CN112111056A - High-activity bi-component catalytic system for preparing polyether polyol or polyether ester polyol and application thereof - Google Patents
High-activity bi-component catalytic system for preparing polyether polyol or polyether ester polyol and application thereof Download PDFInfo
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- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
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- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
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- C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
Abstract
The invention relates to a high-activity bi-component catalytic system for preparing polyether polyol or polyether ester polyol and application thereof. The catalytic system comprises a double metal cyanide catalyst and a promoter; wherein the mass ratio of the active promoter to the double metal cyanide catalyst is 0.01-100: 1; the accelerant is: one or more of quaternary ammonium salt, quaternary phosphonium salt, metal salt and Lewis base. The invention can efficiently catalyze the ring-opening homopolymerization of epoxy compounds or the copolymerization of the epoxy compounds and one or two of carbon dioxide and acid anhydride to prepare the polyether ester polyol by using the catalytic system, and the activity can reach more than 11kg of polymer/g DMC when the reaction is carried out for 6 hours.
Description
Technical Field
The invention belongs to the field of catalytic systems, and particularly relates to a bi-component catalytic system and application thereof in catalyzing ring-opening homopolymerization of epoxy compounds or copolymerization of the epoxy compounds and one or two of carbon dioxide and anhydride to efficiently prepare polyether polyol and polyether ester polyol.
Background
Carbon dioxide is a main greenhouse gas, and the emission of carbon dioxide is rapidly increased along with the continuous promotion of industrialization. Meanwhile, the carbon dioxide is the cheapest and most extensive non-toxic renewable C1 resource, so how to efficiently utilize CO2Are of great interest to many researchers. The degradable aliphatic polycarbonate synthesized by copolymerization of carbon dioxide and epoxy compounds as raw materials has a good development prospect, and is applied to a plurality of fields such as novel polyurethane materials, biomedical materials, gas barrier materials, battery electrolyte materials, phase change materials, adhesives, photoresists, composite materials, rubber material reinforcing agents and the like.
Inoue reports CO for the first time in 19692Copolymerization of propylene oxide with diethyl zinc/water catalytic system to produce polycarbonate is of great interest to scientists who have subsequently developed a variety of catalytic systems, such as: diethyl zinc/multi-proton catalyst, metal carboxylate system, rare earth ternary system, metalloporphyrin system, Salen system, etc.
In the 60 s of the 20 th century, the U.S. general purpose tire rubber company developed for the first time a Double Metal Cyanide (DMC) catalyst capable of catalyzing the ring-opening homopolymerization of epoxy compounds, and the obtained polymer has the advantages of low unsaturation degree, narrow molecular weight distribution and the like, and is obviously superior to the traditional KOH catalyst. In 1985, Kuyper et al first used Zn3[Fe(CN)6]2Catalyzing the copolymerization of carbon dioxide and epoxide, the polymerization temperature is 35 ℃, the reaction time is more than 48 hours, and the catalytic activity is only 44g polymer/g catalyst (US 2500704). Then, Kuyper et al prepared double metal cyanide catalysts of different metal compositions based on Zn3[Co(CN)6]2The DMC is used as a catalyst, and the polypropylene glycol-400 is used as a starter to catalyze PO and CO2Copolymerization, with a reactivity of less than 2g of polymer per g of DMC, a carbonate unit content of the product of about 15% and a cyclic carbonate content of the by-product of more than 20% by weight (U.S. Pat. No. 4,4826887, 4826953, 4826952). Metal hydride catalysts prepared by solution precipitation method for PO and CO, such as Cheniban2Copolymerization, the molecular weight is controlled at 2000-20000, and the product functionality and the initiator functionality are oneThus (CN 1060299). King-donating red, et al, use different carboxy compounds as initiators for PO and CO2And (2) copolymerization, wherein the content of a carbonate unit reaches 45 percent, the catalytic activity is 2.2kg polymer/g DMC, the content of a by-product PC is about 7wt percent, the molecular weight is controlled to be 2000-5000, and the molecular weight distribution is only about 1.5 (J.Polym.Sci.part A: Polym.Chem.,2012,50, 5177-.
The 2004 Rough project group used DMC-catalyzed copolymerization of propylene oxide and phthalic anhydride to prepare an alternating copolymer polyester, the catalytic activity reached 10kg polymer/g DMC, but the molecular weight average molecular weight of the resulting polyester was less than 3000(Journal of applied polymer science,2004,93, 1788-1792). In 2006, Wang et al, catalyzed by DMC catalysts, maleic anhydride, succinic anhydride and phthalic anhydride were copolymerized with PO to prepare polyetherester polyols, and the obtained polyetherester polyols had better mechanical properties than polyurethanes prepared from conventional polyetherpolyols (Journal of applied polymer science,103,2007, 417-. In 2014, Bayer corporation disclosed a method for preparing polyether ester polyol by ternary polymerization of an epoxy compound, carbon dioxide and acid anhydride under the catalysis of DMC. The anhydride compound was able to react completely into the polymer chain with a reactivity of up to 5kg polymer/g DMC (CN 103998489).
Despite the tremendous advances made in DMC catalysts, the copolymerization of PO with DMC to prepare polyetherester polyols still faces a number of problems: 1) the catalyst efficiencies were all below 4kg polymer/g DMC; 2) high selectivity and high activity cannot be considered; 3) the molecular weight distribution is wide, and a high molecular weight polymer tail exists; 4) the reaction induction period is longer. Therefore, further improvement of the DMC catalyst preparation process, improvement of product quality, and reduction of industrial costs are needed.
Sebastian et al investigated the effect of Cl content during the preparation of DMC catalysts, when Cl content was 11.3 wt% and acidity was 2.27mmol NH3DMC-catalyzed cyclohexene oxide and CO in g2There was almost no induction period during the copolymerization and the carbonate unit content reached 86%, but the activity was only 53g polymer/g DMC (appl. Catal. A-Gen.,2014,482, 300-308).
US 5482908 and US 6867162 report that the addition of alkali chloride or alkali oxometallate can reduce the molecular weight tail when DMC-catalyzed PO homopolymerization.
Adding 18-crown ether in the CO-precipitation process of preparing DMC, complexing to generate potassium ion, coordinating, and catalyzing PO and CO2During the copolymerization, the highest content of the product carbonate unit was 48.3%, the content of by-product PC was 3% by weight, and the catalytic activity was 4.8kg of polymer/g of DMC (CN 102731764).
Zhang Xinghuo et al introduces electron-donating N-methylimidazole in the pulping process of preparing DMC to catalyze PO and CO2The copolymerization results in a carbonate unit content of more than 95% and a catalytic activity of 2kg of polymer per g of DMC (CN 101942081).
Kim et al found that the use of DMC as a catalyst and a quaternary ammonium salt and an ionic liquid as a cocatalyst for catalyzing the homopolymerization of epoxy compounds greatly shortened the induction period and increased the reaction rate (Polymer,2007,48, 4361-54767; Catal. today,2008,131, 541-547). While many researchers found that cyclic carbonates could only be obtained with high selectivity when DMC was used as the catalyst, quaternary ammonium salt and quaternary phosphonium salt as the cocatalyst for catalyzing the reaction of epoxy compounds with carbon dioxide (J.mol.Catal.A: chem.,2013,379: 38-45; Green chem.,2009,11, 1754-1757; appl.Catal.A-Gen.,2012,419: 178-184; Mater.Lett.,2014,124, 184-187; J.Org.chem.,2005,70, 8583-8586); catalytic PO and CO Using Co-Ni bimetallic cyanide Complex catalysts in Mengdong et al2In copolymerization of wPC0.5%, fPPC48% and W after addition of PPNCl as cocatalystPCIncrease to 19.5% while fPPCDown to 27% (catalysis, 2019,9, 632); after using ionic liquid as cocatalyst, such as cinnabar, the TON value is raised from 0.53 to 4.40, and the by-product fPCFrom 29.89% to 48.28% (RSC adv.,2018,8, 6565-.
In summary, different components are introduced in the DMC-catalyzed epoxy polymerization process, which has great influence on catalytic activity, reaction selectivity and molecular weight distribution, but the prior art cannot achieve satisfactory effects of all indexes at the same time.
The invention content is as follows:
the invention aims to overcome the defects of the prior art and provide a two-component catalytic system for preparing polyether polyol and polyether ester polyol, wherein the catalytic system and a DMC catalyst form the two-component catalytic system by adding an active promoter; wherein the activity promoter is one or more of quaternary ammonium salt, quaternary phosphonium salt, metal salt or Lewis alkali. The invention can efficiently catalyze the ring-opening polymerization of epoxy compounds to prepare polyether polyol and polyether ester polyol by using the catalytic system, and the activity can reach more than 11kg of polymer/g DMC in 6 hours of reaction.
The technical scheme of the invention is as follows:
a two-component catalyst system for preparing polyether polyol or polyether ester polyol with high activity, wherein the catalyst system comprises a double metal cyanide catalyst and an accelerator;
wherein the mass ratio of the active promoter to the double metal cyanide catalyst is 0.01-100: 1;
the accelerant is: one or more of quaternary ammonium salt, quaternary phosphonium salt, metal salt and Lewis base.
The chemical general formulas of the quaternary ammonium salt or the quaternary phosphonium salt are respectively as follows:
wherein R is1，R2，R3，R4Independently selected from phenyl, phenoxy, 1-5 substituted aryl, heterocyclic radical or C2～30Alkyl groups of (a); x-Is F-、Cl-、Br-、I-、NO3 -、AlCl4 -、BF4 -、PF6 -、CF3COO-、CH3COO-Or CF3SO3 -。
The quaternary ammonium salt or quaternary phosphonium salt is preferably tetrabutylammonium halide, tetraethylammonium halide, tetraoctylammonium halide, or a quaternary phosphonium salt containing one C5～C30Alkyl trimethyl ammonium halides containing one C5～C30Alkyl triethyl ammonium halide, triphenyl phosphonium halide containing a 1-5 substituted aryl group, and a C1～C30Alkyl triphenyl phosphonium halides, bis triphenyl phosphonium ammonium chloride, tetrabutyl phosphonium halides, [ Bmim ]][BF4]、[Emim][BF4]、[Bmim][PF6]、[Emim][PF6]、[Et4N][BF4]、[Et4N][PF6]、[Pr4N][PF6]、[Me4N][PF6]、[Bmim][OOCCH3]、[Emim][OOCCH3]Or [ Bmim ]][NO3]。
The metal salt has the general formula: MXn, wherein M is a metal element in the third and fourth periods of the periodic table, and is preferably magnesium (Mg), aluminum (Al), calcium (Ca), titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), or zinc (Zn); x is F-、Cl-、Br-、I-、C1～30Carboxylate radical of alkyl radical, C7～30Carboxylate radical of alkylaryl radical, C6～30Carboxylate, carbonate, hydroxide, sulfate, oxalate, alkoxy, aryloxy, acyl, or phosphate of phenyl; n is a positive integer of 1-5, and satisfies the valence balance of the system.
The Lewis base comprises a general chemical structure formula as follows:
wherein n is 1-5; r1，R2，R3Independently selected from H, C1～30Alkyl of (C)1～30Alkoxy, 1-5 substituted aryl, phenoxy or cyclohexyl;
rx is selected from C1～30Alkyl groups of (a); ry is independently selected from H, nitrile group, fluorine, chlorine, bromine, iodine, nitro, acetamido, C1～30Alkyl, 1-5 substituted aryl or C1～30Alkoxy group of (2).
The initiator is a compound having the general formula:
wherein n or m is 1-2000;
R1，R3，R5independently selected from hydrogen, hydroxyl, amino, sulfhydryl, phenolic hydroxyl or carboxyl;
R2，R4，R6，R7independently selected from C2～30A branched isomer, aryl, ether, ester, carbonate or thioether thereof;
the initiator is preferably one or more of methanol, ethanol, n-butanol, formic acid, acetic acid, propionic acid, benzoic acid, oxalic acid, succinic acid, terephthalic acid, isophthalic acid, butanediol, glycerol, pentaerythritol, dipentaerythritol, phenol, hydroquinone, or polyether polyol, polyester polyol, polyether polyol, polytetrahydrofuran, polyacrylate polyol, vegetable oil-based polyol, polyvinyl alcohol, polyether amine, polyether thiol, or polycarbonate polyol with the number average molecular weight of 100-5000 g/mol.
The application of the bi-component catalytic system in the preparation of polyether polyol or polyether ester polyol is one of the following two methods:
the method I comprises the following steps:
adding a double metal cyanide catalyst, an accelerant, an initiator and an epoxy compound into a high-pressure reaction kettle, and reacting for 1-20 hours at 30-150 ℃ to obtain polyether ester polyol;
or, the second method comprises the following steps:
adding a double metal cyanide catalyst, an accelerant, an initiator, an epoxy compound and a substance A into a high-pressure reaction kettle, and reacting for 1-20 hours at 30-150 ℃ to obtain polyether ester polyol; the substance A is one or two of anhydride or 0.1-8 MPa carbon dioxide;
wherein, in the two methods, the adding amount of the epoxy compound is 10 of the mass of the double metal cyanide catalyst3～105Doubling;the mass ratio of the promoter to the double metal cyanide catalyst is 0.01-100: 1; the molar ratio of the acid anhydride to the epoxy compound is 0.01-1: 1; the molar ratio of the epoxy compound to the initiator is 5-200: 1.
The epoxy group functionality of the epoxy compound is 1-10, and the epoxy compound has the following structural general formula:
wherein R is1-R13Independently selected from H, C2～30Alkyl, cycloalkyl, haloalkyl, alkoxy or aryl.
The epoxy compound is preferably ethylene oxide, propylene oxide, epichlorohydrin, cyclohexene oxide, cyclobutane, tetrahydrofuran, 4-vinyl cyclohexene oxide, allyl glycidyl ether, styrene oxide, alkyl substituted styrene oxide, bisphenol A epoxy resin, phenol type phenol-formaldehyde resin, bisphenol S epoxy resin, 1, 4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether or epoxidized animal and vegetable oils.
The acid anhydride is a compound having the following structural formula:
wherein R is1、R2、R3、R4Selected from H, C2～30Alkyl, cycloalkyl, haloalkyl, alkoxy or aryl;
the acid anhydride is preferably: succinic anhydride, maleic anhydride, phthalic anhydride, nadic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, 2-methylsuccinic anhydride, 2-benzylsuccinic anhydride, hexahydrophthalic anhydride, cyclopentane-1, 2-dicarboxylic anhydride, chlorendic anhydride, cyclobutane-1, 2-dicarboxylic anhydride, 3-oxabicyclo [3.1.0] hexane-2, 4-dione or 1,2,3, 4-cyclopentanetetracarboxylic dianhydride.
The invention has the beneficial effects that:
according to the invention, on the basis of the traditional double metal cyanide catalyst, an active promoter is introduced to form a double-component catalytic system, the added active promoter participates in coordination of a metal center, the catalyst can be activated more quickly during the catalytic polymerization reaction, the ring opening of an epoxy compound is assisted, the reaction rate is accelerated, the reaction activity is greatly improved, and the precise regulation and control of high polymerization selectivity and molecular weight are realized. The concrete embodiment is as follows:
(1) the catalytic activity of the double-component catalytic system is obviously improved compared with that of a single double-metal cyanide catalyst.
(2) The two-component catalyst system shortens the induction period to a certain extent compared with a single double metal cyanide catalyst.
(3) Compared with polyether polyol or polyether ester polyol prepared by a single double metal cyanide catalyst, the double-component catalytic system has high activity and narrower molecular weight distribution, and the molecular weight tailing phenomenon is obviously improved.
(4) When the two-component catalyst is used for preparing the polyether ester polyol, the reaction rate is further accelerated by adding the anhydride, the anhydride can participate in the reaction quantitatively, the polymerization reaction has high selectivity, and the by-product of the cyclic carbonate is less than 10 wt%.
The catalytic activity of the invention can reach 4.3kg polymer/g DMC within 2 hours of reaction, the activity can reach more than 11kg polymer/g DMC within 6 hours of reaction, the number average molecular weight can be accurately regulated and controlled within 1000-100000, the molecular weight distribution becomes narrow, and the molecular weight tailing phenomenon is obviously improved. And can obviously shorten the induction period to about 1.5 h.
Drawings
FIG. 1 is a GPC curve of polyether ester polyols prepared in examples 2 and 3;
Detailed Description
The following examples are provided to clearly and completely describe the technical solutions, but the present invention is not limited thereto. Those skilled in the art will recognize many variations that are within the spirit of the invention and scope of the claims.
Example 1
Preparation of double metal cyanide catalysts (DMC catalysts) reference is made to the process disclosed in patent CN102179262A, example 1.
Example 2
Preparation of polyether ester polyol:
to a dry autoclave was added 10mg of the DMC catalyst prepared in example 1, accelerator: 3.32mg tetrabutylammonium bromide (TBAB: DMC 1:1mol/mol), epoxy compound: 100mL propylene oxide (PO, 83g), initiator: 20g of polyether polyol (polypropylene glycol 400, abbreviated as PPG-400), cyclic acid anhydride compound: 15g Phthalic Anhydride (PA) (molar ratio of anhydride to epoxy compound 0.07: 1), then the autoclave was closed and charged with CO2And (3) gas, when the temperature in the kettle is stabilized at about 100 ℃, the system pressure is not changed and is stabilized at about 5MPa, after the reaction is carried out for 4 hours, cooling to room temperature, and removing the gas in the kettle to obtain the polyether ester polyol.
The carbonate unit content was calculated from nuclear magnetic hydrogen spectroscopy and the molecular weight and its distribution were obtained by gel permeation chromatography tests, see table 1.
Example 3
The polymerization run and polyol analysis were the same as in example 2 except that no accelerator was added.
FIG. 1 shows that the polyetherester polyol prepared with the addition of the accelerator (example 2) has a narrower molecular weight distribution and the molecular weight tail is significantly improved than that obtained without the addition of the accelerator (3).
Example 4
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar replaced with tetrabutylammonium iodide (TBAI).
Example 5
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar changed to tetrabutylammonium chloride (TBAC).
Example 6
The polymerization run and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar changed to tetrabutylammonium fluoride (TBAF).
Example 7
The polymerization run and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar changed to tetraoctylammonium bromide (TTAB).
Example 8
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar converted to benzyltrimethylammonium chloride (BTMAC).
Example 9
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar to cetyltrimethylammonium bromide (CTAB).
Example 10
The polymerization run and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar replaced with tetramethylammonium hydroxide (TMNOH).
Example 11
The polymerization run and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar changed to tetraethylammonium bromide (TEAB).
Example 12
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar replaced with tetrapropylammonium bromide (TPAB).
Example 13
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar replaced with methyltriethylammonium bromide (TEMAB).
Example 14
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar replaced with benzyltriethylammonium bromide (TEBA).
Example 15
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar replaced with tetrabutylphosphonium bromide (TBPB).
Example 16
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar to butyltriphenylphosphonium bromide (ButPPB).
Example 17
The polymerization run and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar changed to hexadecyltriphenylphosphonium bromide (HTPB).
Example 18
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar replaced with [ Et4N][PF6]。
Example 19
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar replaced with [ Et4N][BF4]。
Example 20
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar replaced by [ Bmim ]][PF6]。
Example 21
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar replaced by [ Bmim ]][OOCCH3]。
Example 22
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar changed to zinc acetate.
Example 23
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar changed to calcium acetate.
Example 24
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar changed to magnesium acetate.
Example 25
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar changed to zinc sulfate.
Example 26
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar replaced with zinc oxalate.
Example 27
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar replaced with Triethylamine (TEA).
Example 28
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar changed to 4-Dimethylaminopyridine (DMAP).
Example 29
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar changed to 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (TBD).
Example 30
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar changed to 1, 8-diazacyclo [5,4,0] undecene-7 (DBU).
Example 31
The polymerization procedure and polyol analysis were the same as in example 2 except that tetrabutylammonium bromide was equimolar to triphenylphosphine (PPh)3)。
Example 32
The polymerization procedure and polyol analysis were the same as in example 2 except for equimolar conversion of tetrabutylammonium bromide to tricyclohexylphosphorus (PCy)3)。
Example 33
The polymerization procedure and polyol analysis were the same as in example 2 except that the amount of tetrabutylammonium bromide added was changed to TBAB: DMC 2:1 mol/mol.
Example 34
The polymerization procedure and polyol analysis were the same as in example 2 except that the amount of tetrabutylammonium bromide added was changed to TBAB: DMC 5:1 mol/mol.
Example 35
The polymerization procedure and polyol analysis were the same as in example 2 except that the amount of tetrabutylammonium bromide added was changed to 10:1 mol/mol.
Examples 36 to 45
The polymerization procedure and polyol analysis were the same as in example 2, except that different pressures, reaction times and reaction temperatures were used.
Examples 46 to 55
The polymerization run and polyol analysis were the same as in example 2, except that different initiators and amounts were used.
TABLE 1 double metal cyanide catalysts for the terpolymerization of carbon dioxide, phthalic anhydride and propylene oxide using different promoters
Note: 10mg DMC, 100ml PO, 20g PPG-400, reaction temperature 100 ℃, pressure 5MPa, 4 h.
TABLE 2 terpolymerization of carbon dioxide, phthalic anhydride and propylene oxide under different reaction conditions
Note: 10mg DMC, TBAB: DMC 1:1mol/mol, 100ml PO, 20g PPG-400.
TABLE 3 terpolymerization of carbon dioxide, phthalic anhydride and propylene oxide with different initiators
Note: 10mg DMC, TBAB: DMC 1:1mol/mol, 100ml PO, 100 ℃, 5MPa, 4 h.aAdd 3mg DMC catalyst, TBAB: DMC 1:1 mol/mol.
It is concluded from the above examples that the addition of the promoter (examples 2 and 4-35) significantly increases the catalytic activity compared to the case of no promoter (example 3), and the induction period is shortened from 150 minutes to 75 minutes, while the content of the by-product cyclic carbonate is reduced from 12% wt to less than 10% wt, the molecular weight distribution is significantly narrowed, and the molecular weight tailing phenomenon is significantly improved.
The invention is not the best known technology.
Claims (8)
1. A two-component catalyst system for the highly active preparation of polyether polyols or polyether ester polyols, characterized in that the catalyst system comprises a double metal cyanide catalyst and an accelerator;
wherein the mass ratio of the active promoter to the double metal cyanide catalyst is 0.01-100: 1;
the accelerant is: one or more of quaternary ammonium salt, quaternary phosphonium salt, metal salt and Lewis base;
the chemical general formulas of the quaternary ammonium salt or the quaternary phosphonium salt are respectively as follows:
wherein R is1，R2，R3，R4Independently selected from phenyl, phenoxy, 1-5 substituted aryl, heterocyclic radical or C2～30Alkyl groups of (a); x-Is F-、Cl-、Br-、I-、NO3 -、AlCl4 -、BF4 -、PF6 -、CF3COO-、CH3COO-Or CF3SO3 -；
The metal salt has the general formula: MXn, wherein M is a metal element in the third period and the fourth period of the periodic table of metal elements; x is F-、Cl-、Br-、I-、C1～30Carboxylate radical of alkyl radical, C7～30Carboxylate radical of alkylaryl radical, C6～30Carboxylate, carbonate, hydroxide, sulfate, oxalate, alkoxy, aryloxy of phenylAcyl or phosphate; n is a positive integer of 1-5, and satisfies the valence balance of the system.
2. Two-component catalytic system for highly reactive preparation of polyether polyols or polyether ester polyols according to claim 1, wherein the quaternary ammonium salts or quaternary phosphonium salts are preferably tetrabutylammonium halides, tetraethylammonium halides, tetraoctylammonium halides, catalysts containing one C5～C30Alkyl trimethyl ammonium halides containing one C5～C30Alkyl triethyl ammonium halide, triphenyl phosphonium halide containing a 1-5 substituted aryl group, and a C1～C30Alkyl triphenyl phosphonium halides, bis triphenyl phosphonium ammonium chloride, tetrabutyl phosphonium halides, [ Bmim ]][BF4]、[Emim][BF4]、[Bmim][PF6]、[Emim][PF6]、[Et4N][BF4]、[Et4N][PF6]、[Pr4N][PF6]、[Me4N][PF6]、[Bmim][OOCCH3]、[Emim][OOCCH3]Or [ Bmim ]][NO3]。
3. The two-component catalytic system for highly reactive preparation of polyether polyols or polyether ester polyols of claim 1, wherein said Lewis base comprises a compound having the general chemical structure:
wherein n is 1-5; r1，R2，R3Independently selected from H, C1～30Alkyl of (C)1～30Alkoxy, 1-5 substituted aryl, phenoxy or cyclohexyl;
rx is selected from C1～30Alkyl groups of (a); ry is independently selected from H, nitrile group, fluorine, chlorine, bromine, iodine, nitro, acetamido, C1～30Alkyl, 1-5 substituted aryl or C1～30Alkoxy group of (2).
4. The two-component catalyst system for highly active preparation of polyether polyols or polyether ester polyols according to claim 1, wherein M in the metal salt is preferably magnesium (Mg), aluminum (Al), calcium (Ca), titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) or zinc (Zn).
5. Use of the two-component catalyst system according to claim 1 for the preparation of polyether polyols or polyether ester polyols, characterized by one of the following two methods:
the method I comprises the following steps:
adding a double metal cyanide catalyst, an accelerant, an initiator and an epoxy compound into a high-pressure reaction kettle, and reacting for 1-20 hours at 30-150 ℃ to obtain polyether ester polyol;
or, the second method comprises the following steps:
adding a double metal cyanide catalyst, an accelerant, an initiator, an epoxy compound and a substance A into a high-pressure reaction kettle, and reacting for 1-20 hours at 30-150 ℃ to obtain polyether ester polyol; the substance A is one or two of anhydride or 0.1-8 MPa carbon dioxide;
wherein, in the two methods, the adding amount of the epoxy compound is 10 of the mass of the double metal cyanide catalyst3～105Doubling; the mass ratio of the promoter to the double metal cyanide catalyst is 0.01-100: 1; the molar ratio of the acid anhydride to the epoxy compound is 0.01-1: 1; the molar ratio of the epoxy compound to the initiator is 5-200: 1;
the initiator is a compound having the general formula:
wherein n or m is 1-2000;
R1，R3，R5independently selected from hydrogen, hydroxyl, amino, sulfhydryl, phenolic hydroxyl or carboxyl;
R2，R4，R6，R7independently selected from C2～30A branched isomer, aryl, ether, ester, carbonate or thioether thereof;
the epoxy group functionality of the epoxy compound is 1-10, and the epoxy compound has the following structural general formula:
wherein R is1-R13Independently selected from H, C2～30Alkyl, cycloalkyl, haloalkyl, alkoxy or aryl of (a);
the acid anhydride is a compound having the following structural formula:
wherein R is1、R2、R3、R4Independently selected from H, C2～30Alkyl, cycloalkyl, haloalkyl, alkoxy or aryl.
6. The use of the two-component catalyst system according to claim 5 for preparing polyether polyols or polyether ester polyols, wherein the initiator is preferably one or more of methanol, ethanol, n-butanol, formic acid, acetic acid, propionic acid, benzoic acid, oxalic acid, succinic acid, terephthalic acid, isophthalic acid, butanediol, glycerol, pentaerythritol, dipentaerythritol, phenol, hydroquinone, polyether polyols having a number average molecular weight of 100 to 5000g/mol, polyester polyols, polyether ester polyols, polytetrahydrofuran, polyacrylate polyols, vegetable oil based polyols, polyvinyl alcohol, polyether amines, polyether thiols, or polycarbonate polyols.
7. Use of a two-component catalytic system according to claim 5 for the preparation of polyether polyols or polyether ester polyols, characterized in that the epoxy compound is preferably ethylene oxide, propylene oxide, epichlorohydrin, cyclohexene oxide, cyclobutane, tetrahydrofuran, 4-vinylcyclohexene oxide, allyl glycidyl ether, styrene oxide, alkyl-substituted styrene oxide, epoxy resins of the bisphenol A type, phenol-type phenolic resins, epoxy resins of the bisphenol S type, 1, 4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether or epoxidized animal or vegetable oils.
8. Use of the two-component catalyst system according to claim 5 for the preparation of polyether polyols or polyether ester polyols, characterized in that the anhydrides are preferably: succinic anhydride, maleic anhydride, phthalic anhydride, nadic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, 2-methylsuccinic anhydride, 2-benzylsuccinic anhydride, hexahydrophthalic anhydride, cyclopentane-1, 2-dicarboxylic anhydride, chlorendic anhydride, cyclobutane-1, 2-dicarboxylic anhydride, 3-oxabicyclo [3.1.0] hexane-2, 4-dione or 1,2,3, 4-cyclopentanetetracarboxylic dianhydride.
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