A DMC catalyst and its preparation method and application

Abstract

The invention relates to a DMC catalyst and a preparation method and application thereof. The raw materials for preparing the DMC catalyst include alkaline metal salt, double metal cyanide salt, ligand, dispersion medium, emulsifier and castor oil. The DMC catalyst of the invention can be uniformly dispersed with castor oil even when its own average particle size is large; the DMC catalyst can be continuously produced when preparing castor oil polyether polyol, and the castor oil polyether polyol produced by the preparation method has the characteristics of narrow molecular weight distribution, low castor oil residue and good smell.

Description

Technical Field

[0001] The invention relates to the technical field of polyether polyol preparation, and in particular to a DMC catalyst and a preparation method and application thereof. Background Art

[0002] Castor oil has a hydroxyl functionality of 2.7, which meets the application requirements of soft foam polyether polyols and is an ideal initiator for soft foam polyether.

[0003] CN101121784A discloses a method for preparing castor oil-based polyether polyols that can be used for polyurethane soft foams, wherein castor oil is polymerized with an epoxy compound at 100-200°C in the presence of a bimetallic catalyst at a pressure of 0-0.6 MPa to generate castor oil-based polyether polyols, wherein the main component of the bimetallic catalyst disclosed is zinc hexacyanocobaltate (III), and the amount of the catalyst is 40-200 ppm of the total amount of the synthesized polyether. However, the method adopts intermittent production, which has the disadvantages of large production fluctuations and high costs compared with the continuous method.

[0004] CN103694465A discloses a continuous synthesis method of polyether, wherein a low molecular weight polyether is added to a reactor, and a DMC catalyst is added, and after nitrogen replacement, an alkylene oxide compound is introduced to perform an induction reaction, and when the pressure drops significantly and the temperature rises rapidly, it indicates that the DMC catalyst has been induced; then a small molecule alcohol is used as an initiator, and the alkylene oxide compound is mixed with the initiator and continuously added to the reactor, and at the same time, the DMC catalyst is continuously added through an external circulation pipeline to continuously synthesize a polyether product. However, the polyether initiators used are all small molecule alcohol compounds with a molecular weight of less than 200g / mol. Compared with small molecule alcohol compounds, castor oil has significant differences. First, the molecular weight of castor oil is about 1000g / mol, which is much larger than low molecular weight alcohols. Taking glycerol as an example, if the same molecular weight product is produced under the same residence time conditions, the feed rate of castor oil is about 10 times that of glycerol. Too fast a feed rate causes the castor oil to not mix evenly with the catalyst, and the reaction with the epoxide is not sufficient, resulting in castor oil residue, which in turn causes the product to have a high odor. Secondly, castor oil is an oil-soluble compound, and the DMC catalyst has poor compatibility with it. The catalyst is not easy to disperse when mixed with castor oil, and there is a problem of reduced catalytic activity during use.

[0005] In summary, it is crucial to develop a DMC catalyst that can overcome the above problems and is suitable for the continuous preparation of castor oil polyether polyols. Summary of the invention

[0006] In view of the deficiencies in the prior art, the present invention aims to provide a DMC catalyst and a preparation method and application thereof. The DMC catalyst can be uniformly dispersed with castor oil even when its own average particle size is large; the DMC catalyst can be produced continuously when preparing castor oil polyether polyols; and the castor oil polyether polyols produced by the preparation method have the characteristics of narrow molecular weight distribution, low castor oil residue and good smell.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a DMC catalyst, wherein raw materials for preparing the DMC catalyst include alkaline metal salt, double metal cyanide salt, ligand, dispersion medium, emulsifier and castor oil.

[0009] In the present invention, castor oil is added to the DMC catalyst, so that the DMC catalyst has good compatibility with castor oil when preparing castor oil polyether polyol, is easy to disperse when mixed with castor oil, and has high catalytic activity when used; moreover, it also has the effect of reducing the crystallinity of the catalyst, thereby increasing the active sites of the catalyst and improving the activity of the catalyst; in addition, the addition of the emulsifier can promote better dispersion of the components of the DMC catalyst, and obtain a low crystallinity, easy-to-disperse catalyst. Therefore, the DMC catalyst of the present invention can still be uniformly dispersed with castor oil even when its own average particle size is large; the DMC catalyst can be continuously produced when preparing castor oil polyether polyol, and the castor oil polyether polyol produced by the preparation method has the characteristics of narrow molecular weight distribution, low castor oil residue, and good smell.

[0010] Preferably, the molar ratio of the double metal cyanide salt to the alkaline metal salt is 1:(2-5), wherein 2-5 can be 2.5, 3, 3.5, 4, 4.5, etc., and more preferably 1:(3-4).

[0011] Preferably, the molar ratio of the double metal cyanide salt to castor oil is 1:(1-1.5), wherein 1-1.5 can be 1.1, 1.2, 1.3, 1.4, etc., and more preferably 1:(1.2-1.4).

[0012] In the present invention, the molar ratio of the double metal cyanide salt to castor oil is preferably in the range of 1:(1-1.5) because: if the addition ratio of the two is too high, a small amount of castor oil will lead to poor catalyst dispersibility and low catalytic activity; if the addition ratio of the two is too low, a small amount of double metal cyanide salt will lead to a small number of catalytic active centers per unit mass, resulting in low catalytic activity.

[0013] Preferably, the mass ratio of castor oil to emulsifier is 1:(0.01-0.05), wherein 0.01-0.05 can be 0.02, 0.03, 0.04, etc., and 1:0.03 is further preferred.

[0014] Preferably, the mass ratio of castor oil to ligand is 1:(2-5), wherein 2-5 can be 2.5, 3, 3.5, 4, 4.5, etc., and more preferably 1:(3-4).

[0015] In the present invention, the mass ratio of castor oil to ligand is preferably in the range of 1:(2-5) because: if the addition ratio of the two is too high, less ligand will lead to insufficient coordination with the salt, resulting in low catalytic activity; if the addition ratio of the two is too low, too much ligand will not participate in the reaction, resulting in increased catalyst cost.

[0016] Preferably, the mass ratio of castor oil to dispersion medium is 1:(5-10), wherein 5-10 can be 6, 7, 8, 9, etc., and more preferably 1:(6-8).

[0017] In the present invention, the mass ratio of castor oil to dispersion medium is preferably in the range of 1:(5-10), because: if the addition ratio of the two is too high, less dispersion medium will lead to supersaturated crystallization of metal salt, resulting in inactivity of the catalyst; if the addition ratio of the two is too low, more dispersion medium will lead to low salt concentration and ligand concentration, affecting the coordination reaction of the two, resulting in low catalyst activity.

[0018] Preferably, the basic metal salt comprises a basic metal salt of Group VIII and / or a basic metal salt of Group IIB.

[0019] Preferably, the alkaline metal salt comprises any one of zinc salt, iron salt or nickel salt or a combination of at least two thereof, wherein typical but non-limiting combinations include: a combination of zinc salt and iron salt, a combination of iron salt and nickel salt, a combination of zinc salt, iron salt and nickel salt, etc., and zinc salt is further preferred.

[0020] Preferably, the zinc salt comprises any one of zinc chloride, zinc sulfate, zinc bromide or zinc nitrate, or a combination of at least two thereof, wherein typical but non-limiting combinations include: a combination of zinc chloride and zinc sulfate, a combination of zinc sulfate, zinc bromide and zinc nitrate, a combination of zinc chloride, zinc sulfate, zinc bromide and zinc nitrate, etc., and zinc chloride is further preferred.

[0021] Preferably, the double metal cyanide salt comprises any one of potassium hexacyanocobaltate, sodium hexacyanocobaltate, potassium hexacyanocobalt ferrate or potassium hexacyanoferrate, or a combination of at least two thereof, wherein typical but non-limiting combinations include: a combination of potassium hexacyanocobaltate and sodium hexacyanocobaltate, a combination of sodium hexacyanocobaltate, potassium hexacyanocobalt ferrate and potassium hexacyanoferrate, a combination of potassium hexacyanocobaltate, sodium hexacyanocobaltate, potassium hexacyanocobalt ferrate and potassium hexacyanoferrate, and the like, with potassium hexacyanocobaltate being further preferred.

[0022] Preferably, the ligand comprises any one of isopropanol, n-butanol or isobutanol, or a combination of at least two thereof, wherein typical but non-limiting combinations include: a combination of isopropanol and n-butanol, a combination of n-butanol and isobutanol, a combination of isopropanol, n-butanol and isobutanol, etc., and isopropanol is further preferred.

[0023] Preferably, the emulsifier includes sodium dodecylbenzene sulfonate and / or sodium dodecyl sulfonate, and sodium dodecyl sulfonate is more preferred.

[0024] Preferably, the dispersion medium comprises water.

[0025] Preferably, the prepared raw material also includes desalted water.

[0026] Preferably, the alkaline metal salt and the double metal cyanide salt are each independently formed into a solution with desalted water.

[0027] Preferably, the mass concentration of the alkaline metal salt and the double metal cyanide salt in the solution is independently 10%-20%, such as 12%, 14%, 16%, 18%, etc., more preferably 14%-16%.

[0028] In a second aspect, the present invention provides a method for preparing the DMC catalyst according to the first aspect, the preparation method comprising the following steps:

[0029] The DMC catalyst is obtained by mixing an alkaline metal salt, a double metal cyanide salt, a ligand, a dispersion medium, an emulsifier and castor oil.

[0030] The preparation method of the invention can be used for continuous production. The castor oil polyether polyol produced by the preparation method has the characteristics of narrow molecular weight distribution, low castor oil residue and good smell.

[0031] Preferably, the preparation method comprises the following steps:

[0032] (1) dissolving an alkaline metal salt and a double metal cyanide salt in desalted water respectively to obtain an alkaline metal salt solution and a double metal cyanide salt solution;

[0033] mixing castor oil, an emulsifier, a dispersant and a ligand to form a ligand solution;

[0034] (2) Mixing an alkaline metal salt solution, a double metal cyanide salt solution and a ligand solution to obtain the DMC catalyst.

[0035] Preferably, in step (2), the mixing method comprises: simultaneously dropping the double metal cyanide salt solution and the ligand solution into the alkaline metal salt solution.

[0036] Preferably, after the mixing, filtering, washing and drying are further included.

[0037] In a third aspect, the present invention provides a method for preparing castor oil polyether polyol, the preparation method comprising the following steps:

[0038] Castor oil and an epoxy compound are reacted with the DMC catalyst described in the first aspect to form castor oil polyether polyol.

[0039] Preferably, the epoxide comprises propylene oxide and / or ethylene oxide.

[0040] Preferably, the preparation method comprises the following steps:

[0041] Castor oil and a DMC catalyst are mixed, and then subjected to polymerization reaction and aging reaction with epoxide to obtain the castor oil polyether polyol.

[0042] Preferably, based on the total mass of the castor oil as 100%, the added amount of the DMC catalyst is 0.003%-0.010%, such as 0.004%, 0.006%, 0.008%, etc.

[0043] Preferably, the mass ratio of castor oil to epoxide is 1:(2-5), wherein 2-5 can be 2.5, 3, 3.5, 4, 4.5, etc., and more preferably 1:(3-4).

[0044] Preferably, the mixing is carried out in a formulation kettle.

[0045] Preferably, the polymerization reaction is carried out in a polymerization kettle.

[0046] Preferably, the aging reaction is carried out in an aging kettle.

[0047] Preferably, after the castor oil and the DMC catalyst are mixed, the particle size of the DMC catalyst is less than 1 μm, such as 0.8 μm, 0.6 μm, 0.4 μm, etc.

[0048] Preferably, after the castor oil and the DMC catalyst are mixed, the temperature is raised to 130-150° C., such as 135° C., 140° C., 145° C., etc.

[0049] Preferably, the polymerization reaction temperature is 100-180°C, such as 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, etc., more preferably 130-150°C.

[0050] Preferably, the polymerization reaction pressure is 0.1-1 MPaG, such as 0.2 MPaG, 0.3 MPaG, 0.4 MPaG, 0.5 MPaG, 0.6 MPaG, 0.7 MPaG, 0.8 MPaG, 0.9 MPaG, etc., more preferably 0.3-0.5 MPaG.

[0051] Preferably, the residence time of the polymerization reaction is 1-5 h, for example, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, etc.

[0052] Preferably, the temperature of the aging reaction is 130-150°C, such as 135°C, 140°C, 145°C, etc.

[0053] Preferably, the residence time of the aging reaction is 10-120 min, for example, 20 min, 40 min, 60 min, 80 min, 100 min, etc.

[0054] As a preferred technical solution, the preparation method comprises the following steps:

[0055] (1') mixing castor oil and DMC catalyst in a preparation kettle until the particle size of the DMC catalyst is less than 1 μm, and heating to 130-150° C.;

[0056] (2') introducing the materials in the preparation kettle and epoxide into a polymerization kettle at a mass ratio of castor oil to epoxide of 1:(2-5), and carrying out polymerization reaction at 100-180° C. and 0.1-1 MPaG. After the kettle is full, the materials overflow into the aging kettle, and the residence time in the polymerization kettle is 1-5 h;

[0057] (3') controlling the temperature in the aging kettle to be 130-150° C., carrying out an aging reaction, and controlling the residence time to be 10-120 min to obtain the castor oil polyether polyol.

[0058] Compared with the prior art, the present invention has the following beneficial effects:

[0059] (1) The average particle size of the DMC catalyst of the present invention is 100-300 μm; even if the average particle size of the DMC catalyst of the present invention is larger, it can still be uniformly dispersed with castor oil, and the dispersed particle size is <1 μm under physical mixing conditions.

[0060] (2) The DMC catalyst of the present invention can be used for continuous production when preparing castor oil polyether polyols. The castor oil polyether polyols produced by the preparation method have the characteristics of narrow molecular weight distribution, low castor oil residue and good smell. The castor oil polyether polyols obtained by the preparation method of the present invention have a hydroxyl value of 26.8-53.7 mgKOH / g, a molecular weight distribution of 1.03-1.15, an odor value of less than 3.1, and a castor oil residue of less than 2.3%. DETAILED DESCRIPTION

[0061] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0062] In the present invention, all materials involved in various embodiments are provided by Inotech Reagents unless otherwise specified, and the purity of the product is analytical grade unless otherwise specified.

[0063] Example 1

[0064] This embodiment provides a DMC catalyst, wherein raw materials for preparing the DMC catalyst include zinc chloride, potassium hexacyanocobaltate, isopropanol, water, sodium dodecyl sulfate and castor oil.

[0065] Wherein, the molar ratio of potassium hexacyanocobaltate and zinc chloride is 1:3;

[0066] The molar ratio of potassium hexacyanocobaltate and castor oil is 1:1.3;

[0067] The mass ratio of castor oil to sodium dodecyl sulfate is 1:0.03;

[0068] The mass ratio of castor oil to isopropyl alcohol is 1:4;

[0069] The mass ratio of castor oil to water is 1:7.

[0070] The DMC catalyst is obtained by the following preparation method, which comprises the following steps:

[0071] (1) Dissolving 6.1 g of zinc chloride and 5 g of potassium hexacyanocobaltate in 34.8 g and 28.3 g of desalted water, respectively, to prepare a metal salt solution;

[0072] 18.3 g of castor oil, 0.55 g of sodium dodecyl sulfate, 65 g of water, and 73 g of isopropanol were mixed to prepare a ligand emulsion;

[0073] (2) 33.3 g of potassium hexacyanocobaltate solution and 156.8 g of ligand emulsion were added dropwise to 40.9 g of zinc chloride solution at the same time under stirring at 500 rpm, and stirring was continued for 1 h after the addition was completed, and the crude DMC catalyst was obtained by filtration;

[0074] (3) The obtained crude DMC catalyst was washed three times with 100 mL of desalted water respectively, and the filter cake was placed in an oven at 100° C. for 3 h for drying. The dried catalyst was dispersed into powder using a mortar to obtain the DMC catalyst.

[0075] Example 2

[0076] This embodiment provides a DMC catalyst, wherein raw materials for preparing the DMC catalyst include zinc chloride, potassium hexacyanocobaltate, isopropanol, water, sodium dodecyl sulfate and castor oil.

[0077] Wherein, the molar ratio of potassium hexacyanocobaltate and zinc chloride is 1:2;

[0078] The molar ratio of potassium hexacyanocobaltate and castor oil is 1:1;

[0079] The mass ratio of castor oil to sodium dodecyl sulfate is 1:0.01;

[0080] The mass ratio of castor oil to isopropyl alcohol is 1:2;

[0081] The mass ratio of castor oil to water is 1:5.

[0082] The DMC catalyst is obtained by the following preparation method, which comprises the following steps:

[0083] (1) Dissolving 4.1 g of zinc chloride and 5 g of potassium hexacyanocobaltate in 16.4 g and 20 g of desalted water, respectively, to prepare a metal salt solution;

[0084] 14 g of castor oil, 0.14 g of sodium dodecyl sulfate, 33.9 g of water, and 28.1 g of isopropanol were mixed to prepare a ligand emulsion;

[0085] (2) 25 g of the prepared potassium hexacyanocobaltate solution and 76.1 g of the ligand emulsion were added dropwise to 20.5 g of the zinc chloride solution at the same time under a stirring condition of 500 rpm, and the stirring was continued for 1 hour after the addition was completed, and the crude DMC catalyst was obtained by filtration;

[0086] (3) The obtained crude DMC catalyst was washed three times with 100 mL of desalted water respectively, and the filter cake was placed in an oven at 100° C. for 3 h for drying. The dried catalyst was dispersed into powder using a mortar to obtain the DMC catalyst.

[0087] Example 3

[0088] This embodiment provides a DMC catalyst, wherein raw materials for preparing the DMC catalyst include zinc chloride, potassium hexacyanocobaltate, isopropanol, water, sodium dodecyl sulfate and castor oil.

[0089] Wherein, the molar ratio of potassium hexacyanocobaltate and zinc chloride is 1:5;

[0090] The molar ratio of potassium hexacyanocobaltate and castor oil is 1:1.5;

[0091] The mass ratio of castor oil to sodium dodecyl sulfate is 1:0.05;

[0092] The mass ratio of castor oil to isopropyl alcohol is 1:5;

[0093] The mass ratio of castor oil to water is 1:10.

[0094] The DMC catalyst is obtained by the following preparation method, which comprises the following steps:

[0095] (1) Dissolving 10.2 g of zinc chloride and 5 g of potassium hexacyanocobaltate in 92.2 g and 45 g of desalted water, respectively, to prepare a metal salt solution;

[0096] 21 g of castor oil, 1.05 g of sodium dodecyl sulfate, 73.6 g of water, and 105.4 g of isopropanol were mixed to prepare a ligand emulsion;

[0097] (2) 50 g of the prepared potassium hexacyanocobaltate solution and 201 g of the ligand emulsion were added dropwise to 102.4 g of the zinc chloride solution at the same time under a stirring condition of 500 rpm, and the stirring was continued for 1 hour after the addition was completed, and the crude DMC catalyst was obtained by filtration;

[0098] (3) The obtained crude DMC catalyst was washed three times with 100 mL of desalted water respectively, and the filter cake was placed in an oven at 100° C. for 3 h for drying. The dried catalyst was dispersed into powder using a mortar to obtain the DMC catalyst.

[0099] Embodiment 4-5

[0100] The difference between Example 4-5 and Example 1 is that the molar ratio of potassium hexacyanocobaltate to castor oil is 1:0.9 (Example 4) and 1:1.6 (Example 5), respectively, and the rest is the same as Example 1, as follows:

[0101] Example 4: In step (1), the amount of potassium hexacyanocobaltate added is 7.23 g, and the amount of castor oil added is 18.3 g; in step (2), the amount of potassium hexacyanocobaltate salt solution added is 35.6 g, and the amount of ligand emulsion added is 156.8 g;

[0102] The rest are the same as in Example 1.

[0103] Example 5: In step (1), the amount of hexacyanocobaltate added is 4.07 g, and the amount of castor oil added is 18.3 g; in step (2), the amount of hexacyanocobaltate potassium salt solution added is 32.4 g, and the amount of ligand emulsion added is 156.8 g;

[0104] The rest are the same as in Example 1.

[0105] Example 6

[0106] This embodiment provides a DMC catalyst, wherein raw materials for preparing the DMC catalyst include zinc chloride, potassium hexacyanocobalt ferrate, n-butanol, water, sodium dodecyl sulfate and castor oil.

[0107] Wherein, the molar ratio of potassium hexacyanocobalt ferrate to zinc chloride is 1:3;

[0108] The molar ratio of potassium hexacyanocobalt ferrate to castor oil is 1:1.3;

[0109] The mass ratio of castor oil to sodium dodecyl sulfate is 1:0.03;

[0110] The mass ratio of castor oil to n-butanol is 1:4;

[0111] The mass ratio of castor oil to water is 1:7.

[0112] The DMC catalyst is obtained by the following preparation method, which comprises the following steps:

[0113] (1) dissolving 6.1 g of zinc chloride and 5.3 g of potassium hexacyanocobalt ferrate in 34.8 g and 28.3 g of desalted water, respectively, to prepare a metal salt solution;

[0114] 18.3 g of castor oil, 0.55 g of sodium dodecyl sulfate, 65 g of water, and 73 g of n-butanol were mixed to prepare a ligand emulsion;

[0115] (2) 33.6 g of potassium hexacyanocobalt ferrate solution and 156.8 g of ligand emulsion were added dropwise to 40.9 g of zinc chloride solution at the same time under stirring at 500 rpm. After the addition was completed, stirring was continued for 1 hour, and a crude DMC catalyst was obtained by filtration;

[0116] (3) The obtained crude DMC catalyst was washed three times with 100 mL of desalted water respectively, and the filter cake was placed in an oven at 100° C. for 3 h for drying. The dried catalyst was dispersed into powder using a mortar to obtain the DMC catalyst.

[0117] Example 7

[0118] This embodiment provides a DMC catalyst, wherein raw materials for preparing the DMC catalyst include nickel chloride, potassium hexacyanoferrate, isoamyl alcohol, water, sodium dodecyl sulfate and castor oil.

[0119] Wherein, the molar ratio of potassium hexacyanoferrate to nickel chloride is 1:3;

[0120] The molar ratio of potassium hexacyanoferrate to castor oil is 1:1.3;

[0121] The mass ratio of castor oil to sodium dodecyl sulfate is 1:0.03;

[0122] The mass ratio of castor oil to isoamyl alcohol is 1:4;

[0123] The mass ratio of castor oil to water is 1:7.

[0124] The DMC catalyst is obtained by the following preparation method, which comprises the following steps:

[0125] (1) dissolving 5.9 g of nickel chloride and 5 g of potassium hexacyanoferrate in 34.8 g and 28.3 g of desalted water, respectively, to prepare a metal salt solution;

[0126] 18.3 g of castor oil, 0.55 g of sodium dodecyl sulfate, 65 g of water, and 73 g of isoamyl alcohol were mixed to prepare a ligand emulsion;

[0127] (2) 33.3 g of potassium hexacyanoferrate solution and 156.8 g of ligand emulsion were added dropwise to 40.7 g of nickel chloride solution at the same time under stirring at 500 rpm. After the addition was completed, stirring was continued for 1 hour, and a crude DMC catalyst was obtained by filtration;

[0128] (3) The obtained crude DMC catalyst was washed three times with 100 mL of desalted water respectively, and the filter cake was placed in an oven at 100° C. for 3 h for drying. The dried catalyst was dispersed into powder using a mortar to obtain the DMC catalyst.

[0129] Comparative Example 1

[0130] The difference between this comparative example and Example 1 is that castor oil is not added in the preparation of the DMC catalyst, and the rest is the same as Example 1.

[0131] Comparative Example 2

[0132] The difference between this comparative example and Example 1 is that sodium dodecyl sulfate is not added in the preparation of the DMC catalyst, and the rest is the same as Example 1.

[0133] Comparative Example 3

[0134] This comparative example provides a commercially available DMC catalyst purchased from Huaian Bader Polyurethane Technology Co., Ltd.

[0135] Application Example 1

[0136] This application example provides a castor oil polyether polyol, and the preparation method of the castor oil polyether polyol comprises the following steps:

[0137] (1) 10 kg of castor oil and 0.6 g of the DMC catalyst described in Example 1 were added into a preparation kettle, stirred and mixed, and then heated to 130° C., and a sample was taken to test the particle size of the DMC catalyst after dispersion;

[0138] (2) adding the materials in the configuration kettle and propylene oxide continuously into the polymerization kettle at a mass ratio of castor oil to propylene oxide of 1:3.5, maintaining the reaction temperature at 140°C and the reaction pressure at 0.2 MPaG. After the kettle is full, the materials overflow into the aging kettle, and the residence time in the polymerization kettle is 2.0 h;

[0139] (3) The aging kettle was kept at 140° C. for 20 min, and then cooled to 60° C. to obtain castor oil polyether polyol.

[0140] Application Example 2

[0141] This application example provides a castor oil polyether polyol, and the preparation method of the castor oil polyether polyol comprises the following steps:

[0142] (1) 10 kg of castor oil and 0.3 g of the DMC catalyst described in Example 2 were added into a preparation kettle, stirred and mixed, and then heated to 140° C., and a sample was taken to test the particle size of the DMC catalyst after dispersion;

[0143] (2) adding the materials in the configuration kettle and propylene oxide continuously into the polymerization kettle at a mass ratio of castor oil to propylene oxide of 1:2, maintaining the reaction temperature at 100°C and the reaction pressure at 0.5 MPaG. After the kettle is full, the materials overflow into the aging kettle, and the residence time in the polymerization kettle is 5 hours;

[0144] (3) The aging kettle was kept at 130° C. for 120 min, and then cooled to 60° C. to obtain castor oil polyether polyol.

[0145] Application Example 3

[0146] This application example provides a castor oil polyether polyol, and the preparation method of the castor oil polyether polyol comprises the following steps:

[0147] (1) 10 kg of castor oil and 6 g of the DMC catalyst described in Example 3 were added into a preparation kettle, stirred and mixed, and then heated to 150° C., and a sample was taken to test the particle size of the DMC catalyst after dispersion;

[0148] (2) adding the materials in the configuration kettle and propylene oxide continuously into the polymerization kettle at a mass ratio of castor oil to propylene oxide of 1:5, maintaining the reaction temperature at 180°C and the reaction pressure at 1 MPaG. After the kettle is full, the materials overflow into the aging kettle, and the residence time in the polymerization kettle is 1 hour;

[0149] (3) The aging kettle was kept at 150° C. for 50 min, and then cooled to 60° C. to obtain castor oil polyether polyol.

[0150] Application Examples 4-7 and Comparative Application Examples 1-3

[0151] The difference between Application Examples 4-7 and Comparative Examples 1-3 and Application Example 1 is that the DMC catalyst described in Example 1 is replaced by the DMC catalyst described in Examples 4-7 and Comparative Examples 1-3, respectively, and the rest is the same as Application Example 1.

[0152] Performance Testing

[0153] 1. The DMC catalysts described in Examples 1-7 and Comparative Examples 1-3 were tested as follows:

[0154] Average particle size: measured by Malvern laser particle size analyzer. Take a small amount of DMC catalyst and disperse it in tert-butanol for 10 minutes by ultrasonic. Use tert-butanol as the dispersion medium and measure it twice to take the average value.

[0155] The test results are summarized in Table 1.

[0156] Table 1

[0157] Average particle size (μm) Example 1 280 Example 2 260 Example 3 110 Example 4 300 Example 5 190 Example 6 200 Example 7 190 Comparative Example 1 80 Comparative Example 2 350 Comparative Example 3 50

[0158] 2. The castor oil polyether polyols described in Application Examples 1-5 and Comparative Application Examples 1-3 were tested as follows:

[0159] (1) Hydroxyl value: The hydroxyl value test reference standard GB / T 12008.3-2009 Plastic polyether polyols Part 3: Determination of hydroxyl value.

[0160] (2) Molecular weight distribution and castor oil residue: The molecular weight distribution and castor oil residue were determined by gel permeation chromatography using a Waters 1525 / 2414 instrument with three columns (Styragel HR5, HR4, and HR3) connected in series. The mobile phase was tetrahydrofuran and polystyrene was used as a standard for calibration. The castor oil percentage was calculated by integrating the spectrum.

[0161] (3) Odor rating: 100 mL of castor oil polyether polyol was placed in a 200 mL glass bottle, sealed, and placed in an oven at 80 °C for 2 h. Five people were asked to smell the odor and give scores. The average value was taken as the odor value.

[0162] Decimal values ​​such as 0.5 are allowed in scoring.

[0163] (4) After castor oil and DMC catalyst are dispersed, the average particle size of DMC catalyst is:

[0164] The test results are summarized in Table 2.

[0165] Table 2

[0166]

[0167]

[0168] Analysis of the data in Table 1 and Table 2 shows that the average particle size of the DMC catalyst of the present invention is 110-300 μm, and the average particle size can be further dispersed into a smaller range as required. The reason for controlling the particle size here in the present invention is mainly to illustrate the dispersibility of the DMC catalyst in castor oil. The DMC catalyst of the present invention can still be uniformly dispersed with castor oil when its own average particle size is large, and the dispersed particle size is <1 μm under physical mixing conditions. The obtained castor oil polyether polyol has a hydroxyl value of 26.8-53.7 mgKOH / g, a molecular weight distribution of 1.03-1.15, an odor value of less than 3.1, and a castor oil residue of less than 2.3%. The DMC catalyst of the present invention can be continuously produced when preparing castor oil polyether polyol, and the castor oil polyether polyol produced by the preparation method has the characteristics of narrow molecular weight distribution, low castor oil residue and good odor.

[0169] Analysis of application comparative examples 1-2 and application example 1 shows that the performance of application comparative examples 1-2 is not as good as that of application example 1, which proves that the DMC catalyst of the present invention is more conducive to the preparation of castor oil polyether polyol.

[0170] Analysis of Application Comparative Example 3 and Application Example 1 shows that the performance of Application Comparative Example 3 is not as good as that of Application Example 1, which proves that the DMC catalyst of the present invention is more conducive to the preparation of castor oil polyether polyols than commercially available DMC catalysts with better performance.

[0171] Analysis of Application Examples 4-5 and Application Example 1 shows that the performance of Application Examples 4-5 is not as good as that of Application Example 1, which proves that when preparing castor oil polyether polyol, the molar ratio of the double metal cyanide salt to castor oil in the range of 1: (0.8-1.5) is more conducive to the preparation of castor oil polyether polyol.

[0172] The present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A DMC catalyst, characterized in that The raw materials for preparing the DMC catalyst include alkaline metal salt, double metal cyanide salt, ligand, dispersion medium, emulsifier and castor oil; The molar ratio of the double metal cyanide salt to castor oil is 1:(1-1.5); The mass ratio of castor oil to emulsifier is 1:(0.01-0.05); The alkaline metal salt includes an alkaline metal salt of Group VIII and / or an alkaline metal salt of Group IIB; The molar ratio of the double metal cyanide salt to the alkaline metal salt is 1:(2-5); The mass ratio of the castor oil to the ligand is 1:(2-5).

2. The DMC catalyst according to claim 1, characterized in that The mass ratio of the castor oil to the dispersion medium is 1:(5-10).

3. The DMC catalyst according to claim 1, characterized in that The alkaline metal salt is selected from any one of zinc salt, iron salt or nickel salt, or a combination of at least two of them.

4. The DMC catalyst according to claim 3, characterized in that The zinc salt is selected from any one of zinc chloride, zinc sulfate, zinc bromide or zinc nitrate, or a combination of at least two thereof.

5. The DMC catalyst according to claim 1, characterized in that The double metal cyanide salt is selected from any one of potassium hexacyanocobaltate, sodium hexacyanocobaltate, potassium hexacyanocobalt ferrate or potassium hexacyanoferrate, or a combination of at least two thereof.

6. The DMC catalyst according to claim 1, characterized in that The ligand is selected from any one of isopropanol, n-butanol or isopentanol or a combination of at least two thereof.

7. The DMC catalyst according to claim 1, characterized in that The emulsifier is selected from sodium dodecylbenzene sulfonate and / or sodium dodecyl sulfonate.

8. The DMC catalyst according to claim 1, characterized in that The dispersion medium includes water.

9. The DMC catalyst according to claim 1, characterized in that The prepared raw materials also include desalted water.

10. The DMC catalyst according to claim 1, characterized in that The alkaline metal salt and the double metal cyanide salt are each independently formed into a solution with desalted water.

11. The DMC catalyst according to claim 10, characterized in that The mass concentrations of the alkaline metal salt and the double metal cyanide salt in the solution are independently 10%-20%.

12. A method for preparing the DMC catalyst according to any one of claims 1 to 11, characterized in that: The preparation method comprises the following steps: The DMC catalyst is obtained by mixing an alkaline metal salt, a double metal cyanide salt, a ligand, a dispersion medium, an emulsifier and castor oil.

13. The preparation method according to claim 12, characterized in that: The preparation method comprises the following steps: (1) dissolving an alkaline metal salt and a double metal cyanide salt in desalted water respectively to obtain an alkaline metal salt solution and a double metal cyanide salt solution; mixing castor oil, an emulsifier, a dispersant and a ligand to form a ligand solution; (2) Mixing an alkaline metal salt solution, a double metal cyanide salt solution and a ligand solution to obtain the DMC catalyst.

14. The preparation method according to claim 13, characterized in that: In step (2), the mixing method includes: simultaneously adding the double metal cyanide salt solution and the ligand solution dropwise to the alkaline metal salt solution.

15. The preparation method according to claim 13, characterized in that: After the mixing, the process further includes filtering, washing and drying.

16. A method for preparing castor oil polyether polyol, characterized in that: The preparation method comprises the following steps: Castor oil and an epoxy compound are reacted with the DMC catalyst described in any one of claims 1 to 11 to form castor oil polyether polyol.

17. The preparation method according to claim 16, characterized in that: The epoxide is selected from propylene oxide and / or ethylene oxide.

18. The preparation method according to claim 16, characterized in that: The preparation method comprises the following steps: Castor oil and a DMC catalyst are mixed, and then subjected to polymerization reaction and aging reaction with epoxide to obtain the castor oil polyether polyol.

19. The preparation method according to claim 16, characterized in that: Based on the total mass of the castor oil as 100%, the added amount of the DMC catalyst is 0.003%-0.010%.

20. The preparation method according to claim 16, characterized in that: The mass ratio of castor oil to epoxide is 1:(2-5).

21. The preparation method according to claim 18, characterized in that: The mixing is carried out in a formulation kettle.

22. The preparation method according to claim 18, characterized in that: The polymerization reaction is carried out in a polymerization kettle.

23. The preparation method according to claim 18, characterized in that: The aging reaction is carried out in an aging kettle.

24. The preparation method according to claim 18, characterized in that: After the castor oil and the DMC catalyst are mixed, the particle size of the DMC catalyst is less than 1 μm.

25. The preparation method according to claim 18, characterized in that: After the castor oil and the DMC catalyst are mixed, the temperature is raised to 130-150°C.

26. The preparation method according to claim 18, characterized in that: The polymerization temperature is 100-180°C.

27. The preparation method according to claim 18, characterized in that: The polymerization reaction pressure is 0.1-1 MPaG.

28. The preparation method according to claim 18, characterized in that: The residence time of the polymerization reaction is 1-5 h.

29. The preparation method according to claim 18, characterized in that: The temperature of the aging reaction is 130-150°C.

30. The preparation method according to claim 18, characterized in that: The residence time of the aging reaction is 10-120 min.

31. The preparation method according to claim 16, characterized in that: The preparation method comprises the following steps: (1') Mixing castor oil and DMC catalyst in a preparation kettle until the particle size of DMC catalyst is less than 1 μm, and heating to 130-150°C; (2') introducing the materials in the preparation kettle and epoxide into a polymerization kettle at a mass ratio of castor oil to epoxide of 1:(2-5), and carrying out polymerization reaction at 100-180°C and 0.1-1 MPaG. After the kettle is full, the materials overflow into the aging kettle, and the residence time in the polymerization kettle is 1-5 h; (3') Controlling the temperature in the aging kettle to 130-150° C., carrying out aging reaction, and controlling the residence time to 10-120 min to obtain the castor oil polyether polyol.

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