CN114957674B - Organosilicon polyol and preparation method thereof - Google Patents

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

A kind of organosilicon polyol and preparation method thereof

technical field

The invention relates to the technical field of polymer synthesis, in particular to an organosilicon polyol and a preparation method thereof.

Background technique

Silicone polymer materials have excellent properties such as high and low temperature resistance, weather resistance, electrical insulation, radiation resistance, flame retardancy and good biocompatibility, and are widely used in aerospace, national defense, electronic appliances, petroleum, chemical, pharmaceutical, and Daily-use chemical industry and other fields are indispensable new polymer materials in the development of the national economy. Since Ladenburg obtained the first siloxane polymer in 1872, silicon-containing polymer materials have developed very rapidly. In addition to the earliest polysiloxane, polycarbosilane and polysilazane have also been applied. But up to now, polysiloxane is still the most concentrated and widely used silicon-containing polymer material.

Polysiloxane is a general term for a class of polymers with repeating Si-O bonds as the main chain, and silicon atoms are directly connected to alkyl or phenyl groups. The Si-O-Si bond of the main chain belongs to the "inorganic structure". , the bond energy is 462.0kJ/mol, which is much higher than the bond energy of the C-C bond (346.9kJ/mol), which makes it have the properties of an inorganic material; at the same time, the "organic group" on its side chain makes it both organic Material properties. Polysiloxane has outstanding properties such as low surface tension, excellent heat resistance, low-temperature flexibility, high air permeability, anti-oxidation, anti-ultraviolet, flame retardant, and good biocompatibility, but pure silicone materials have outstanding performance There are also defects in the surface, mainly reflected in the poor surface adhesion and mechanical properties (strength, hardness, etc.), and it is difficult to use it alone as a structural material. Another key factor is its high cost and its application is limited.

In recent years, organosilicon-modified polyurethane materials have been developed rapidly. The application fields of the two have been well expanded through complementary performance. However, as mentioned above, hydroxypolysiloxane has poor stability and hydrolysis resistance. There are also deficiencies in performance. Previous work generally achieved improvement in material performance through polyether or polyester modification. However, this scheme is mostly realized by bonding polyether/ester and polysiloxane to prepare blocks, and the molecular weight of the polyether/ester segment is relatively high, so the compatibility problem between the siloxane segment and the urethane segment still exists. As a result, the material performance is still lacking.

In view of the above reasons, the present invention aims to develop a kind of organic (ether, ester, carbonate)-inorganic (silicone) macromolecular copolymer (random or block) material with controllable alternating chain segments, through the silicon oxygen in the molecular chain The adjustment of the composition of the bond, carbonate bond and ether bond can realize the regulation of the mechanical properties and surface properties of the material, and it is possible to realize the development of a new type of high-performance silicon-containing polymer material.

Contents of the invention

Aiming at the problems of the prior art, the object of the present invention is to provide a silicone polyol with a structure of silicon-oxygen bond, carbonate bond and ether bond in the polymer chain and a preparation method thereof; the structure of the silicone polyol can effectively avoid Traditional silicon-containing polyols such as polydimethylsiloxane are prone to hydrolysis and poor compatibility when synthesizing polyurethane materials, and the mechanical properties and The control of surface properties is an ideal raw material for synthesizing polyurethane materials.

In order to solve the above problems, the technical scheme adopted in the present invention is as follows:

The present invention provides a kind of organosilicon polyol and preparation method thereof, described organosilicon polyol has the structure shown in formula (I):

The number average molecular weight of the silicone polyol is 500-12000, and the molecular weight distribution is 1.01-6.60;

R ₁ , R ₂ , and R ₃ are selected from hydrogen, halogen, C1-C12 aliphatic groups, C1-C12 substituted aliphatic groups, C2-C18 substituted heteroaliphatic groups, aryl groups, substituted aryl or substituted heteroaryl,

Said 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 molecule alcohols, phenols, carboxylic acids, mercaptans, and hydroxyl-containing oligomers.

According to the present invention, it is necessary to add an active hydrogen initiator as a chain transfer agent in the implementation process, which mainly plays a role in regulating the molecular weight of the product. The active hydrogen initiator is selected from small molecule alcohols, carboxylic acids, phenols, mercaptans, and One or more of the oligomers of hydroxyl groups.

The small molecule alcohol is ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 1,5- Pentylene glycol, 1,5-hexanediol, 1,6-hexanediol, octanediol, decanediol, 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, three One or more of methylolethane, trimethylolpropane, glycerin, 1,2,4-butanetriol, polyestertriol or pentaerythritol;

The hydroxyl-containing oligomer is one or more of polyethylene glycol, polypropylene glycol, polybutylene adipate or polytetrahydrofuran diol with a molecular weight lower than 2000;

The phenol is catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 4,4'-ethylene bisphenol, bisphenol A, 4,4'-( One or more of 2-methylpropylene)bisphenol, 4,4-(2-ethylhexylene)bisphenol, and 2,2'-methylenebisphenol;

The thiol is one or more of methanethiol, 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, oil acid, lactic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxysuccinic acid, tartaric acid, citric acid, or salicylic acid.

According to different active hydrogen initiators, the present invention can synthesize polyol materials such as silicone diols, triols, tetraols, etc., and can be applied to fields such as polyurethane elastomers, adhesives, coatings, and foams.

The present invention provides a kind of preparation method of organosilicon polyol, and this preparation method comprises the following steps:

Under anhydrous and oxygen-free conditions, weigh the catalyst and add it to the reactor, then add the epoxy compound, active hydrogen initiator and cyclic siloxane into the reactor, then add or not add solvent, close the reactor and flush Into carbon dioxide, carry out polymerization reaction, obtain organosilicon polyol;

The catalyst is selected from porphyrin aluminum complex/promoter system, porphyrin cobalt complex/cocatalyst system, Schiff base cobalt complex/cocatalyst system, zinc-cobalt double metal cyanide complex, salicylaldimine cobalt Or one or more of chromium complexes, zinc carboxylate complexes and zinc diimide complexes.

The cocatalyst is a quaternary ammonium salt or an organic base, and the molar ratio of the porphyrin aluminum complex, the porphyrin cobalt complex, the Schiff base cobalt complex to the cocatalyst is preferably 1 to (5:1), more preferably 1 ~(2:1).

The quaternary ammonium salt or organic base is selected from tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, bistriphenylphosphine ammonium chloride, bistriphenyl Phosphine ammonium bromide, bistriphenylphosphorylnitroamine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene-4-dimethylaminopyridine and γ-chloropropylmethyl One or more of dimethoxysilanes.

Preferred are bistriphenylphosphine ammonium chloride, bistriphenylphosphine ammonium bromide, bistriphenylphosphorylnitroamine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene -4-dimethylaminopyridine, more preferably bistriphenylphosphine ammonium chloride, 1,5,7-triazabicyclo[4.4.0]dec-5-ene-4-dimethylaminopyridine.

The present invention does not limit the sources of the above catalysts and epoxides, which may be commercially available or prepared by methods well known to those skilled in the art.

Typically, porphyrin aluminum complexes can be synthesized with reference to literature (Macromolecules.,1981,14(5):1166), and porphyrin cobalt complexes can be synthesized with reference to literature (J Polym Sci Part A:Polym Chem.,2008,46 (17): 5959) synthesis, Schiff base cobalt complex can refer to bibliographic information (J Am Chem Soc.,2006,128 (5): 1664) synthesis, zinc-cobalt double metal cyanide complex reference patent (CN101942081A) Other catalysts can also be synthesized by referring to the methods reported in relevant literature.

According to the present invention, the polymerization reaction of carbon dioxide and epoxide under the action of a catalyst is preferably carried out under anhydrous and oxygen-free conditions, and the water content is below 80ppm. The polymerization reaction of the present invention is preferably carried out in an autoclave.

According to the present invention, the polymerization reaction can be carried out in bulk or solution reaction, and when solution polymerization is adopted, the solvent is preferably toluene, tetrahydrofuran, dioxane and chlorinated alkanes.

According to the present invention, the epoxy compound is ethylene oxide, propylene oxide, butylene oxide, 3-methylbutylene oxide, 1,2-epoxy-2-methylpropane, 1,2- Butylene oxide, cyclohexane oxide, cyclopentene oxide, epichlorohydrin, styrene oxide, alkyl substituted styrene oxide, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidol Ether, styrene oxide alkylene, 1,2-epoxy-4-vinylcyclohexane, 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, One or more of glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether or epoxidized animal and vegetable oil.

The epoxy compound is preferably ethylene oxide, propylene oxide, butylene oxide, epoxycyclopentane, epichlorohydrin, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether , allyl-2,3-epoxypropyl ether, 3,4-epoxy-1-butene, one or more of limonene oxide.

More preferably, it is one or more of ethylene oxide, propylene oxide, butylene oxide, glycidyl methacrylate, and limonene oxide.

The cyclic siloxane is hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, hexaphenylcyclotrisiloxane, 2,4,6-trimethyl-2,4,6 -Triphenylcyclotrisiloxane, 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane alkane, tetramethyltetraphenylcyclotetrasiloxane, octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane One or more of siloxane, tetradecylmethylcycloheptasiloxane, octadecylmethylcyclohexasiloxane;

The mass ratio of the catalyst to the total weight of the epoxy compound and the cyclic siloxane is 1:(1000-200000).

Catalysts used in the present invention include porphyrin aluminum complexes, porphyrin cobalt complexes, Schiff base cobalt complexes, zinc-cobalt double metal cyanide complexes, salicylaldimine cobalt or chromium complexes, zinc carboxylate complexes And diimide 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 reaction temperature is 20-150°C; preferably 50-120°C, more preferably 60-100°C. The pressure of the polymerization reaction is 0.1-12 MPa, preferably 1-10 MPa, more preferably 2-8 MPa.

The time for the polymerization reaction is 0.5-48 hours, more preferably 1-20 hours, most preferably 2-8 hours.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

The present invention successfully utilizes the ternary copolymerization method of carbon dioxide, alkylene oxide and cyclosilane to realize the preparation of silicon-containing polycarbonate polyols. Polymer polyols with ether bonds are expected to provide a new type of polyol raw material for the synthesis of polyurethane materials. The carbonate bond introduced in the silicone polyol structure can effectively avoid the problems of easy hydrolysis of traditional silicon-containing polyols such as polydimethylsiloxane and poor compatibility when synthesizing polyurethane materials, and through the silicon-oxygen bond in the molecular chain, The adjustment of the composition ratio of carbonate bonds and ether bonds can realize the control of the mechanical properties and surface properties of the material. It is an ideal raw material for the synthesis of polyurethane materials. At the same time, a certain amount of carbon dioxide can be fixed in the material, which is low-carbon and environmentally friendly. Advantage.

Detailed ways

In order to further illustrate the present invention, the preparation method of a polyester material provided by the present invention is described in detail below in conjunction with the examples, but they should not be understood as limiting the protection scope of the present invention.

The Schiff base cobalt catalyst (Salen Co(Ⅲ)-Cl) was synthesized by referring to the literature steps (J Am Chem Soc.,2006,128(5):1664); the zinc-cobalt double metal cyanide complex was synthesized by referring to the patent steps (CN101942081A ); porphyrin cobalt complex reference materials (J Polym Sci Part A: Polym Chem., 2008,46 (17): 5959) synthesis.

Example 1

Add 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 autoclave that has been pre-treated to remove water and oxygen, and pass through the The CO ₂ supply line with pressure adjustment function filled the kettle with CO ₂ to a pressure of 2MPa, controlled the temperature at 20°C and stirred for 8h. After the polymerization reaction, the reactor was cooled to room temperature, and the carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide to obtain 60.5 g of organosilicon polyol. The number-average molecular weight of the polymer measured by gel permeation chromatography is 1500 g/mol, and the molecular weight distribution is 1.07; ¹ H-NMR analysis results show that the by-product of cyclic carbonate is 7%, and the content of carbonate units in the polymer is about 48.0% , the siloxane unit content is 45.2%, the ether bond content is 2.8%, and the titrated hydroxyl value is 74.5.

Example 2

Add 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 to the In a 500ml high-pressure reactor, quickly fill the kettle with CO ₂ to 3.0MPa through the CO ₂ supply line with pressure adjustment function, and control the temperature at 25°C and stir for 10 hours. After the polymerization reaction, the reactor was cooled to room temperature, and the carbon dioxide was slowly released, and the product was vacuum-dried to remove unreacted propylene oxide to obtain 45.5 g of organosilicon polyol. The number-average molecular weight of the polymer measured by gel permeation chromatography is 2400, and the molecular weight distribution is 1.18. ¹ H-NMR analysis results show that the by-product of cyclic carbonate is less than 5%, and the content of carbonate units in the polymer is 59.2%. The oxane unit content is 38.7%, the ether bond content is 2.1%, and the titrated hydroxyl value is 45.0.

Example 3

Add 20mg of zinc-cobalt double metal cyanide complex, 30mmol of 1,4-cyclohexanediol, 0.7mol of propylene oxide, and 0.3mol of hexamethylcyclotrisiloxane to the 500ml In the high-pressure reaction kettle, quickly fill the kettle with CO ₂ to 4.0MPa through the CO ₂ supply line with pressure adjustment function, and control the temperature at 80°C and stir for 8 hours. After the polymerization reaction is over, cool the reactor to room temperature, slowly release carbon dioxide, and vacuum-dry the product to remove unreacted propylene oxide. 52.2 g of silicone polyol was obtained. The number-average molecular weight of the polymer measured by gel permeation chromatography is 1700, and the molecular weight distribution is 1.04. ¹ H-NMR analysis results show that the by-product of cyclic carbonate is less than 4%, and the content of carbonate units in the polymer is 32.5%. The oxane unit content is 21.7%, the ether bond content is 45.8%, and the titrated hydroxyl value is 65.0.

Example 4

Add 20mg of zinc-cobalt double metal cyanide complex, 30mmol of 1,2-cyclohexanedimethanol, 0.8mol of propylene oxide, and 0.2mol of hexamethylcyclotrisiloxane to the In a 500ml high-pressure reactor, quickly fill the kettle with CO ₂ to 4.0MPa through the CO ₂ supply line with pressure adjustment function, and control the temperature at 80°C and stir for 8 hours. After the polymerization reaction is over, cool the reactor to room temperature, slowly release carbon dioxide, and vacuum-dry the product to remove unreacted propylene oxide. 62 g of silicone polyol was obtained. The number-average molecular weight of the polymer measured by gel permeation chromatography is 2000, and the molecular weight distribution is 1.30. ¹ H-NMR analysis results show that the by-product of cyclic carbonate is less than 5%, and the carbonate unit content in the polymer is 40.2%. The oxane unit content is 18.7%, the ether bond content is 41.1%, and the titrated hydroxyl value is 56.5.

Example 5

Add 50mg of zinc-cobalt double metal cyanide complex, 20mmol of hydroquinone, 0.8mol of propylene oxide, and 1.2mol of hexaethylcyclotrisiloxane into a 500ml high-pressure reactor that has been pre-treated with water and oxygen removal In the process, quickly fill the kettle with CO ₂ to 5.0 MPa through the CO ₂ supply line with pressure adjustment function, and control the temperature at 60°C and stir for 8 hours. After the polymerization reaction is over, cool the reactor to room temperature, slowly release carbon dioxide, and vacuum-dry the product to remove unreacted propylene oxide. 48 g of silicone polyol was obtained. The number-average molecular weight of the polymer measured by gel permeation chromatography is 2500, and the molecular weight distribution is 1.85. ¹ H-NMR analysis results show that the by-product of cyclic carbonate is less than 6%, and the content of carbonate units in the polymer is 32.2%. The oxane unit content is 43.2%, the ether bond content is 24.6%, and the titrated hydroxyl value is 44.4.

Example 6

Add 30 mg of zinc-cobalt double metal cyanide complex, 9 mmol of dipropylene glycol, 0.3 mol of propylene oxide, and 0.7 mol of hexaethylcyclotrisiloxane into a 500 ml high-pressure reactor that has been previously treated with dehydration and oxygen removal, Quickly fill the kettle with CO ₂ to 5.0MPa through the CO ₂ supply line with pressure adjustment function, and control the temperature at 90°C and stir for 8 hours. After the polymerization reaction is over, cool the reactor to room temperature, slowly release carbon dioxide, and vacuum-dry the product to remove unreacted propylene oxide. 29 g of silicone polyol was obtained. The number-average molecular weight of the polymer measured by gel permeation chromatography is 1000, and the molecular weight distribution is 1.26. ¹ H-NMR analysis results show that the by-product of cyclic carbonate is less than 8%, and the carbonate unit content in the polymer is 30.2%. The oxane unit content is 53.3%, the ether bond content is 16.5%, and the titrated hydroxyl value is 111.8.

Example 7

Add 20mg of zinc-cobalt double metal cyanide complex, 100ml of tetrahydrofuran, 30mmol of 1,4-cyclohexanediol, 58g (1mol) of propylene oxide, and 0.3mol of hexamethylcyclotrisiloxane to the pre-dehydrated, In the 500ml high-pressure reaction kettle treated with oxygen removal, quickly fill the kettle with CO ₂ to 4.0MPa through the CO ₂ supply line with pressure adjustment function, and control the temperature at 60°C and stir for 12 hours. After the polymerization reaction is over, cool the reactor to room temperature, slowly release carbon dioxide, and vacuum-dry the product to remove unreacted propylene oxide. 75.8 g of silicone polyol was obtained. The number-average molecular weight of the polymer measured by gel permeation chromatography is 2600, and the molecular weight distribution is 1.04. ¹ H-NMR analysis results show that the cyclic carbonate by-product is less than 3%, and the content of carbonate units in the polymer is 22.7%. The oxane unit content is 25.2%, the ether bond content is 52.1%, and the titrated hydroxyl value is 44.0.

Example 8

Add 30mg of zinc-cobalt double metal cyanide complex, 100ml of dioxane, 9mmol of terephthalic acid, 0.4mol of epoxy cyclohexane, and 0.5mol of hexaethylcyclotrisiloxane to the pre-dehydrated, In the 500ml high-pressure reaction kettle treated with oxygen removal, quickly fill the kettle with CO ₂ to 3.0MPa through the CO ₂ supply line with pressure adjustment function, and control the temperature at 90°C and stir for 24 hours. After the polymerization reaction is over, cool the reactor to room temperature, slowly release carbon dioxide, and vacuum-dry the product to remove unreacted propylene oxide. 51 g of silicone polyol was obtained. The number-average molecular weight of the polymer measured by gel permeation chromatography is 5700, and the molecular weight distribution is 1.03. ¹ H-NMR analysis results show that the by-product of cyclic carbonate is less than 6%, and the carbonate unit content in the polymer is 25.2%. The oxane unit content is 43.3%, the ether bond content is 31.5%, and the titrated hydroxyl value is 20.5.

Example 9

Add 30mg of zinc-cobalt double metal cyanide complex, 100ml of tetrahydrofuran, 20mmol of phloroglucinol, 58g (1mol) of propylene oxide, and 0.5mol of hexamethylcyclotrisiloxane to the In a 500ml high-pressure reactor, quickly fill the kettle with CO ₂ to 2.0MPa through the CO ₂ supply line with pressure adjustment function, and control the temperature at 70°C and stir for 10 hours. After the polymerization reaction is over, cool the reactor to room temperature, slowly release carbon dioxide, and vacuum-dry the product to remove unreacted propylene oxide. 63.5 g of silicone polyol was obtained. The number-average molecular weight of the polymer measured by gel permeation chromatography is 3000, and the molecular weight distribution is 1.09. ¹ H-NMR analysis results show that the by-product of cyclic carbonate is less than 9%, and the content of carbonate units in the polymer is 23.7%. The oxane unit content is 26.1%, the ether bond content is 50.2%, and the titrated hydroxyl value is 57.5.

Example 10

Add 15mg of zinc-cobalt double metal cyanide complex, 30mmol of 1,4-cyclohexanediol and 0.7mol of propylene oxide into a 500ml high-pressure reaction kettle that has been pre-treated to remove water and oxygen. Fill the kettle with CO ₂ to 4.0MPa through the CO ₂ supply line, control the temperature at 80°C and stir the reaction for 4h. After the polymerization reaction is over, cool the reactor to room temperature, slowly release carbon dioxide, and vacuum-dry the product to remove unreacted propylene oxide. 50.8 g of a polycarbonate ether polyol containing no siloxane segment was obtained. The number-average molecular weight of the polymer measured by gel permeation chromatography is 1800, and the molecular weight distribution is 1.06. The ¹ H-NMR analysis results show that the cyclic carbonate by-product is less than 7%, and the carbonate unit content in the polymer is 36.8%. The bond content is 63.2%, and the titrated hydroxyl value is 62.9.

Example 11

Add 30mg of zinc-cobalt double metal cyanide complex, 40mmol of 1,4-cyclohexanediol, 0.7mol of propylene oxide, and 0.3mol of hexamethylcyclotrisiloxane to the 500ml In the autoclave, without adding CO ₂ , the temperature was controlled at 80° C. and the reaction was stirred for 6 h. After the polymerization reaction is finished, the reactor is cooled to room temperature, and the product is vacuum-dried to remove unreacted propylene oxide. 67.8 g of silicone polyether polyols not containing carbonate segments were obtained. The number average molecular weight of the polymer measured by gel permeation chromatography is 1750, the molecular weight distribution is 1.05, and the ¹ H-NMR analysis results show that there is no cyclic carbonate, the content of siloxane units in the polymer is 28.6%, and the content of ether bonds is 71.4%. , The titrated hydroxyl value is 66.2.

Application example 1

Take 60 g of the silicon-containing polycarbonate ether polyol prepared in Example 3 and heat it to 80° C., and dehydrate it under reduced pressure for 2 hours while stirring. After the dehydration is completed, weigh 18.7g of diphenylmethane diisocyanate and add it to the reactor. After reacting for 1 hour, add 4.5g of 1,4-butanediol to the system, stir vigorously for 1 minute, and pour the obtained product into the polytetrafluoroethylene In the mold, put it in an oven at 80°C for 24 hours to obtain polyurethane elastomer A. The obtained polyurethane was prepared according to GB/T 1040.3-2006 and tested for its mechanical properties. The results showed that the prepared polyurethane A had a tensile strength of 35.3 MPa and was The elongation was 502.3%. According to ASTM D2240-2015, the hardness is 68A, and the hardness is 71A after being placed at -18°C for 24 hours.

Application example 2

Take 60 g of the polycarbonate ether polyol prepared in Example 10 and heat it to 80° C., and dehydrate it under reduced pressure for 2 h under stirring. After dehydration, weigh 18.7g of diphenylmethane diisocyanate and add it into the reactor. After 1 hour of reaction, add 4.5g of 1,4-butanediol into the system, stir vigorously for 1 minute, and pour the obtained product into a polytetrafluoroethylene mold placed in an oven at 80°C for 24 hours to obtain polyurethane elastomer B. The obtained polyurethane was sample prepared according to GB/T 1040.3-2006 and its mechanical properties were tested. The results showed that the prepared polyurethane A had a tensile strength of 31.5 MPa and an elongation at break The elongation rate is 350.9%. According to ASTM D2240-2015, the hardness is 75A, and the hardness is 84A after being stored at -18°C for 24 hours.

Application example 3

Take 60 g of the silicone polyether polyol prepared in Example 11 and heat it to 80° C., and dehydrate it under reduced pressure for 2 hours while stirring. After dehydration, weigh 18.7g of diphenylmethane diisocyanate and add it into the reactor. After 1 hour of reaction, add 4.5g of 1,4-butanediol into the system, stir vigorously for 1 minute, and pour the obtained product into a polytetrafluoroethylene mold placed in an oven at 80°C for 24 hours to obtain polyurethane elastomer C, and the obtained polyurethane was prepared according to GB/T1040.3-2006 and its mechanical properties were tested. The results showed that the prepared polyurethane A had a tensile strength of 27.1MPa and was The elongation was 370.1%. According to ASTM D2240-2015, the hardness is 65A, and the hardness is 80A after being placed at -18°C for 24 hours.

The results of the above application examples show that the polyurethane material synthesized by adopting the silicone polycarbonate ether polyol prepared by introducing carbon dioxide, alkylene oxide and cyclosiloxane copolymerization of the present invention has excellent mechanical properties, and has good strength and toughness. Compared with polyurethane materials prepared by polycarbonate ether polyol without siloxane segment and silicone polyether polyol without carbonate segment, it has better mechanical properties and excellent low temperature resistance. Hardness changes little. In addition to preparing the above-mentioned polyurethane elastomers, polyol materials such as silicone diols, triols, and tetraols synthesized by the present invention can also be applied to the fields of polyurethane adhesives, coatings, foams, and surfactants.

The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

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.