and Table 1). After the injection of PO is maintained at 95 ° C until a constant pressure is maintained, that is, the polymerization of PO is completed. In order to remove the unreacted PO in the reactor, it is maintained in a vacuum at 60 ~ 80 ℃ for 30 minutes. The polymer is cooled and recovered.

The effects of the catalyst on the polymerization rate, activation induction time, and unsaturation are summarized in Table 1.

Example 13

Preparation of Polyol Using DMC7H Catalyst (1): Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of Example 12 is followed. Only the catalyst of DMC7H is used. The product is recovered in the same way.

Example 14

Preparation of Polyol Using DMC7I Catalyst (1): Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of Example 12 is followed. Only the catalyst of DMC7I is used. The product is recovered in the same way.

Example 15

Preparation of Polyol Using DMC7J-20a Catalyst (1): Effect of Catalyst on Polymerization Rate, Activation Induction Time, and Unsaturation

The order of Example 12 is followed. Only the catalyst of DMC7J-20a is used. The product is recovered in the same way.

Example 16

Preparation of Polyol Using DMC7J-20b Catalyst (1): Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of Example 12 is followed. Only the catalyst of DMC7J-20b is used. The product is recovered in the same way.

Example 17

Preparation of Polyol Using DMC7J-20c Catalyst (1): Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of Example 12 is followed. Only the catalyst of DMC7J-20c is used. The product is recovered in the same way.

Example 18

Preparation of Polyol Using DMC7J-20d Catalyst (1): Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of Example 12 is followed. Only the catalyst of DMC7J-20d is used. The product is recovered in the same way.

Example 19

Preparation of Polyol Using DMC7J-10 Catalyst (1): Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of Example 12 is followed. Only the catalyst of DMC7J-10 is used. The product is recovered in the same way.

Example 20

Preparation of Polyol Using DMC7J-10 Catalyst (1): Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of Example 12 is followed. Only the catalyst of DMC7J-7 is used. The product is recovered in the same way.

Example 21

Preparation of Polyol Using DMC7J-10 Catalyst (1): Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of Example 12 is followed. Only the catalyst of DMC7J-5 is used. The product is recovered in the same way.

Example 22

Preparation of Polyol Using DMC8 Catalyst (1): Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of Example 12 is followed. Only the catalyst of DMC8 is used. The product is recovered in the same way.

Example 23

Preparation of Polyol Using DMC7J-20c Catalyst (1): Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of Example 12 is followed. Only maintain the reactor temperature at 100 ° C instead of 115 ° C. The product is recovered in the same way.

Example 24

Preparation of Polyol Using DMC7J-20c Catalyst (1): Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of Example 12 is followed. Only maintain the temperature of the reactor at 85 ° C instead of 115 ° C. The product is recovered in the same way.

Example 25

Preparation of Polyol Using DMC7J-20c Catalyst (1): Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of Example 12 is followed. Only maintain the temperature of the reactor at 70 ° C instead of 115 ° C. The product is recovered in the same way.

Comparative Example 3

Preparation of polyol using tertiary butyl alcohol and Poly (THF) as organic complexing agent and using (DMC-5) catalyst

The order of Example 12 is followed. Use the (DMC-5) catalyst instead of the (THF-1800) catalyst only and maintain the reactor temperature at 115 ° C. The product is recovered in the same way.

Comparative Example 4

Synthesis of Polyol Using Catalyst (DMC6) Containing Ethyl Lactate, the Main Organic Complexing Agent

The order of Example 12 is followed. Use the (DMC-6) catalyst instead of just the (THF-1800) catalyst and maintain the reactor temperature at 115 ° C. The product is recovered in the same way.

Characteristics of Catalysts by Powder X-ray Diffraction

Table 2 shows the results for typical X-ray diffraction for the zinc hexacyanocobaltate catalyst. Looking at the X-ray diffraction peaks disclosed in the existing patents, when tertiary butyl alcohol was used to synthesize DMC or MMC cyanide catalysts, very sharp peaks were observed at d-spacing of 3.76 angstroms. However, in the case of using the organic complexing agent ethyl lactate, which is mainly used in the present invention, a sharp peak having a very high intensity was observed in d-spacing of 5.07 angstroms than in 3.76 angstroms d-spacing.

Run No. catalyst Polymerization temperature ( ^o C) Induction time (minutes) Polymerization speed
(g POP / g-cat h) Unsaturation (meq / g) KOH 2000 - - - 0.02608 KOH 3000 - - - 0.03591 Comparative Example 3 DMC5 115 176 4215 0.00507 Comparative Example 4 DMC6 115 155 - - Example 12 DMC7G 115 174 1038 0.01021 Example 13 DMC7H 115 275 1281 0.00451 Example 14 DMC7I 115 77 1239 0.00468 Example 17 DMCJ-20c 115 24 1529 0.00225 Example 15 DMCJ-20a 115 40 1242 0.00341 Example 16 DMCJ-20b 115 28 1238 0.00284 Example 17 DMCJ-20c 115 24 1529 0.00225 Example 18 DMCJ-20d 115 29 744 0.00817 Example 17 DMCJ-20c 115 24 1529 0.00225 Example 19 DMCJ-10 115 47 1015 0.00229 Example 20 DMCJ-7 115 29 607 0.00186 Example 21 DMCJ-5 115 154 1052 0.00195 Example 17 DMCJ-20c 115 24 1529 0.00225 Example 22 DMC8 115 200 1265 0.00531 Example 23 DMCJ-20c 100 160 1015 0.00226 Example 24 DMCJ-20c 85 281 1509 0.00167 Example 25 DMCJ-20c 70 471 2002 0.00131

catalyst Characteristics of DMC Catalyst X-ray Diffraction Trends
(d-spacings, angstroms) 5.75 5.07 4.82 3.76 3.59 2.54 2.28 DMC5 none x x x none none none DMC7G x x none x none none none DMC7H none x none x none none none DMC7I none x none x none none none DMC7J-20c none x none x x none none

X means that X-ray diffraction peaks are present.

Run No. catalyst polymerization
Temperature ( ^oC ) Judo
Minutes Maximum polymerization
speed
(g POP
/ g-cat h) GPC Viscosity
(cp) Unsaturation (meq / g)
Mn
PDI KOH 2000 - - - 2000 - - 0.02608 KOH 3000 - - - 3000 - - 0.03591 Comparative Example 3 DMC5 115 176 4215 6545 1.26 1024 0.00507 Comparative Example 4 DMC6 115 155 - - - 848 - Example 11 DMC7G 115 174 1038 5846 1.27 666 0.01021 Example 12 DMC7H 115 275 1281 5582 1.24 950 0.00451 Example 13 DMC7I 115 77 1239 5968 1.26 950 0.00468 Example 16 DMC7J-20c 115 24 - 6714 1.30 652 0.00225 Example 14 DMC7J-20a 115 40 - 6139 1.24 872 0.00341 Example 15 DMC7J-20b 115 28 - 7658 1.29 1140 0.00284 Example 16 DMC7J-20c 115 24 1529 6714 1.30 652 0.00225 Example 17 DMC7J-20d 115 29 - 6538 1.31 1013 0.00817 Example 16 DMC7J-20c 115 24 1529 6714 1.30 652 0.00225 Example 18 DMC7J-10 115 47 1015 - - 1128 0.00229 Example 19 DMC7J-7 115 29 607 - - 892 0.00186 Example 20 DMC7J-5 115 154 1052 - - 886 0.00195 Example 16 DMC7J-20c 115 24 1529 6714 1.30 652 0.00225 Example 21 DMC7J-20c 100 160 1015 - - - 0.00226 Example 22 DMC7J-20c 85 281 1509 - - - 0.00167 Example 23 DMC7J-20c 70 471 2002 - - - 0.00131

catalyst Characteristics of DMC Catalyst X-ray Diffraction Trends
(d-spacings, angstroms) 5.75 5.07 4.82 3.76 3.59 2.54 2.28 DMC5 none x x x none none none DMC8 x none none x x none none DMC7G x x none x none none none DMC7H none x none x none none none DMC7I none x none x none none none DMC7J-20c none x none x x none none

X means that X-ray diffraction peaks are present.

1 depicts the propylene oxide consumption versus time during the polymerization using catalysts (DMC7G, DMC7H, DMC7I, DMC7J-20c, DMC5, DMC8) according to the present invention and prior art catalysts (DMC5). The activity of the catalyst (typically expressed in kg / g / min of propylene oxide) is determined by the slope at the steepest point in the figure. (a) DMC7J-20c, (b) DMC7I, (c) DMC5, (d) DMC7G, (e) DMC8, (f) DMC7H.

2 is a plot of propylene oxide consumption versus time during a polymerization reaction at various polymerization temperatures using a catalyst (DMC7J-20c) according to the present invention. The activity of the catalyst (typically expressed in g / min of kg / cobalte of propylene oxide) is obtained by the slope at the steepest point in the figure. (a) 115 ° C, (b) 100 ° C, (c) 85 ° C, and (d) 70 ° C.

Figure 3 plots propylene oxide consumption versus time during the polymerization using catalysts according to the invention (DMC7J-20C, DMC7J-10, DMC7J-7, DMC7J-5). The activity of the catalyst (typically expressed in g / min of kg / cobalte of propylene oxide) is obtained by the slope at the steepest point in the figure. (a) DMC7J-20c, (b) DMC7J-10, (c) DMC7J-7, (d) DMC7J-5.

Figure 4 is a data analysis of the structure of the catalyst (DMC7G, DMC7H, DMC7I, DMC7J-20c, DMC5, DMC8) according to the present invention through X-ray powder diffraction analysis. (a) DMC7G, (b) DMC7H, (c) DMC7I, (d) DMC7J-20c, (e) DMC5, (f) DMC8.

Claims (19)

Double metal cyanide or multi metal cyanide compounds; Lactate compounds; Heating the epoxide to produce a polyol, optionally in the presence of a catalyst comprising a polyether compound. The process of claim 1 wherein the epoxide is ethylene oxide and / or propylene oxide. The process according to claim 1, wherein the lactate compound is represented by the following formula (I). R ₁ COOC (H) n (OH) R ₂ R ₃ (I) Wherein R ₁ represents H, an aryl group, a C ₁ -C ₂₀ alkyl group, or a group containing R ₄ -NH-, In the case of R ₂ , R ₃ , H, C ₁ -C ₂₀ alkyl group, R ₄ -NH- group, -R ₆ -C (O) OR ₇ group, or cyanide Group, Wherein R 4 comprises H, C ₁ -C ₂₀ alkyl groups, R 6 includes C ₂ -C ₁₅ alkylene groups or substituted alkylene groups, and R ₇ Is H, a C ₁ -C ₂₀ alkyl group, or a substituted alkyl group, n is 0 or 1. According to claim 3, The lactate compound is methyl lactate (methyl lactate), ethyl lactate (ethyl lactate), propyl lactate (propyl lactate), isopropyl lactate (isopropyl lactate), butyl lactate (butyl lactate) lactate, isobutyl lactate, amyl lactate, isoamyl lactate, hexyl lactate, 2-ethyl butyl lactate, 2-ethyl hexyl lactate, characterized in that selected from the group consisting of two or more mixtures thereof. The process of claim 1 wherein the lactate compound is from 1 to 80% by weight of the catalytic amount. The process of claim 1 wherein the polyether compound is a polyether polyol. The process according to claim 6, wherein the polyether polyol is selected from the group consisting of poly (propylene glycol), poly (ethylene glycol), or block copolymers of ethylene oxide and propylene oxide. The process of claim 1 wherein the double metal cyanide compound is zinc hexacyanocobaltate. A method for producing a solid double metal cyanide or multimetal cyanide catalyst, characterized by using a lactate compound as a complexing agent. The method of claim 9, wherein the lactate compound is represented by the following formula (I). R ₁ COOC (H) n (OH) R ₂ R ₃ (I) Wherein R ₁ represents H, an aryl group, a C ₁ -C ₂₀ alkyl group, or a group containing R ₄ -NH-, In the case of R ₂ , R ₃ , H, C ₁ -C ₂₀ alkyl group, R ₄ -NH- group, -R ₆ -C (O) OR ₇ group, or cyanide Group, Wherein R 4 comprises H, C ₁ -C ₂₀ alkyl groups, R 6 comprises C ₂ -C ₁₅ alkylene groups or substituted alkylene groups, and in the case of R ₇ Is H, a C ₁ -C ₂₀ alkyl group, or a substituted alkyl group, n is 0 or 1. The method of claim 10 wherein the lactate compound is ethyl lactate. 10. The process of claim 9, wherein the bimetal cyanide catalyst is zinc hexacyanocobaltate. 10. The method of claim 9, wherein the polyether compound is used as an adjuvant. The process of claim 10 wherein the lactate compound is from several percent to several percent of the catalyst. (a) mixing and reacting an excess aqueous metal salt solution with a metal cyanide salt in the presence of a lactate compound to produce a catalyst slurry; (b) compounding the catalyst slurry with a polyether compound; (c) separating the catalyst from the slurry; (d) washing the catalyst with an aqueous lactate compound solution; And (e) drying to recover the solid catalyst Solid double metal cyanide catalyst production method comprising a. Double metal cyanide or multi metal cyanide compounds; Lactate compounds; Optionally polyether compound Solid metal double or multiple cyanide metal catalyst comprising a. The catalyst according to claim 16, wherein the lactate compound is represented by the following formula (I). R ₁ COOC (H) n (OH) R ₂ R ₃ (I) Wherein R ₁ represents H, an aryl group, a C ₁ -C ₂₀ alkyl group, or a group containing R ₄ -NH-, In the case of R ₂ , R ₃ , H, C ₁ -C ₂₀ alkyl group, R ₄ -NH- group, -R ₆ -C (O) OR ₇ group, or cyanide Group, Wherein R 4 comprises H, C ₁ -C ₂₀ alkyl groups, R 6 comprises C ₂ -C ₁₅ alkylene groups or substituted alkylene groups, and in the case of R ₇ Is H, a C ₁ -C ₂₀ alkyl group, or a substituted alkyl group, n is 0 or 1. The method of claim 17, wherein the lactate compound is methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate lactate, isobutyl lactate, amyl lactate, isoamyl lactate, hexyl lactate, 2-ethyl butyl lactate, 2-ethyl hexyl lactate, a catalyst characterized in that it is selected from the group consisting of two or more thereof. 17. The catalyst of claim 16 wherein the lactate compound is used at several to several weight percent with respect to the catalyst.

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