CN114957674B - Organosilicon polyol and preparation method thereof - Google Patents
Organosilicon polyol and preparation method thereof Download PDFInfo
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- CN114957674B CN114957674B CN202210715027.3A CN202210715027A CN114957674B CN 114957674 B CN114957674 B CN 114957674B CN 202210715027 A CN202210715027 A CN 202210715027A CN 114957674 B CN114957674 B CN 114957674B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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Abstract
The invention provides an organosilicon polyol and a preparation method thereof, wherein carbon dioxide, an epoxy compound, an active hydrogen initiator and cyclic siloxane can realize the preparation of the organosilicon polyol with a new structure and a molecular weight of 1000-5700 under the action of a catalyst, the molecular weight of the polyol and the adjustment of carbonate, silica and ether linkage chain segments in a high molecular chain structure can be realized by adjusting the proportion of the catalyst to a polymerization monomer, the content of carbonate units can be up to 59.2%, and the content of silica chain segments can be up to 45.2%. The organosilicon polyol can be used for preparing polyurethane materials with excellent performance by reacting with isocyanate.
Description
Technical Field
The invention relates to the technical field of polymer synthesis, in particular to an organosilicon polyol and a preparation method thereof.
Background
The organic silicon polymer material has the excellent characteristics of high and low temperature resistance, weather resistance, electrical insulation, radiation resistance, flame retardance, good biocompatibility and the like, is widely applied to the fields of aerospace, national defense and military industry, electronic and electric appliances, petroleum, chemical industry, medicine, daily chemical industry and the like, and is an indispensable polymer new material in national economy development. Since the first siloxane polymer was obtained in Ladenburg 1872, silicon-containing polymeric materials have developed very rapidly, and polycarbosilanes, polysilazanes, and the like have been used in addition to the earliest polysiloxanes studied. However, at present, polysiloxane is still the most studied and widely used silicon-containing polymer material.
The polysiloxane is a general term that a repeated Si-O bond is taken as a main chain, and polymers such as alkyl, phenyl and the like are directly connected to silicon atoms, wherein the Si-O-Si bond of the main chain belongs to an inorganic structure, and the bond energy is 462.0kJ/mol which is far higher than the bond energy (346.9 kJ/mol) of a C-C bond, so that the polysiloxane has the performance of an inorganic material; meanwhile, the organic group on the side chain of the modified polymer has the performance of an organic material. Polysiloxane has very outstanding properties such as low surface tension, excellent heat resistance, low-temperature flexibility, high air permeability, oxidation resistance, ultraviolet resistance, flame resistance, good biocompatibility and the like, but a simple organic silicon material has defects in performance, is mainly reflected in poor surface adhesion and mechanical properties (strength, hardness and the like), is difficult to be used alone when being used as a structural material, and has another key factor in higher cost and limited application.
In recent years, organosilicon modified polyurethane materials have been rapidly developed, and the application fields of the organosilicon modified polyurethane materials are well expanded through complementation of performances, but as mentioned above, the hydroxyl polysiloxane has poor stability and poor hydrolysis resistance, and the traditional work generally realizes improvement of the material performances through polyether or polyester modification and other schemes. However, the scheme is realized by adopting a mode of preparing a block by bonding polyether/ester and polysiloxane, and the molecular weight of the polyether/ester block is higher, so that the problem of compatibility between a siloxane chain segment and a urethane chain segment still exists, and the material performance still has a defect.
For the above reasons, the invention aims to develop an organic (ether, ester, carbonate) -inorganic (silica) high polymer copolymerization (random or block) material with controllable alternating chain segments, and the regulation and control of the mechanical property and the surface property of the material are realized through the adjustment of the composition of silica bonds, carbonate bonds and ether bonds in a molecular chain, so that the development of a novel high-performance silicon-containing high polymer material variety is possible.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an organosilicon polyol with a structure of a silicon-oxygen bond, a carbonate bond and an ether bond in a polymer chain and a preparation method thereof; the organic silicon polyol structure can effectively avoid the problems that traditional silicon-containing polyol such as polydimethylsiloxane is easy to hydrolyze, the compatibility is poor when polyurethane materials are synthesized, and the like, and can realize the regulation and control of the mechanical property and the surface property of the materials through the adjustment of the composition of a silicon bond, a carbonate bond and an ether bond in a molecular chain, so that the organic silicon polyol structure is an ideal raw material for synthesizing the polyurethane materials.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention provides an organosilicon polyol and a preparation method thereof, wherein the organosilicon polyol has a structure shown in a formula (I):
the number average molecular weight of the organosilicon polyol is 500-12000, and the molecular weight distribution is 1.01-6.60;
R 1 、R 2 、R 3 selected from hydrogen, halogen, C1-C12 aliphatic, C1-C12 substituted aliphatic, C2-C18 substituted heteroaliphatic, aryl, substituted aryl or substituted heteroaryl,
x is 1-99%, y is 1-99%, z is 1-99%, and x+y+z=1.
STA is a group after dehydrogenation of an active hydrogen-containing initiator.
The active hydrogen initiator is selected from one or more of small molecular alcohols, phenols, carboxylic acids, thiols and oligomers containing hydroxyl groups.
According to the invention, an active hydrogen initiator is needed to be added as a chain transfer agent in the implementation process, and the active hydrogen initiator mainly plays a role in regulating the molecular weight of a product, and is selected from one or more of small molecular alcohols, carboxylic acids, phenols, thiols and hydroxyl-containing oligomers.
The small molecular alcohol is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, octanediol, sunflower glycol, 1, 3-cyclopentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, isosorbide, trimethylolethane, trimethylolpropane, glycerol, 1,2, 4-butanetriol, polyester triol or pentaerythritol;
the oligomer containing hydroxyl is one or more of polyethylene glycol, polypropylene glycol, polybutylene adipate or polytetrahydrofuran dihydric alcohol with molecular weight lower than 2000;
the phenol is one or more of catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 4' -ethylene bisphenol, bisphenol A, 4' - (2-methylpropylene) bisphenol, 4- (2-ethylhexyl) bisphenol and 2,2' -methylene bisphenol;
the mercaptan is one or more of methyl mercaptan, dithiol or oligomeric polythiol.
The carboxylic acid is preferably malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, terephthalic acid, phthalic acid, isophthalic acid, maleic acid, oleic acid, lactic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxysuccinic acid, tartaric acid, citric acid or salicylic acid.
According to different active hydrogen initiators, the invention can synthesize polyhydric alcohol materials such as organosilicon dihydric alcohol, triol, tetraol and the like, and can be applied to the fields of polyurethane elastomer, adhesive, coating, foam and the like.
The invention provides a preparation method of organosilicon polyol, which comprises the following steps:
under the anhydrous and anaerobic condition, weighing a catalyst, adding an epoxy compound, an active hydrogen initiator and cyclic siloxane into a reactor, adding or not adding a solvent, closing the reactor, and then flushing carbon dioxide for polymerization reaction to obtain organosilicon polyol;
the catalyst is selected from one or more of porphyrin aluminum complex/cocatalyst system, porphyrin cobalt complex/cocatalyst system, schiff base cobalt complex/cocatalyst system, zinc-cobalt double metal cyanide complex, salicylaldehyde imine cobalt or chromium complex, zinc carboxylate complex and diimine zinc complex.
The cocatalyst is quaternary ammonium salt or organic base, and the molar ratio of the porphyrin aluminum complex, the porphyrin cobalt complex and the Schiff base cobalt complex to the cocatalyst is preferably 1 to (5:1), and more preferably 1 to (2:1).
The quaternary ammonium salt or the organic base is selected from one or more of tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, ditolylphosphine ammonium chloride, ditolylphosphine ammonium bromide, ditolylphosphine nitroamine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene-4-dimethylaminopyridine and gamma-chloropropyl methyldimethoxy silane.
Preferably ditriphenylphosphine ammonium chloride, ditriphenylphosphine ammonium bromide, ditriphenylphosphine nitroamine, 1,5, 7-triazabicyclo [4.4.0] dec-5-en-4-dimethylaminopyridine, more preferably ditriphenylphosphine ammonium chloride, 1,5, 7-triazabicyclo [4.4.0] dec-5-en-4-dimethylaminopyridine.
The sources of the catalyst and epoxide are not limited and may be commercially available or may be prepared by methods well known to those skilled in the art.
Typically, porphyrin aluminum complexes can be synthesized by reference (macromolecules, 1981,14 (5): 1166), porphyrin cobalt complexes can be synthesized by reference (J Polym Sci Part A: polym Chem.,2008,46 (17): 5959), schiff base cobalt complexes can be synthesized by reference (J Am Chem Soc.,2006,128 (5): 1664), zinc-cobalt double metal cyanide complexes can be synthesized by reference to the process of patent CN101942081A, and other catalysts can also be synthesized by reference to the relevant literature reporting processes.
According to the invention, the polymerization of carbon dioxide and epoxide is carried out under the action of a catalyst, preferably under anhydrous and anaerobic conditions, with a water content of less than 80 ppm. The polymerization according to the invention is preferably carried out in an autoclave.
According to the present invention, the polymerization reaction may be carried out in bulk or in solution, and when solution polymerization is employed, the solvent is preferably toluene, tetrahydrofuran, dioxane or a chloro-substituted alkane solvent.
According to the present invention, the epoxy compound is one or more of ethylene oxide, propylene oxide, butylene oxide, 3-methyl butylene oxide, 1, 2-epoxy-2-methyl propane, 1, 2-butylene oxide, cyclohexane oxide, cyclopentane oxide, epichlorohydrin, styrene oxide, alkyl-substituted styrene oxide, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether, styrene alkylene oxide, 1, 2-epoxy-4-vinyl cyclohexane, allyl-2, 3-epoxypropyl ether, 3, 4-epoxy-1-butene, limonene oxide, bisphenol A type epoxy resin, phenol type phenolic resin, bisphenol S type 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 epoxy compound is preferably one or more of ethylene oxide, propylene oxide, butylene oxide, cyclopentane oxide, epichlorohydrin, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether, allyl-2, 3-epoxypropyl ether, 3, 4-epoxy-1-butene, and limonene oxide.
More preferably one or more of ethylene oxide, propylene oxide, butylene oxide, glycidyl methacrylate, and limonene oxide.
The cyclic siloxane is one or more of hexamethyl cyclotrisiloxane, hexaethyl cyclotrisiloxane, hexaphenyl cyclotrisiloxane, 2,4, 6-trimethyl-2, 4, 6-triphenyl cyclotrisiloxane, 2,4, 6-trivinyl-2, 4, 6-trimethyl cyclotrisiloxane, 1,3,5, 7-tetramethyl cyclotrisiloxane, tetramethyl tetraphenyl cyclotrisiloxane, octamethyl cyclotrisiloxane, tetramethyl tetravinyl cyclotrisiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, tetradecyl cycloheptasiloxane and octadecyl cyclorisiloxane;
the mass ratio of the catalyst to the total weight of the epoxy compound and the cyclic siloxane is 1 (1000-200000).
The catalysts used in the present invention include porphyrin aluminum complexes, porphyrin cobalt complexes, schiff base cobalt complexes, zinc-cobalt double metal cyanide complexes, salicylaldehyde imine cobalt or chromium complexes, zinc carboxylate complexes and diimine zinc complexes.
The molar ratio of the epoxy compound to the cyclic siloxane is 1: (0.1-10); the molar ratio of the epoxy compound to the active hydrogen initiator is 1000 (1-12).
The polymerization temperature is 20-150 ℃; preferably 50 to 120℃and more preferably 60 to 100 ℃. The pressure of the polymerization reaction is 0.1 to 12MPa, preferably 1 to 10MPa, more preferably 2 to 8MPa.
The polymerization time is 0.5 to 48 hours, more preferably 1 to 20 hours, most preferably 2 to 8 hours.
Compared with the prior art, the invention has the following advantages:
the invention successfully utilizes a ternary polymerization method of carbon dioxide, alkylene oxide and cyclosilane to prepare the silicon-containing polycarbonate polyol, and the scheme realizes the one-step synthesis of the high polymer polyol with the carbonate chain segment, the siloxane bond and the ether bond in the chain segment, and is expected to provide a novel polyol raw material for polyurethane material synthesis. The carbonate bond introduced in the organic silicon polyol structure can effectively avoid the problems of easy hydrolysis of traditional silicon-containing polyol such as polydimethylsiloxane, poor compatibility during polyurethane material synthesis and the like, and can realize the regulation and control of the mechanical property and the surface property of the material through the adjustment of the composition proportion of the silicon bond, the carbonate bond and the ether bond in a molecular chain, thereby being an ideal raw material for polyurethane material synthesis, and simultaneously, a certain amount of carbon dioxide can be fixed in the material, so that the organic silicon polyol has the advantages of low carbon and environmental protection.
Detailed Description
In order to further illustrate the present invention, the following examples are provided to illustrate the preparation of a polyester material according to the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Schiff base cobalt catalysts (Salen Co (III) -Cl) were synthesized by reference to literature procedures (J Am Chem Soc.,2006,128 (5): 1664); zinc-cobalt double metal cyanide complexes were synthesized by reference to the patent procedure (CN 101942081 a); porphyrin cobalt complex reference (J Polym Sci Part A: polym chem.,2008,46 (17): 5959) was synthesized.
Example 1
Adding 0.02mmol of SalenCoCl, 0.020mmol of PPNCl, 20mmol of dipropylene glycol, 0.5mol of propylene oxide and 0.5mol of hexamethylcyclotrisiloxane into a 500ml high-pressure reaction kettle which is subjected to dehydration and deoxidization treatment in advance, and rapidly passing CO with a pressure regulating function 2 The supply line is filled with CO into the kettle 2 The reaction was stirred at 20℃until the pressure was 2MPa for 8 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was dried in vacuo to remove unreacted propylene oxide, whereby 60.5g of an organosilicon polyol was obtained. The polymer has a number average molecular weight of 1500g/mol and a molecular weight distribution of 1.07 as measured by gel permeation chromatography; 1 the results of the H-NMR analysis showed that the cyclic carbonate by-product was 7%, the carbonate unit content in the polymer was about 48.0%, the siloxane unit content was 45.2%, and the etherBond content 2.8% and titer hydroxyl number 74.5.
Example 2
Adding 0.05mmol of porphyrin cobalt complex, 0.004mmol of PPNCl, 18mmol of 1, 4-butanediol, 0.6mol of propylene oxide and 0.4mol of hexamethylcyclotrisiloxane into a 500ml high-pressure reaction kettle which is subjected to dehydration and deoxidization treatment in advance, and rapidly passing CO with a pressure regulating function 2 The supply line is filled with CO into the kettle 2 To 3.0MPa, the temperature was controlled at 25℃and the reaction was stirred for 10 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the product was dried in vacuo to remove unreacted propylene oxide, to obtain 45.5g of an organosilicon polyol. The number average molecular weight of the polymer was 2400, the molecular weight distribution was 1.18, 1 the H-NMR analysis showed that the cyclic carbonate by-product was less than 5%, the carbonate unit content in the polymer was 59.2%, the siloxane unit content was 38.7%, the ether bond content was 2.1%, and the titrimetric hydroxyl number was 45.0.
Example 3
20mg of zinc-cobalt double metal cyanide complex, 30mmol of 1, 4-cyclohexanediol, 0.7mol of propylene oxide and 0.3mol of hexamethylcyclotrisiloxane are added into a 500ml high-pressure reaction kettle which is subjected to dehydration and deoxidization treatment in advance, and the mixture is quickly passed through CO with a pressure regulating function 2 The supply line is filled with CO into the kettle 2 To 4.0MPa, the temperature was controlled at 80℃and the reaction was stirred for 8 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, carbon dioxide is slowly discharged, and the product is dried in vacuum to remove unreacted propylene oxide. 52.2g of silicone polyol was obtained. The number average molecular weight of the polymer was 1700, the molecular weight distribution was 1.04, 1 the H-NMR analysis showed that the cyclic carbonate by-product was less than 4%, the carbonate unit content in the polymer was 32.5%, the siloxane unit content was 21.7%, the ether bond content was 45.8%, and the titrimetric hydroxyl number was 65.0.
Example 4
20mg of zinc-cobalt double metal cyanide complex, 30mmol of 1, 2-cyclohexanedimethanol and 0.8mol of propylene oxide, 0.2mol of hexamethylcyclotrisiloxane are added to 500ml of high-pressure reaction which has been previously treated with water and oxygen removalIn the reaction kettle, CO with pressure regulating function is quickly passed through 2 The supply line is filled with CO into the kettle 2 To 4.0MPa, the temperature was controlled at 80℃and the reaction was stirred for 8 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, carbon dioxide is slowly discharged, and the product is dried in vacuum to remove unreacted propylene oxide. 62g of silicone polyol was obtained. The number average molecular weight of the polymer was 2000, the molecular weight distribution was 1.30, 1 the H-NMR analysis showed that the cyclic carbonate by-product was less than 5%, the carbonate unit content in the polymer was 40.2%, the siloxane unit content was 18.7%, the ether bond content was 41.1%, and the titrimetric hydroxyl number was 56.5.
Example 5
50mg of zinc-cobalt double metal cyanide complex, 20mmol of hydroquinone, 0.8mol of propylene oxide and 1.2mol of hexaethylcyclotrisiloxane are added into a 500ml high-pressure reaction kettle which is subjected to dehydration and deoxidization treatment in advance, and the mixture is quickly passed through CO with a pressure regulating function 2 The supply line is filled with CO into the kettle 2 To 5.0MPa, the temperature was controlled at 60℃and the reaction was stirred for 8 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, carbon dioxide is slowly discharged, and the product is dried in vacuum to remove unreacted propylene oxide. 48g of silicone polyol was obtained. The number average molecular weight of the polymer was 2500 as measured by gel permeation chromatography, the molecular weight distribution was 1.85, 1 the H-NMR analysis showed that the cyclic carbonate by-product was less than 6%, the carbonate unit content in the polymer was 32.2%, the siloxane unit content was 43.2%, the ether bond content was 24.6%, and the titrimetric hydroxyl number was 44.4.
Example 6
30mg of zinc-cobalt double metal cyanide complex, 9mmol of dipropylene glycol, 0.3mol of propylene oxide and 0.7mol of hexaethyl cyclotrisiloxane are added into a 500ml high-pressure reaction kettle which is subjected to dehydration and deoxidization treatment in advance, and the mixture is quickly passed through CO with a pressure regulating function 2 The supply line is filled with CO into the kettle 2 To 5.0MPa, the temperature was controlled at 90℃and the reaction was stirred for 8 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, carbon dioxide is slowly discharged, and the product is dried in vacuum to remove unreacted propylene oxide. 29g of a silicone polyol was obtained. By gelThe number average molecular weight of the polymer was 1000 as measured by permeation chromatography, the molecular weight distribution was 1.26, 1 the H-NMR analysis showed that the cyclic carbonate by-product was less than 8%, the carbonate unit content in the polymer was 30.2%, the siloxane unit content was 53.3%, the ether bond content was 16.5%, and the titrimetric hydroxyl number was 111.8.
Example 7
20mg of zinc-cobalt double metal cyanide complex, 100ml of tetrahydrofuran, 30mmol of 1, 4-cyclohexanediol and 58g (1 mol) of propylene oxide, 0.3mol of hexamethylcyclotrisiloxane are added into a 500ml high-pressure reaction kettle which is subjected to dehydration and deoxidation treatment in advance, and the mixture is quickly passed through CO with a pressure regulating function 2 The supply line is filled with CO into the kettle 2 To 4.0MPa, the temperature was controlled at 60℃and the reaction was stirred for 12 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, carbon dioxide is slowly discharged, and the product is dried in vacuum to remove unreacted propylene oxide. 75.8g of silicone polyol was obtained. The number average molecular weight of the polymer was 2600 as measured by gel permeation chromatography, the molecular weight distribution was 1.04, 1 the H-NMR analysis showed that the cyclic carbonate by-product was less than 3%, the carbonate unit content in the polymer was 22.7%, the siloxane unit content was 25.2%, the ether bond content was 52.1%, and the titrimetric hydroxyl number was 44.0.
Example 8
30mg of zinc-cobalt double metal cyanide complex, 100ml of dioxane, 9mmol of terephthalic acid, 0.4mol of epoxycyclohexane and 0.5mol of hexaethylcyclotrisiloxane are added into a 500ml of high-pressure reaction kettle which is subjected to dehydration and deoxidization treatment in advance, and CO with a pressure regulating function is quickly passed through 2 The supply line is filled with CO into the kettle 2 To 3.0MPa, the temperature was controlled at 90℃and the reaction was stirred for 24 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, carbon dioxide is slowly discharged, and the product is dried in vacuum to remove unreacted propylene oxide. 51g of silicone polyol was obtained. The polymer had a number average molecular weight of 5700, a molecular weight distribution of 1.03, 1 the H-NMR analysis showed that the cyclic carbonate by-product was less than 6%, the carbonate unit content in the polymer was 25.2%, the siloxane unit content was 43.3%, the ether bond content was 31.5%, and the titrimetric hydroxyl number was 20.5.
Example 9
30mg of zinc-cobalt double metal cyanide complex, 100ml of tetrahydrofuran, 20mmol of phloroglucinol, 58g (1 mol) of propylene oxide and 0.5mol of hexamethylcyclotrisiloxane are added into a 500ml high-pressure reaction kettle which is subjected to dehydration and deoxidation treatment in advance, and CO with a pressure regulating function is quickly passed through 2 The supply line is filled with CO into the kettle 2 To 2.0MPa, the temperature was controlled at 70℃and the reaction was stirred for 10 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, carbon dioxide is slowly discharged, and the product is dried in vacuum to remove unreacted propylene oxide. 63.5g of silicone polyol was obtained. The number average molecular weight of the polymer was 3000, the molecular weight distribution was 1.09, 1 the H-NMR analysis showed that the cyclic carbonate by-product was less than 9%, the carbonate unit content in the polymer was 23.7%, the siloxane unit content was 26.1%, the ether bond content was 50.2%, and the titrimetric hydroxyl number was 57.5.
Example 10
15mg of zinc-cobalt double metal cyanide complex, 30mmol of 1, 4-cyclohexanediol and 0.7mol of propylene oxide are added into a 500ml high-pressure reaction kettle which is subjected to dehydration and deoxidation treatment in advance, and the mixture is quickly passed through CO with a pressure regulating function 2 The supply line is filled with CO into the kettle 2 To 4.0MPa, the temperature was controlled at 80℃and the reaction was stirred for 4 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, carbon dioxide is slowly discharged, and the product is dried in vacuum to remove unreacted propylene oxide. 50.8g of a polycarbonate ether polyol containing no silicone segment was obtained. The number average molecular weight of the polymer was 1800 as measured by gel permeation chromatography, the molecular weight distribution was 1.06, 1 the H-NMR analysis showed that the cyclic carbonate by-product was less than 7%, the carbonate unit content in the polymer was 36.8%, the ether bond content was 63.2%, and the titrimetric hydroxyl number was 62.9.
Example 11
30mg of zinc-cobalt double metal cyanide complex, 40mmol of 1, 4-cyclohexanediol and 0.7mol of propylene oxide, and 0.3mol of hexamethylcyclotrisiloxane are added into a 500ml autoclave which has been previously treated with water and oxygen removal, without adding CO 2 Stirring at 80deg.CShould be 6 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, and the product was dried in vacuo to remove unreacted propylene oxide. 67.8g of a silicone polyether polyol containing no carbonate segment was obtained. The number average molecular weight of the polymer was 1750 as measured by gel permeation chromatography, the molecular weight distribution was 1.05, 1 the H-NMR analysis showed that the acyclic carbonate, the siloxane unit content in the polymer was 28.6%, the ether linkage content was 71.4%, and the titrimetric hydroxyl number was 66.2.
Application example 1
60g of the silicon-containing polycarbonate ether polyol prepared in example 3 was heated to 80℃and dehydrated under reduced pressure with stirring for 2 hours. After dehydration, 18.7g of diphenylmethane diisocyanate is weighed and added into a reactor, after reaction for 1h, 4.5g of 1, 4-butanediol is added into the system, the reaction is carried out for 1min under vigorous stirring, the obtained product is poured into a polytetrafluoroethylene mould, the polytetrafluoroethylene mould is placed in an oven at 80 ℃ for 24h, the polyurethane elastomer A is obtained, the obtained polyurethane is prepared by referring to GB/T1040.3-2006 sample preparation and testing the mechanical properties of the polyurethane elastomer A, and the result shows that the tensile strength of the prepared polyurethane A is 35.3MPa, and the elongation at break is 502.3%. The hardness was 68A according to ASTM D2240-2015, and 71A after 24 hours of low temperature storage at-18 ℃.
Application example 2
60g of the polycarbonate ether polyol prepared in example 10 was heated to 80℃and dehydrated under reduced pressure with stirring for 2 hours. After dehydration, 18.7g of diphenylmethane diisocyanate is weighed and added into a reactor, after reaction for 1h, 4.5g of 1, 4-butanediol is added into the system, the reaction is carried out for 1min under vigorous stirring, the obtained product is poured into a polytetrafluoroethylene mould, the polytetrafluoroethylene mould is placed in an oven at 80 ℃ for 24h, the polyurethane elastomer B is obtained, the obtained polyurethane is prepared by referring to GB/T1040.3-2006, and the mechanical properties of the polyurethane are tested, and the result shows that the tensile strength of the prepared polyurethane A is 31.5MPa, and the elongation at break is 350.9%. The hardness was 75A according to ASTM D2240-2015, and 84A after 24 hours of low temperature storage at-18 ℃.
Application example 3
60g of the silicone polyether polyol prepared in example 11 was heated to 80℃and dehydrated under reduced pressure with stirring for 2 hours. After dehydration, 18.7g of diphenylmethane diisocyanate is weighed and added into a reactor, after reaction for 1h, 4.5g of 1, 4-butanediol is added into the system, the reaction is carried out for 1min under vigorous stirring, the obtained product is poured into a polytetrafluoroethylene mould, the polytetrafluoroethylene mould is placed in an oven at 80 ℃ for 24h, the polyurethane elastomer C is obtained, the obtained polyurethane is prepared by referring to GB/T1040.3-2006 sample preparation and mechanical properties are tested, and the result shows that the tensile strength of the prepared polyurethane A is 27.1MPa, and the elongation at break is 370.1%. The hardness was 65A according to ASTM D2240-2015, and 80A after 24 hours of low temperature storage at-18 ℃.
The results of the application examples show that the polyurethane material synthesized by the organic silicon polycarbonate ether polyol prepared by introducing carbon dioxide and copolymerizing alkylene oxide and cyclosiloxane has excellent mechanical properties and better strength and toughness. Compared with polyurethane materials prepared from polycarbonate ether polyol without introducing a siloxane segment and organic silicon polyether polyol without introducing a carbonate segment, the polyurethane material has better mechanical property, excellent low-temperature resistance and smaller hardness change after being placed at a low temperature. Besides the preparation of the polyurethane elastomer, the organic silicon dihydric alcohol, the trihydric alcohol, the tetrahydric alcohol and other polyhydric alcohol materials synthesized by the invention can be applied to the fields of polyurethane adhesives, coatings, foams, surfactants and the like.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (10)
1. A silicone polyol, characterized in that the silicone polyol has a structure represented by formula (I):
the number average molecular weight of the organosilicon polyol is 500-12000, and the molecular weight distribution is 1.01-6.60;
R 1 、R 2 、R 3 selected from hydrogen, halogen, C1-C12 aliphatic, C1-C12 substituted aliphatic, C2-C18 substituted heteroaliphatic, aryl, substituted aryl or substituted heteroaryl,
x is 1-99%, y is 1-99%, z is 1-99%, and x+y+z=1;
STA is a group after dehydrogenation of an active hydrogen-containing initiator;
the active hydrogen initiator is selected from one or more of small molecular alcohols, phenols, carboxylic acids, thiols and oligomers containing hydroxyl groups.
2. A silicone polyol according to claim 1, wherein the small molecule alcohol is one or more of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, octanediol, sunflower glycol, 1, 3-cyclopentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, isosorbide, trimethylolethane, trimethylolpropane, glycerol, 1,2, 4-butanetriol, polyester triol, or pentaerythritol;
the oligomer containing hydroxyl is one or more of polyethylene glycol with molecular weight lower than 2000, polypropylene glycol with molecular weight lower than 2000, polybutylene adipate with molecular weight lower than 2000 or polytetrahydrofuran glycol with molecular weight lower than 2000;
the phenol is one or more of catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 4' -ethylene bisphenol, bisphenol A, 4' - (2-methylpropylene) bisphenol, 4- (2-ethylhexyl) bisphenol and 2,2' -methylene bisphenol;
the mercaptan is one or more of methyl mercaptan, dithiol or oligomeric polythiol;
the carboxylic acid is one or more of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, terephthalic acid, phthalic acid, isophthalic acid, maleic acid, oleic acid, lactic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxysuccinic acid, tartaric acid, citric acid or salicylic acid.
3. A method of preparing a silicone polyol according to claim 1 or 2, characterized in that the method of preparing a silicone polyol comprises the steps of:
under the anhydrous and anaerobic condition, weighing a catalyst, adding an epoxy compound, an active hydrogen initiator and cyclic siloxane into a reactor, adding or not adding a solvent, closing the reactor, and then flushing carbon dioxide for polymerization reaction to obtain organosilicon polyol;
the catalyst is selected from one or more of porphyrin aluminum complex/cocatalyst system, porphyrin cobalt complex/quaternary ammonium salt system, schiff base cobalt complex/cocatalyst system, zinc-cobalt double metal cyanide complex, salicylaldehyde imine cobalt or chromium complex, zinc carboxylate complex and diimine zinc complex;
the cocatalyst is quaternary ammonium salt or organic base, and the molar ratio of the porphyrin aluminum complex, the porphyrin cobalt complex, the Schiff base cobalt complex and the cocatalyst is 1 to (5:1);
the quaternary ammonium salt or the organic base is selected from one or more of tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, ditolylphosphine ammonium chloride, ditolylphosphine ammonium bromide, ditolylphosphine nitroamine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene-4-dimethylaminopyridine and gamma-chloropropyl methyldimethoxy silane;
the solvent is toluene, tetrahydrofuran, dioxane or chloro-substituted alkane.
4. The method for producing an organosilicon polyol according to claim 3, wherein the epoxy compound is one or more of ethylene oxide, propylene oxide, butylene oxide, 3-methyl butylene oxide, 1, 2-epoxy-2-methyl propane, 1, 2-butylene oxide, cyclohexane oxide, cyclopentane oxide, epichlorohydrin, styrene oxide, alkyl-substituted styrene oxide, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether, styrene alkylene oxide, 1, 2-epoxy-4-vinyl cyclohexane, allyl-2, 3-propylene oxide, 3, 4-epoxy-1-butene, bergapten oxide, bisphenol a-type epoxy resin, bisphenol S-type epoxy resin, 1, 4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and epoxidized animal and vegetable oils.
5. A method of preparing an organosilicon polyol according to claim 3, wherein the cyclic siloxane is one or more of hexamethyl cyclotrisiloxane, hexaethyl cyclotrisiloxane, hexaphenyl cyclotrisiloxane, 2,4, 6-trimethyl-2, 4, 6-triphenyl cyclotrisiloxane, 2,4, 6-trivinyl-2, 4, 6-trimethyl cyclotrisiloxane, 1,3,5, 7-tetramethyl cyclotrisiloxane, tetramethyl tetraphenyl cyclotrisiloxane, octamethyl cyclotrisiloxane, tetramethyl cyclotrisiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, tetradecyl cyclotrisiloxane, octadecyl cyclorisiloxane.
6. The method for producing a silicone polyol according to claim 3, wherein the mass ratio of the catalyst to the total weight of the epoxy compound and the cyclic siloxane is 1 (1000-200000).
7. A method of preparing a silicone polyol according to claim 3, wherein the molar ratio of epoxy compound to cyclic siloxane is 1: (0.1-10); the molar ratio of the epoxy compound to the active hydrogen initiator is 1000 (1-12).
8. A method of preparing a silicone polyol according to claim 3, wherein the polymerization reaction temperature is 20 to 150 ℃; the pressure of the polymerization reaction is 0.1-12 MPa.
9. A method for preparing a silicone polyol according to claim 3, wherein the polymerization time is from 0.5 to 48 hours.
10. Use of a silicone polyol according to claim 1 or 2 in the field of reaction with isocyanates for the preparation of polyurethane materials.
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