CN114790293A - Poly (siloxane-hetero thioether) dihydric alcohol, waterborne polyurethane and polyurethane elastomer and preparation method thereof - Google Patents
Poly (siloxane-hetero thioether) dihydric alcohol, waterborne polyurethane and polyurethane elastomer and preparation method thereof Download PDFInfo
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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
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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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
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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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
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
Abstract
The invention belongs to the technical field of preparation of polyurethane materials, and discloses poly (siloxane-heterosulfide) dihydric alcohol and a preparation method thereof. The invention also discloses organosilicon waterborne polyurethane and organosilicon polyurethane elastomer prepared from the poly (siloxane-heterosulfide) dihydric alcohol. The preparation method has the advantages of simple preparation process, mild reaction, high efficiency, low energy consumption, good water resistance and stability of the prepared product, high film forming speed, wide raw material source, low price and soft and comfortable hand feeling of the glue film. And the reaction process has high atom utilization rate, few byproducts and extremely low harm to the environment and human bodies.
Description
Technical Field
The invention relates to the technical field of polyurethane material preparation, in particular to poly (siloxane-heterosulfide) dihydric alcohol, waterborne polyurethane and a polyurethane elastomer and a preparation method thereof.
Background
Polyurethane is short for polyurethane, and polyurethane is generally obtained by interaction of di-or poly-organic isocyanate and polyol compound. The traditional polyurethane is widely used due to the characteristics of good film forming property, strong adhesion, stability, strong mechanical property and the like. However, the traditional polyurethane coating takes volatile organic compounds as a solvent, and has huge hidden dangers to the environment, the human health and the like. In recent years, the breathing of green chemistry is higher and higher, people have stronger environmental awareness and ecological awareness, and the water-based polyurethane taking water as a solvent is produced. It not only retains the excellent characteristics of polyurethane, but also uses water as continuous phase, greatly reduces the content of organic solvent, and the product meets the environmental protection index, and has low toxicity and nonflammability. However, the water-based polyurethane has many hydrophilic groups, which tend to reduce the hydrophobicity, water resistance, weather resistance, aging resistance and the like of the polyurethane, and in order to make up for these disadvantages, research on polyurethane has been focused on modification of water-based polyurethane. The organosilicon polymer takes Si-O-Si as a main chain skeleton, and has the performances such as high and low temperature resistance, weather resistance, aging resistance, electrical insulation, hydrophobicity, flame retardancy, physiological inertia and the like which cannot be compared with other polymer materials. Therefore, a major research on the modification of the waterborne polyurethane is to introduce the organosilicon polymer into the polyurethane so as to exert the synergistic effect of the organosilicon and the waterborne polyurethane. At present, a small amount of polysiloxane chain segments are mostly introduced into the side chain or the main chain of the organosilicon waterborne polyurethane, and the polysiloxane and the polyether are arranged in a disordered way. For example, CN105693980A describes that the waterborne polyurethane is prepared by the hydrosilylation reaction of hydroxyl-terminated modified silicone oil and allyl polyether to generate dihydric alcohol. However, the reaction efficiency is low, high-temperature heating is required, the energy consumption is high, and the operation cost and the equipment cost are high.
The polyurethane elastomer has high elasticity and strength and good wear resistance, and is widely applied to various industries such as packaging, building materials, electronic communication, traffic and the like. But the development of the composite material is limited due to poor ultraviolet aging resistance and poor high and low temperature resistance. In order to solve the problems, the modification methods adopted at present are mostly organosilicon modification, but polysiloxane has large compatibility with polyurethane, and is easy to generate spontaneous separation tendency, thus destroying the internal structure of the polyurethane elastomer. CN102391455A discloses a preparation method of a bi-component organic silicon polyurethane elastomer, which has the advantages of good ultraviolet aging resistance, wear resistance, solvent resistance and the like. However, the polyurethane elastomer prepared by the method needs to be added with a plasticizer, a reinforcing agent and an inorganic filler to ensure the excellent performance, the preparation process is more complicated, and the storage stability is not strong. CN112979962A discloses a branched-chain type organosilicon modified polyurethane elastomer, which is prepared by introducing double bonds into a main chain of the polyurethane elastomer and grafting polysiloxane through the double bonds. However, polysiloxane is introduced by hydrosilylation, the reaction conditions are harsh, and the platinum-based catalyst is expensive.
Therefore, the development of the organosilicon modified polyurethane elastomer with simple process, low cost and mild reaction conditions becomes an urgent need in the field.
Disclosure of Invention
In view of this, the invention provides a poly (siloxane-hetero thioether) diol, aqueous polyurethane, a polyurethane elastomer and a preparation method thereof, so as to solve the problems of complex process, high cost, high energy consumption and harsh reaction conditions of the existing method for synthesizing the organosilicon polyurethane elastomer.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a poly (siloxane-heterosulfide) dihydric alcohol, which has the structural formula:
wherein R is independently a hydrocarbyl or aryl group; n is any value of 2-10; a is any value of 1 to 4.
The invention also provides a preparation method of the poly (siloxane-hetero thioether) dihydric alcohol, which comprises the following steps:
(1) preparation of vinyl-terminated poly (siloxane-heterosulfide): reacting polyethoxy dithiol, 1,3, 3-tetraalkyl-1, 3-divinyldisiloxane and an initiator to obtain vinyl-terminated poly (siloxane-heterpulfide);
(2) preparation of poly (siloxane-heterethioether) diol: reacting vinyl-terminated poly (siloxane-heterosulfide), 2-mercaptoethanol and an initiator to obtain poly (siloxane-heterosulfide) dihydric alcohol;
the structural formula of the vinyl-terminated poly (siloxane-heterosulfide) is as follows:
wherein R is independently a hydrocarbyl or aryl group; n is any value of 2-10; a is any value of 1-4;
the structural formula of the polyethoxy dithiol is as follows:
wherein a is any value of 1-4.
Preferably, the initiator is independently one or more of benzoin dimethyl ether, benzophenone, diethoxy acetophenone, diphenyl methyl ether, bis (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, anthraquinone, thioxanthone and naphthalimide.
Preferably, in the step (1), the mass ratio of the polyethoxy dithiol to the 1,1,3, 3-tetraalkyl-1, 3-divinyl disiloxane is 1: 1.4-1.6; the amount of the initiator is 0.05-0.1 wt% of the total mass of the polyethoxy dithiol and the 1,1,3, 3-tetraalkyl-1, 3-divinyl disiloxane.
Preferably, in the step (2), the mass ratio of the vinyl-terminated poly (siloxane-hetero sulfide) to the 2-mercaptoethanol is 1: 2-3; the amount of the initiator is 0.05-0.1 wt% of the total mass of the vinyl-terminated poly (siloxane-heterosulfide) and the 2-mercaptoethanol.
Preferably, in the step (1) and the step (2), the reaction temperature is independently 20-30 ℃, and the reaction time is independently 15-30 min.
The invention also provides a method for preparing the organosilicon waterborne polyurethane by the poly (siloxane-hetero thioether) dihydric alcohol, which comprises the following steps:
step A1: mixing an isocyanate compound and a first solvent to obtain a first mixture; mixing poly (siloxane-heterosulfide) dihydric alcohol, polysiloxane dihydric alcohol, a catalyst and a second solvent to obtain a second mixture; mixing the first mixture and the second mixture for reaction to obtain an NCO-terminated prepolymer;
step B1: reacting the NCO-terminated prepolymer, a chain extender, a neutralizer and a solvent to obtain a chain-extended prepolymer;
step C1: carrying out an emulsion reaction on the chain extension prepolymer and water to obtain organosilicon waterborne polyurethane;
in the step A1, the mass volume ratio of the isocyanate compound, the first solvent, the poly (siloxane-heterosulfide) diol, the polysiloxane diol and the second solvent is 3.9-6 g: 1-5 mL: 1 g: 1-4 g: 1-5 mL; the amount of the catalyst is 3-6 wt% of the total mass of the isocyanate compound, the poly (siloxane-heterosulfide) diol and the polysiloxane diol;
in the step A1, the temperature of the mixing reaction is 65-75 ℃, and the time of the mixing reaction is 1.5-2.5 h;
in the step B1, the mass volume ratio of the chain extender to the neutralizer to the solvent is 0.36-1.8 g to 0.84-5.04 g to 1-5 mL; the mass ratio of the chain extender in the step B1 to the poly (siloxane-heterosulfide) glycol in the step A1 is 0.36-1.8: 1;
in the step B1, the reaction temperature is 65-70 ℃, and the reaction time is 4-6 h;
the mass-to-volume ratio of the chain extender in the step B1 to the water in the step C1 is 0.36-1.8 g: 5-20 mL;
in the step C1, the temperature of the emulsification reaction is 65-70 ℃, and the time of the emulsification reaction is 0.5-1 h;
the reactions in steps a1, B1 and C1 were independently carried out under an atmosphere of a protective gas.
The invention also provides the organosilicon waterborne polyurethane prepared by the method for preparing the organosilicon waterborne polyurethane from the poly (siloxane-heterosulfide) dihydric alcohol.
The present invention also provides a method of preparing a silicone polyurethane elastomer from the poly (siloxane-heterosulfide) diol comprising the steps of:
step A2: mixing an isocyanate compound and a solvent to obtain a third mixture; mixing poly (siloxane-heterosulfide) glycol, a catalyst and a solvent to obtain a fourth mixture; reacting the third mixture with the fourth mixture to obtain an NCO-terminated prepolymer;
step B2: mixing and reacting the NCO-terminated prepolymer, a chain extender and a solvent, and drying to obtain an organosilicon polyurethane elastomer;
in the step A2, the mass-to-volume ratio of the isocyanate compound to the solvent in the third mixture is 4-8 g: 1-5 mL; the mass ratio of the poly (siloxane-heterosulfide) diol to the isocyanate compound is 1: 4-8; the amount of the catalyst is 3-6 wt% of the total mass of the isocyanate compound and the poly (siloxane-hetero thioether) diol; the mass to volume ratio of poly (siloxane-heterosulfide) glycol to solvent in the fourth mixture is 1 g: 1-5 mL;
in the step A2, the reaction temperature is 65-75 ℃, and the reaction time is 1.5-2.5 h;
the mass ratio of the poly (siloxane-heterosulfide) diol obtained in the step A2 to the chain extender obtained in the step B2 is 1: 2-6; in the step B2, the mass-to-volume ratio of the chain extender to the solvent is 2-6 g: 1-5 mL;
in the step B2, the temperature of the mixing reaction is 65-70 ℃, and the time of the mixing reaction is 3-5 h;
the reactions in steps a2 and B2 were independently carried out under an atmosphere of a protective gas.
The invention also provides the organosilicon polyurethane elastomer prepared by the method for preparing the organosilicon polyurethane elastomer from the poly (siloxane-hetero thioether) dihydric alcohol.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides poly (siloxane-hetero thioether) dihydric alcohol with a novel structure and a preparation method thereof. The method has the advantages of simple reaction condition, convenient operation, low requirement on operation environment, high efficiency, strong reaction directionality, high yield, greenness and no pollution. The obtained poly (siloxane-hetero thioether) dihydric alcohol has excellent thermal stability and reaction activity, and can be used for preparing polyurethane elastomers, waterborne polyurethane, polyurethane foam, polyurethane adhesives, polyurethane coatings and the like;
(2) the waterborne polyurethane material prepared by the poly (siloxane-hetero thioether) dihydric alcohol with the novel structure has good hydrophobicity, water resistance and heat resistance, soft hand feeling, high solid content, high film forming speed and excellent hydrophilicity, and can be dissolved in 10 times of volume of deionized water. The polyurethane elastomer prepared by the poly (siloxane-hetero thioether) diol with the novel structure has good two-phase compatibility and excellent mechanical property;
(3) the preparation process of the waterborne polyurethane material and the polyurethane elastomer is simple, the reaction is mild, the efficiency is high, the energy consumption is low, the prepared product has good water resistance and stability, the film forming speed is high, the raw material source is wide, the price is low, and the glue film is soft and comfortable in hand feeling. And the atom utilization rate in the reaction process is high, the byproducts are few, and the harm to the environment and human bodies is extremely low.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a structural formula of a poly (siloxane-heterosulfide) glycol of the present invention;
FIG. 2 is a structural formula of a vinyl-terminated poly (siloxane-heterosulfide) of the present invention;
FIG. 3 is a graph showing the thermodynamic properties of a sample wafer 5 obtained in example 6 of the present invention;
FIG. 4 is a graph showing the thermodynamic performance test of a sample wafer 6 obtained in example 7 of the present invention;
FIG. 5 is a comparison graph of the water resistance test results of the sample 1 obtained in example 2 of the present invention and the polysiloxane-based waterborne polyurethane and polyether-based waterborne polyurethane, wherein the left graph is the sample state before the test, and the right graph is the sample state after the test; the left and right figures are a polysiloxane type waterborne polyurethane sample, sample 1 obtained in example 2 and a polyether type waterborne polyurethane sample from top to bottom.
Detailed Description
The invention provides a poly (siloxane-hetero sulfide) dihydric alcohol, which has a structural formula shown in figure 1, and specifically comprises the following components:
wherein, R is independently alkyl or aryl; n is preferably any value of 2 to 10, and more preferably any value of 2 to 6; a is preferably any value of 1 to 4, and more preferably 1 or 3.
The invention also provides a preparation method of the poly (siloxane-heterosulfide) dihydric alcohol, which comprises the following steps:
(1) preparation of vinyl-terminated poly (siloxane-heterosulfide): reacting polyethoxy dithiol, 1,3, 3-tetraalkyl-1, 3-divinyl disiloxane and an initiator to obtain vinyl-terminated poly (siloxane-heterosulfide);
(2) preparation of poly (siloxane-heterethioether) diol: reacting vinyl-terminated poly (siloxane-heterosulfide), 2-mercaptoethanol and an initiator to obtain poly (siloxane-heterosulfide) dihydric alcohol;
the structural formula of the vinyl-terminated poly (siloxane-heterosulfide) is shown in figure 2, and specifically comprises the following components:
wherein R is independently a hydrocarbyl or aryl group; n is preferably any value of 2 to 10, and more preferably any value of 2 to 6; a is preferably any value of 1 to 4, and more preferably 1 or 3;
the structural formula of the polyethoxy dithiol is as follows:
among them, a is preferably any value of 1 to 4, and more preferably 1 or 3.
In the present invention, the initiator is independently preferably one or more of benzoin dimethyl ether, benzophenone, diethoxyacetophenone, anisole, bis (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, anthraquinone, thioxanthone and naphthalimide, and further preferably benzoin dimethyl ether, benzophenone or diethoxyacetophenone.
In the present invention, in the step (1), the mass ratio of the polyethoxy dithiol to the 1,1,3, 3-tetraalkyl-1, 3-divinyldisiloxane is preferably 1:1.4 to 1.6, and more preferably 1:1.45 to 1.5; the amount of the initiator is preferably 0.05 to 0.1 wt% of the total mass of the polyethoxy dithiol and the 1,1,3, 3-tetraalkyl-1, 3-divinyldisiloxane, and more preferably 0.06 to 0.08 wt% of the total mass of the polyethoxy dithiol and the 1,1,3, 3-tetraalkyl-1, 3-divinyldisiloxane.
In the invention, in the step (2), the mass ratio of the vinyl-terminated poly (siloxane-hetero sulfide) to the 2-mercaptoethanol is preferably 1:2 to 3, and more preferably 1:2.5 to 2.8; the amount of the initiator is preferably 0.05 to 0.1 wt% based on the total mass of the vinyl-terminated poly (siloxane-heterosulfide) and 2-mercaptoethanol, and more preferably 0.07 to 0.09 wt% based on the total mass of the vinyl-terminated poly (siloxane-heterosulfide) and 2-mercaptoethanol.
In the invention, in the step (1) and the step (2), the reaction temperature is preferably 20-30 ℃ independently, and more preferably 23-28 ℃; the reaction time is preferably 15 to 30min, and more preferably 18 to 25 min.
The invention also provides a method for preparing the organic silicon waterborne polyurethane by using the poly (siloxane-heterosulfide) dihydric alcohol, which comprises the following steps:
step A1: mixing an isocyanate compound and a first solvent to obtain a first mixture; mixing poly (siloxane-heterosulfide) dihydric alcohol, polysiloxane dihydric alcohol, a catalyst and a second solvent to obtain a second mixture; mixing the first mixture and the second mixture for reaction to obtain an NCO-terminated prepolymer;
step B1: reacting the NCO-terminated prepolymer, a chain extender, a neutralizer and a solvent to obtain a chain-extended prepolymer;
step C1: carrying out an emulsion reaction on the chain extension prepolymer and water to obtain organosilicon waterborne polyurethane;
in the present invention, the polysiloxane diol has the structural formula:
wherein, R is independently alkyl or aryl; m is preferably any value of 2 to 4, and more preferably 2 or 3.
In the present invention, the chain extender is preferably one or more of butanediol, ethylene glycol, diethylene glycol, propylene glycol, 1, 6-hexanediol, 1, 4-cyclohexanediol, neopentyl glycol, hydroquinone bis (β -hydroxyethyl) ether, hydrogenated bisphenol a, bis (2-hydroxyethyl) terephthalate, resorcinol dihydroxyethyl ether, α -allyl glyceryl ether, TMP monoallyl ether, ethylenediamine, 1, 4-cyclohexanediamine, N-methyldiethanolamine, diethylenetriamine, triethylenetetramine, trimethylolpropane, 2-dihydroxymethylpropionic acid, 2-dihydroxymethylbutyric acid, sodium ethylenediamine ethanesulfonate, sodium diaminobenzenesulfonate, sodium 1, 4-butanediol sulfonate;
further preferably, when the chain extender is a single chain extender, the single chain extender is butanediol, ethylene glycol, diethylene glycol, propylene glycol, 1, 6-hexanediol, 1, 4-cyclohexanediol, neopentyl glycol, ethylenediamine, 1, 4-cyclohexanediamine, N-methyldiethanolamine, diethylenetriamine, triethylene tetramine, 2-dihydroxymethylpropanoic acid, 2-dihydroxymethylbutyric acid, sodium ethylenediamine sulphonate, sodium diaminobenzenesulphonate or sodium 1, 4-butanediolsulphonate; when the chain extender is a mixed chain extender, the mass ratio of the mixed chain extender to the chain extender is 1-10: 1-10 parts of a mixed chain extender of butanediol and 2, 2-dihydroxy methyl butyric acid, wherein the mass ratio of the chain extender to the mixed chain extender is 1-10: 1-10 parts of a mixed chain extender of butanediol and 2, 2-dihydroxy methyl propionic acid, wherein the mass ratio of the mixed chain extender to the butanediol is 1-10: 1-10 parts of a mixed chain extender of ethylene glycol and 2, 2-dihydroxy methyl butyric acid, wherein the mass ratio of the mixed chain extender to the ethylene glycol to the 2, 2-dihydroxy methyl butyric acid is 1-10: 1-10 parts of a mixed chain extender of butanediol and ethylene diamine ethyl sodium sulfonate, wherein the mass ratio of the mixed chain extender to the ethylene diamine ethyl sodium sulfonate is 1-10: 1-10 parts of a mixed chain extender of ethylene glycol and ethylene diamine ethyl sodium sulfonate.
In the present invention, the neutralizing agent is preferably one or more of trimethylamine, triethylamine, tripropylamine, tributylamine, sodium hydroxide, aqueous ammonia, acetic acid, oxalic acid, glycolic acid, dichloromethyl toluene, dimethylcyclohexylamine, dimethylethylamine, o-dichloromethyl toluene, and p-dichloromethyl toluene, and is further preferably one or more of trimethylamine, triethylamine, tripropylamine, tributylamine, aqueous ammonia, o-dichloromethyl toluene, and p-dichloromethyl toluene.
In the present invention, in the step a1, the first mixture and the second mixture are mixed in the following manner: the second mixture was added dropwise to the first mixture in a three-necked flask equipped with mechanical stirring, a reflux condenser, an argon gas line, and a constant pressure dropping funnel, and mixed.
In the present invention, in the step a1, the mass-to-volume ratio of the isocyanate compound, the first solvent, the poly (siloxane-heterosulfide) diol, the polysiloxane diol, and the second solvent is preferably 3.9 to 6 g: 1-5 mL: 1 g: 1-4 g: 1-5 mL, more preferably 4-5 g: 2-3 mL: 1 g: 2-3 g: 2-4 mL; the amount of the catalyst used is preferably 3 to 6 wt% of the total mass of the isocyanate compound, the poly (siloxane-hetero sulfide) diol and the polysiloxane diol, and more preferably 4 to 5 wt% of the total mass of the isocyanate compound, the poly (siloxane-hetero sulfide) diol and the polysiloxane diol.
In the invention, in the step A1, the mixing reaction temperature is preferably 65-75 ℃, and further preferably 70-72 ℃; the mixing reaction time is preferably 1.5 to 2.5 hours, and more preferably 100 to 130 min.
In the invention, in the step B1, the mass-to-volume ratio of the chain extender to the neutralizer to the solvent is preferably 0.36-1.8 g to 0.84-5.04 g to 1-5 mL, and more preferably 0.5-1.2 g to 0.9-4.5 g to 2-4 mL; the mass ratio of the chain extender in the step B1 to the poly (siloxane-hetero sulfide) glycol in the step A1 is preferably 0.36-1.8: 1, more preferably 0.5 to 1.5: 1.
in the invention, in the step B1, the reaction temperature is preferably 65-70 ℃, and is further preferably 67-69 ℃; the reaction time is preferably 4 to 6 hours, and more preferably 5 to 5.5 hours.
In the invention, the mass volume ratio of the chain extender in the step B1 to the water in the step C1 is preferably 0.36-1.8 g: 5 to 20mL, more preferably 0.6 to 1.2g: 10-15 mL.
In the invention, in the step C1, the temperature of the emulsification reaction is preferably 65-70 ℃, and further preferably 67-69 ℃; the time for the emulsification reaction is preferably 0.5 to 1 hour, and more preferably 40 to 50 min.
In the invention, the emulsification reaction is carried out under the condition of stirring, and the stirring speed is preferably 600-800 r/min, and more preferably 650-700 r/min.
In the present invention, the reactions in steps a1, B1, and C1 are independently performed under an atmosphere of a protective gas.
The invention also provides the organosilicon waterborne polyurethane prepared by the method for preparing the organosilicon waterborne polyurethane from the poly (siloxane-hetero thioether) dihydric alcohol.
The present invention also provides a method of preparing a silicone polyurethane elastomer from the poly (siloxane-heterosulfide) diol comprising the steps of:
step A2: mixing an isocyanate compound and a solvent to obtain a third mixture; mixing poly (siloxane-heterosulfide) glycol, a catalyst and a solvent to obtain a fourth mixture; reacting the third mixture with the fourth mixture to obtain an NCO-terminated prepolymer;
step B2: mixing and reacting the NCO-terminated prepolymer, the chain extender and the solvent, and drying to obtain the organosilicon polyurethane elastomer.
In the present invention, in the step a2, the third mixture and the fourth mixture are mixed in a manner that: the fourth mixture was added dropwise to the third mixture in a three-necked flask equipped with mechanical stirring, a reflux condenser, an argon gas line, and a constant pressure dropping funnel, and mixed.
In the present invention, the chain extender is preferably one or more of 1, 4-butanediol, ethylene glycol, diethylene glycol, propylene glycol, 1, 6-hexanediol, 1, 4-cyclohexanediol, neopentyl glycol, hydroquinone bis (. beta. -hydroxyethyl) ether, hydrogenated bisphenol A, bis (2-hydroxyethyl) terephthalate, resorcinol dihydroxyethyl ether, α -allyl glycerol ether, TMP monoallyl ether, ethylenediamine, 1, 4-cyclohexanediamine, diethylenetriamine, trimethylolpropane, and more preferably one or more of 1, 4-butanediol, ethylene glycol, propylene glycol, 1, 6-hexanediol, 1, 4-cyclohexanediol, neopentyl glycol, ethylenediamine, and 1, 4-cyclohexanediamine.
In the present invention, in the step a2, the mass-to-volume ratio of the isocyanate compound to the solvent in the third mixture is preferably 4 to 8g: 1-5 mL, more preferably 5-6 g: 2-3 mL; the mass ratio of the poly (siloxane-heterosulfide) diol to the isocyanate compound is preferably 1: 4-8, and more preferably 1: 5-7; the using amount of the catalyst is preferably 3-6 wt% of the total mass of the isocyanate compound and the poly (siloxane-hetereo-sulfide) glycol, and more preferably 4-5 wt% of the total mass of the isocyanate compound and the poly (siloxane-hetereo-sulfide) glycol; the mass to volume ratio of poly (siloxane-co-thioether) diol to solvent in the fourth mixture is preferably 1 g: 1-5 mL, more preferably 1 g: 2-4 mL.
In the invention, in the step A2, the reaction temperature is preferably 65-75 ℃, and is further preferably 68-72 ℃; the reaction time is preferably 1.5 to 2.5 hours, and more preferably 110 to 140 min.
In the invention, the mass ratio of the poly (siloxane-heterosulfide) diol obtained in the step A2 to the chain extender obtained in the step B2 is preferably 1: 2-6, and more preferably 1: 3-5; in the step B2, the mass-to-volume ratio of the chain extender to the solvent is preferably 2-6 g: 1-5 mL, more preferably 3-5 g: 2-3 mL.
In the invention, in the step B2, the mixing reaction temperature is preferably 65-70 ℃, and further preferably 67-68 ℃; the mixing reaction time is preferably 3 to 5 hours, and more preferably 3.5 to 4.5 hours.
In the present invention, the reactions in steps a2 and B2 are independently performed under an atmosphere of a protective gas.
In the invention, in the step B2, before drying, a product obtained by mixing and reacting an NCO end-capping prepolymer, a chain extender and a solvent is subjected to standing treatment; the standing treatment is carried out in a polytetrafluoroethylene mold, the temperature of the standing treatment is room temperature, and the time of the standing treatment is 0.5-1.5 d.
The invention also provides the organosilicon polyurethane elastomer prepared by the method for preparing the organosilicon polyurethane elastomer from the poly (siloxane-heterosulfide) dihydric alcohol.
In the preparation process of the organosilicon waterborne polyurethane and the organosilicon polyurethane elastomer, the isocyanate compound, the catalyst and the solvent are specifically as follows:
the structural formula of the isocyanate compound is as follows:
Q(NCO)c
wherein, Q is independently preferably an alkyl group or an aryl group, and more preferably an aryl group; c is 2.
Specifically, the isocyanate compound is preferably one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate, and is further preferably isophorone diisocyanate or diphenylmethane diisocyanate, independently.
The catalyst is independently preferably one or more of dibutyltin dilaurate, dibutyltin diacetate, dibutyltin mercaptide, dibutyltin dimaleate, dioctyltin mercaptide, dioctyltin sulfate, tributyltin chloride, butyltin trichloride, stannous isooctanoate, and dibutyltin diethylhexanoate, and is further independently preferably one or more of dibutyltin dilaurate, dibutyltin mercaptide, stannous isooctanoate, dioctyltin sulfate, and dibutyltin dimaleate.
The solvent is independently preferably one or more of toluene, xylene, acetone, butanone, methyl ethyl ketone, dioxane, tetrahydrofuran, ethyl acetate, butyl acetate, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone;
further independently preferably, when the solvent is a single solvent, the single solvent is acetone, tetrahydrofuran, ethyl acetate, dimethylformamide or dimethylacetamide; when the solvent is a mixed solvent, the mixed solvent is a mixed solvent of ethyl acetate and dimethyl sulfoxide with a mass ratio of 5-20: 1, a mixed solvent of methyl ethyl ketone and dimethyl formamide with a mass ratio of 5-20: 1, a mixed solvent of butanone and dimethyl formamide with a mass ratio of 5-20: 1, a mixed solvent of tetrahydrofuran and dimethyl formamide with a mass ratio of 5-20: 1, a mixed solvent of butanone and dimethyl acetamide with a mass ratio of 5-20: 1, a mixed solvent of tetrahydrofuran and dimethyl sulfoxide with a mass ratio of 5-10: 4-7: 1, a mixed solvent of tetrahydrofuran, acetone and dimethyl formamide with a mass ratio of 5-10: 4-7: 1, and a mixed solvent of petroleum ether, ethyl acetate and dimethyl formamide with a mass ratio of 5-10: 4-7: 1.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparing raw materials:
1 part of 3, 6-dioxa-1, 8-octanedithiol, 1.4 parts of 1,1,3, 3-tetramethyl-1, 3-divinyldisiloxane, 2.4 parts of 2-mercaptoethanol, 3, 6-dioxa-1, 8-octanedithiol, 1% by weight of benzoin dimethyl ether based on the total mass of 1,1,3, 3-tetramethyl-1, 3-divinyldisiloxane;
the preparation process comprises the following steps:
(1) synthesis of vinyl-terminated poly (siloxane-heterosulfide):
3, 6-dioxa-1, 8-octane dithiol and 1,1,3, 3-tetramethyl-1, 3-divinyl disiloxane are filled into a reaction container with stirring, and the bulk polymerization reaction is carried out for 15min at room temperature under a 365nm ultraviolet lamp to synthesize vinyl-terminated poly (siloxane-heterosulfide);
(2) synthesis of poly (siloxane-heterosulfides):
adding 2-mercaptoethanol and benzoin dimethyl ether into the synthesized vinyl-terminated poly (siloxane-heterosulfide), and carrying out bulk polymerization reaction for 20min at room temperature under a 365nm ultraviolet lamp to synthesize poly (siloxane-heterosulfide) dihydric alcohol, wherein the molecular weight of the poly (siloxane-heterosulfide) dihydric alcohol is 2000;
the structural formula of the synthesized poly (siloxane-heterosulfide) diol is shown in figure 1, wherein R is methyl, n is 4.5, and a is 1.
Example 2
Preparing raw materials:
1 part of the poly (siloxane-heterosulfide) diol obtained in example 1, 2 parts of α, ω -bis (hydroxyethoxypropyl) polydimethylsiloxane, 5.8 parts of diphenylmethane diisocyanate, 0.36 part of butanediol, 3.24 parts of triethylamine, diphenylmethane diisocyanate, poly (siloxane-heterosulfide) diol and 3% by weight of stannous isooctanoate based on the total mass of α, ω -bis (hydroxyethyloxypropyl) polydimethylsiloxane;
the preparation process comprises the following steps:
(1) synthesis of NCO-terminated prepolymer
Adding diphenylmethane diisocyanate and 5mL of acetone in proportion into a three-necked bottle provided with a mechanical stirring and condensing reflux device, an argon guide pipe and a constant-pressure dropping funnel, adding poly (siloxane-heterosulfide) dihydric alcohol, alpha, omega-bis (hydroxyethoxypropyl) polydimethylsiloxane, stannous isooctoate and 4mL of acetone into the constant-pressure dropping funnel, dropwise adding under the protection of argon, and reacting for 1.5 hours at the reaction temperature of 65 ℃ after the dropwise adding is finished to obtain an NCO end-capped prepolymer;
(2) neutralizing agent neutralization and prepolymer chain extension
Adding butanediol, triethylamine and 4mL of butanone into the NCO-terminated prepolymer, reacting for 4 hours under the protection of argon gas, and stopping the reaction to obtain a chain-extended prepolymer;
(3) emulsification
And adding 10mL of deionized water into the chain extension prepolymer, and reacting for 0.5h under the stirring conditions of the temperature of 65 ℃ and the rotating speed of 600r/min to obtain a sample sheet 1.
Example 3
Preparing raw materials:
1 part of the poly (siloxane-hethioether) diol obtained in example 1, 2 parts of α, ω -bis (hydroxyethoxypropyl) polydimethylsiloxane, 5.8 parts of isophorone diisocyanate, 1.8 parts of ethylene glycol, 1.8 parts of o-bischloromethylbenzene, isophorone diisocyanate, poly (siloxane-hethioether) diol and 4% by weight, based on the total mass of α, ω -bis (hydroxyethoxypropyl) polydimethylsiloxane, of dibutyltin dilaurate;
the preparation process comprises the following steps:
(1) NCO-terminated prepolymer synthesis
Adding isophorone diisocyanate and 4mL dioxane in proportion into a three-mouth bottle provided with a mechanical stirring and condensing reflux device, an argon guide tube and a constant-pressure dropping funnel, adding poly (siloxane-heterosulfide) dihydric alcohol, alpha, omega-bis (hydroxyethoxypropyl) polydimethylsiloxane, dibutyltin dilaurate and 4mL dioxane into the constant-pressure dropping funnel, dropwise adding under the protection of argon, reacting for 2 hours after dropwise adding is completed, and obtaining NCO end-capping prepolymer, wherein the reaction temperature is 70 ℃;
(2) neutralizing agent neutralization and prepolymer chain extension
Adding ethylene glycol, o-dichloromethyl toluene and 5mL of tetrahydrofuran into the NCO-terminated prepolymer, reacting for 5 hours under the protection of argon, and stopping the reaction to obtain a chain-extended prepolymer;
(3) emulsification
And adding 15mL of deionized water into the chain extension prepolymer, and reacting for 1h under the stirring conditions of the temperature of 70 ℃ and the rotating speed of 750r/min to obtain a sample wafer 2.
Example 4
Preparing raw materials:
1 part of the poly (siloxane-heterosulfide) diol obtained in example 1, 2 parts of α, ω -bis (hydroxyethoxypropyl) polydimethylsiloxane, 5.8 parts of hexamethylene diisocyanate, 0.72 part of ethylene glycol, 2.88 parts of aqueous ammonia, hexamethylene diisocyanate, poly (siloxane-heterosulfide) diol and 6% by weight, based on the total mass of α, ω -bis (hydroxyethoxypropyl) polydimethylsiloxane, of dibutyltin mercaptide;
the preparation process comprises the following steps:
(1) NCO-terminated prepolymer synthesis
Adding hexamethylene diisocyanate and 3mL ethyl acetate in proportion into a three-mouth bottle provided with a mechanical stirring and condensing reflux device, an argon guide pipe and a constant-pressure dropping funnel, adding poly (siloxane-heterosulfide) dihydric alcohol, alpha, omega-bis (hydroxyethoxypropyl) polydimethylsiloxane, dibutyltin mercaptide and 5mL ethyl acetate into the constant-pressure dropping funnel, dropwise adding under the protection of argon, reacting for 2.5 hours after the dropwise adding is finished, and obtaining an NCO end-capping prepolymer at the reaction temperature of 75 ℃;
(2) neutralizing agent neutralization and prepolymer chain extension
Adding ethylene glycol, ammonia water and 5mL of ethyl acetate into the NCO-terminated prepolymer, reacting for 6 hours under the protection of argon gas, and stopping the reaction to obtain a chain-extended prepolymer;
(3) emulsification
And (3) adding 20mL of deionized water into the chain extension prepolymer, and reacting for 1h under the stirring conditions of the temperature of 75 ℃ and the rotating speed of 800r/min to obtain a sample 3.
Example 5
Preparing raw materials:
1 part of the poly (siloxane-heterosulfide) diol obtained in example 1, 2 parts of α, ω -bis (hydroxyethoxypropyl) polydimethylsiloxane, 5.8 parts of toluene diisocyanate, 0.72 part of butanediol, 2.88 parts of p-dichloromethyl toluene, toluene diisocyanate, poly (siloxane-heterosulfide) diol and 3.5% by weight of dioctyltin sulfate based on the total mass of α, ω -bis (hydroxyethoxypropyl) polydimethylsiloxane;
the preparation process comprises the following steps:
(1) NCO-terminated prepolymer synthesis
Adding toluene diisocyanate and 4mL of dimethylacetamide in proportion in a three-necked bottle provided with a mechanical stirring and condensing reflux device, an argon guide pipe and a constant-pressure dropping funnel, adding poly (siloxane-heterosulfide) dihydric alcohol, alpha, omega-bis (hydroxyethoxypropyl) polydimethylsiloxane, dioctyltin sulfate and 4mL of dimethylacetamide in the constant-pressure dropping funnel, dropwise adding under the protection of argon, and reacting for 2 hours after the dropwise adding is finished, wherein the reaction temperature is 68 ℃ to obtain an NCO end-capped prepolymer;
(2) neutralizing agent neutralization and prepolymer chain extension
Adding butanediol, dichloromethyl toluene and 4mL of dimethyl acetamide into the NCO-terminated prepolymer, reacting for 5 hours under the protection of argon, and stopping the reaction to obtain a chain-extended prepolymer;
(3) emulsification
And adding 20mL of deionized water into the chain extension prepolymer, and reacting for 1h under the stirring conditions that the temperature is 68 ℃ and the rotating speed is 650r/min to obtain a sample wafer 4.
Example 6
Preparing raw materials:
1 part of the poly (siloxane-hetrosulfide) diol obtained in example 1, 6.67 parts of diphenylmethane diisocyanate, 5.67 parts of ethylene glycol, 3.3% by weight of stannous isooctoate relative to the total mass of diphenylmethane diisocyanate and poly (siloxane-hetrosulfide) diol;
the preparation process comprises the following steps:
(1) synthesis of NCO-terminated prepolymer
Adding diphenylmethane diisocyanate and 5mL of tetrahydrofuran in proportion into a three-necked bottle provided with a mechanical stirring and condensing reflux device, an argon guide pipe and a constant-pressure dropping funnel, adding poly (siloxane-heterosulfide) dihydric alcohol, stannous isooctanoate and 5mL of tetrahydrofuran in proportion into the constant-pressure dropping funnel, dropwise adding under the protection of argon, and reacting for 2 hours at the reaction temperature of 65 ℃ after the dropwise adding is finished to obtain an NCO end-capping prepolymer;
(2) chain extension of prepolymer
Adding ethylene glycol and 5mL of tetrahydrofuran into the NCO-terminated prepolymer, reacting for 3.5 hours under the protection of argon, and stopping the reaction;
(3) tabletting
Placing the product of the step (2) in a polytetrafluoroethylene mold, and placing for 1 day at room temperature; after 1 day, the sample was placed in a vacuum drying oven for one week to obtain sample 5.
Example 7
Preparing raw materials:
1 part of the poly (siloxane-heterosulfide) diol obtained in example 1, 4.44 parts of toluene diisocyanate, 3.44 parts of 1, 4-butanediol, 4% by weight of dibutyltin dimaleate relative to the total mass of toluene diisocyanate and poly (siloxane-heterosulfide) diol;
the preparation process comprises the following steps:
(1) synthesis of NCO-terminated prepolymer
Adding toluene diisocyanate and 4mL of toluene in proportion into a three-mouth bottle provided with a mechanical stirring and condensing reflux device, an argon guide tube and a constant-pressure dropping funnel, adding poly (siloxane-heterosulfide) dihydric alcohol, dibutyltin dimaleate and 4mL of toluene in proportion into the constant-pressure dropping funnel, dropwise adding under the protection of argon, reacting for 2.5 hours after the dropwise adding is finished, and obtaining an NCO end-capping prepolymer at the reaction temperature of 75 ℃;
(2) chain extension of prepolymer
Adding 1, 4-butanediol and 4mL of methylbenzene into the NCO-terminated prepolymer, reacting for 5 hours under the protection of argon, and stopping the reaction;
(3) tabletting
Placing the product of the step (2) in a polytetrafluoroethylene mold, and placing for 1 day at room temperature; after 1 day, the sample was placed in a vacuum drying oven for one week to obtain a sample 6.
The hydrophobicity of the sample wafers 1 to 4 obtained in examples 2 to 5 was tested, and the test results are shown in table 1:
TABLE 1 Water contact Angle test results for samples 1-4
| Name(s) | Angle of water contact angle |
| Sample 1 | 104.5° |
| Sample 2 | 104.8° |
| Sample 3 | 104° |
| Sample 4 | 109.4° |
The mechanical properties of the sample wafers 1 to 6 obtained in examples 2 to 7 were measured, and the test results are shown in table 2 and fig. 3 to 5:
table 2 mechanical property test results of sample wafers 1-6
Water absorption test was performed on the sample wafers 1 to 4 obtained in examples 2 to 5, and the test results are shown in Table 3.
The test method comprises the following steps: cutting the sample into 2 cm square pieces, and recording the weight as W 1 Soaking the sample in distilled water at room temperature for 24h, taking out carefully, wiping off water on the surface of the sample, and weighing W 2 And calculating the formula:
A＝(W 2 -W 1 )/W 1 ×100％
in the formula: a: water absorption,%; w 1 : g, the mass of the glue film before water absorption; w 2 : quality of the glue film after water absorption, g.
TABLE 3 test results of water absorption of sample 1-4
| Name (R) | Water absorption (%) |
| Sample wafer 1 | 2.56 |
| Sample 2 | 2.38 |
| Sample 3 | 2.27 |
| Sample wafer 4 | 2.32 |
As can be seen from tables 1 to 3 and figures 3 to 5, the waterborne polyurethane material prepared by the invention has the advantages of good hydrophobicity, water resistance and heat resistance, soft hand feeling, high solid content, high film forming speed and excellent hydrophilicity; the polyurethane elastomer material has excellent mechanical properties.
The water resistance test was performed on the sample sheets 1 to 4 obtained in examples 2 to 5 by the following method: the sample wafer uses NAF-H-V level asbestos-free cement flat plate as a base plate, and the periphery of the sample wafer is sealed by vacuum ester. Immersed in laboratory specified GB/T6682-. The coating morbid phenomena such as foaming, cracking, peeling, powder dropping, obvious color change and the like do not appear in 2 of the 3 sample wafers, and the sample wafers can be evaluated as 'no abnormal condition'.
Through detection, three respective sample wafers 1-4 have no coating film pathological phenomena such as foaming, cracking, peeling, powder falling, obvious color change and the like, and can be evaluated as 'no abnormity'.
As can be seen from FIG. 5, the water resistance of the organosilicon waterborne polyurethane material obtained by the invention is stronger than that of polyether waterborne polyurethane and is close to that of polysiloxane waterborne polyurethane.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A poly (siloxane-heterosulfide) glycol, wherein the poly (siloxane-heterosulfide) glycol has the formula:
wherein R is independently a hydrocarbyl or aryl group; n is any value of 2-10; a is any value of 1 to 4.
2. The method of preparing a poly (siloxane-hetrosulfide) diol according to claim 1, comprising the steps of:
(1) preparation of vinyl-terminated poly (siloxane-heterosulfide): reacting polyethoxy dithiol, 1,3, 3-tetraalkyl-1, 3-divinyldisiloxane and an initiator to obtain vinyl-terminated poly (siloxane-heterpulfide);
(2) preparation of poly (siloxane-heterethioether) diol: reacting vinyl-terminated poly (siloxane-heterosulfide), 2-mercaptoethanol and an initiator to obtain poly (siloxane-heterosulfide) diol;
the structural formula of the vinyl-terminated poly (siloxane-heterosulfide) is as follows:
wherein R is independently a hydrocarbyl or aryl group; n is any value of 2-10; a is any value of 1-4;
the structural formula of the polyethoxy dithiol is as follows:
wherein a is any value of 1-4.
3. The method of claim 2, wherein the initiator is independently one or more of benzoin dimethyl ether, benzophenone, diethoxyacetophenone, diphenylmethyl ether, bis (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, anthraquinone, thioxanthone, and naphthalimide.
4. The method for preparing poly (siloxane-hetereosulfide) diol according to claim 2, wherein in the step (1), the mass ratio of polyethoxy dithiol to 1,1,3, 3-tetraalkyl-1, 3-divinyl disiloxane is 1: 1.4-1.6; the amount of the initiator is 0.05-0.1 wt% of the total mass of the polyethoxy dithiol and the 1,1,3, 3-tetraalkyl-1, 3-divinyl disiloxane.
5. The method for preparing poly (siloxane-hetrosulfide) diol according to claim 2 or 4, wherein in the step (2), the mass ratio of the vinyl-terminated poly (siloxane-hetrosulfide) to the 2-mercaptoethanol is 1: 2-3; the amount of the initiator is 0.05-0.1 wt% of the total mass of the vinyl-terminated poly (siloxane-heterosulfide) and the 2-mercaptoethanol.
6. The method for preparing poly (siloxane-hetereosulfide) glycol according to any one of claims 2 to 4, wherein the reaction temperature in step (1) and step (2) is 20 to 30 ℃ independently, and the reaction time is 15 to 30min independently.
7. A method of preparing a silicone aqueous polyurethane from a poly (siloxane-heterosulfide) diol as set forth in claim 1, comprising the steps of:
step A1: mixing an isocyanate compound and a first solvent to obtain a first mixture; mixing poly (siloxane-heterosulfide) dihydric alcohol, polysiloxane dihydric alcohol, a catalyst and a second solvent to obtain a second mixture; mixing the first mixture and the second mixture for reaction to obtain an NCO-terminated prepolymer;
step B1: reacting the NCO-terminated prepolymer, a chain extender, a neutralizer and a solvent to obtain a chain-extended prepolymer;
step C1: carrying out an emulsion reaction on the chain extension prepolymer and water to obtain organosilicon waterborne polyurethane;
in the step A1, the mass volume ratio of the isocyanate compound, the first solvent, the poly (siloxane-heterosulfide) diol, the polysiloxane diol and the second solvent is 3.9-6 g: 1-5 mL: 1 g: 1-4 g: 1-5 mL; the amount of the catalyst is 3-6 wt% of the total mass of the isocyanate compound, the poly (siloxane-heterosulfide) diol and the polysiloxane diol;
in the step A1, the temperature of the mixing reaction is 65-75 ℃, and the time of the mixing reaction is 1.5-2.5 h;
in the step B1, the mass-to-volume ratio of the chain extender to the neutralizer to the solvent is 0.36-1.8 g to 0.84-5.04 g to 1-5 mL; the mass ratio of the chain extender in the step B1 to the poly (siloxane-hetero sulfide) glycol in the step A1 is 0.36-1.8: 1;
in the step B1, the reaction temperature is 65-70 ℃, and the reaction time is 4-6 h;
the mass-to-volume ratio of the chain extender in the step B1 to the water in the step C1 is 0.36-1.8 g: 5-20 mL;
in the step C1, the temperature of the emulsification reaction is 65-70 ℃, and the time of the emulsification reaction is 0.5-1 h;
the reactions in steps a1, B1 and C1 were independently carried out under an atmosphere of a protective gas.
8. The aqueous silicone polyurethane prepared by the method for preparing aqueous silicone polyurethane from poly (siloxane-oxathioether) glycol as defined in claim 7.
9. A method of preparing a silicone polyurethane elastomer from the poly (siloxane-heterosulfide) diol of claim 1, comprising the steps of:
step A2: mixing an isocyanate compound and a solvent to obtain a third mixture; mixing poly (siloxane-heterosulfide) glycol, a catalyst and a solvent to obtain a fourth mixture; reacting the third mixture with the fourth mixture to obtain an NCO-terminated prepolymer;
step B2: mixing and reacting an NCO-terminated prepolymer, a chain extender and a solvent, and drying to obtain an organosilicon polyurethane elastomer;
in the step A2, the mass-to-volume ratio of the isocyanate compound to the solvent in the third mixture is 4-8 g: 1-5 mL; the mass ratio of the poly (siloxane-hetero thioether) diol to the isocyanate compound is 1: 4-8; the amount of the catalyst is 3-6 wt% of the total mass of the isocyanate compound and the poly (siloxane-heterosulfide) diol; the mass to volume ratio of poly (siloxane-heterosulfide) glycol to solvent in the fourth mixture is 1 g: 1-5 mL;
in the step A2, the reaction temperature is 65-75 ℃, and the reaction time is 1.5-2.5 h;
the mass ratio of the poly (siloxane-heterosulfide) diol obtained in the step A2 to the chain extender obtained in the step B2 is 1: 2-6; in the step B2, the mass-to-volume ratio of the chain extender to the solvent is 2-6 g: 1-5 mL;
in the step B2, the temperature of the mixing reaction is 65-70 ℃, and the time of the mixing reaction is 3-5 h;
the reactions in steps a2 and B2 were independently carried out under an atmosphere of a protective gas.
10. A silicone polyurethane elastomer prepared by the method of preparing a silicone polyurethane elastomer from a poly (siloxane-heterosulfide) diol of claim 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694045A (en) * | 2016-03-16 | 2016-06-22 | 烟台大学 | Functionalization method of divinyl double-plywood type oligomeric silsesquioxane |
| EP3263614A1 (en) * | 2016-06-30 | 2018-01-03 | Henkel AG & Co. KGaA | Waterborne hybrid polyurethane/polysiloxane dispersions |
| CN109575233A (en) * | 2018-12-10 | 2019-04-05 | 山东大学 | A kind of silicone polyether type polyurethane elastomer of strong mechanical performance and preparation method thereof |
| CN110759938A (en) * | 2019-11-08 | 2020-02-07 | 山东大学 | Hydroxyalkyl disiloxane containing hetero atoms, preparation method and application thereof |
| US20210269669A1 (en) * | 2018-12-17 | 2021-09-02 | Stahl International B.V. | Process to prepare aqueous polyurethane dispersions in which the polyurethane includes polysiloxane as side chain |
-
2022
- 2022-04-12 CN CN202210380158.0A patent/CN114790293B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694045A (en) * | 2016-03-16 | 2016-06-22 | 烟台大学 | Functionalization method of divinyl double-plywood type oligomeric silsesquioxane |
| EP3263614A1 (en) * | 2016-06-30 | 2018-01-03 | Henkel AG & Co. KGaA | Waterborne hybrid polyurethane/polysiloxane dispersions |
| CN109575233A (en) * | 2018-12-10 | 2019-04-05 | 山东大学 | A kind of silicone polyether type polyurethane elastomer of strong mechanical performance and preparation method thereof |
| US20210269669A1 (en) * | 2018-12-17 | 2021-09-02 | Stahl International B.V. | Process to prepare aqueous polyurethane dispersions in which the polyurethane includes polysiloxane as side chain |
| CN110759938A (en) * | 2019-11-08 | 2020-02-07 | 山东大学 | Hydroxyalkyl disiloxane containing hetero atoms, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| YUJING ZUO, ZHIMING GOU, JINFENG CAO: "From Polymer to Monomer: Cleavage and Rearrangement of Si-O-Si Bonds after Oxidation Yielded an Ordered Cyclic Crystallized Structure" * |
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