CN108610466B - Polyurea elastomer with polysiloxane completely replacing polyether and preparation method thereof - Google Patents
Polyurea elastomer with polysiloxane completely replacing polyether and preparation method thereof Download PDFInfo
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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
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
- C08G18/6529—Compounds of group C08G18/3225 or polyamines of C08G18/38
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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
Abstract
The invention relates to a polyurea elastomer with polysiloxane completely replacing polyether and a preparation method thereof, wherein the preparation method comprises the following steps: (1) respectively adding calculated amounts of aminopropyl terminated polydimethylsiloxane C and diisocyanate compounds into a mixed solvent of an organic solvent A and an organic solvent B, and stirring and reacting for 10-80min at the temperature of 0-50 ℃ to generate an isocyanate group terminated low-molecular-weight prepolymer D; (2) reacting the prepolymer D generated in the step (1) with an amino-terminated compound at 0-30 ℃ for 10-500min to obtain a mixed solution containing a polysiloxane-polyurea polymer; and then volatilizing to remove the solvent to obtain the product. The invention adopts the mixed solvent and reduces sharp microscopic phase separation between the soft segment and the hard segment by regulating and controlling the molecular weight of the aminopropyl terminated polydimethylsiloxane, thereby greatly improving the mechanical property of the elastomer.
Description
Technical Field
The invention relates to a polyurea elastomer with polysiloxane completely replacing polyether and a preparation method thereof, belonging to the technical field of synthesis of organic silicon high polymer materials.
Background
The polysiloxane has a unique molecular structure formed by a Si-O-Si main chain and an organic group side chain, integrates organic-inorganic dual characteristics and functions, and has excellent performances of extremely low glass transition temperature (-123 ℃), high and low temperature resistance, oxidation resistance, weather resistance, low surface energy, good hydrophobicity and the like.
Thermoplastic polyurea elastomers (TPU) are a series of multiphase block polymers with excellent mechanical properties and good elasticity, strong hardness, abrasion and chemical resistance. The polysiloxane-polyurea elastomer prepared by taking polysiloxane as a soft segment has the excellent performances of both polysiloxane and polyurea, overcomes the defect of poor mechanical property of polysiloxane, makes up the defect of poor weather resistance of polyurea, and has wide application in the building industry, the automotive interior, the field of biological materials and the clothing industry.
Of course, the mechanical properties of these silicone-polyurea elastomers are still far inferior to those of the conventional polyureas prepared from polyethers as soft segments. The microscopic phase separation of the soft and hard segments is responsible for the high stable modulus of the thermoplastic polyurea elasticity, but due to the solubility parameter of polydimethylsiloxane (15.6 (Jcm)-3)1/2) And solubility parameter of polyurea (45.6 (Jcm)-3)1/2) Too much difference in the phase, the preparation of polyurea using polysiloxane as soft segment may result in macroscopic phase separation during the reaction, which makes it impossible to form polymer with large molecular weight, and thus, the mechanical properties of the polyurea are affected. Or even if no macroscopic phase separation is formed, the prepared polymer can generate sharp microphase separation at the phase interface of the polysiloxane aggregation phase and the polyurea aggregation phase, and the sharp phase interface can also reduce the effect of transferring the tensile force from the soft segment region to the hard segment region, thereby influencing the mechanical strength of the elastomer.
To avoid sharp microscopic phase separation, it is conventional to use polysiloxanes in combination with polyethers. The solubility parameter of the polyether was 23.5 (Jcm)-3)1/2Interaction energy of ureido group and ether (19.2 kJmol)-1) Greater than the interfacial energy of urea groups and siloxane (7.5 kJmol)-1). This allows the formation of a transition phase between the polysiloxane and polyurea, reducing microphase separation. The specific method is to mix amino-terminated polysiloxane and polyether and then react the mixture with an isocyanate compound to prepare the polyurea elastomer, but the method cannot avoid the connection of the polysiloxane and the isocyanate compound, cannot avoid sharp microphase separation and the influence on the mechanical property of the elastomer, and simultaneously, the introduction of the polyether can influence the performance of the excellent property of the polysiloxane in the elastomer. Meanwhile, the thermoplastic elastomer obtained by the method has unstable performance and poor material performance reproducibility, and the popularization and application of the method are greatly restricted.
Chinese patent document CN103360562A discloses a method for preparing a polysiloxane-polyurea-polyurethane gel material. Stirring and reacting 100-200 parts of polysiloxane with 70-160 parts of diisocyanate at the temperature of 60-90 ℃ for 1-3h to prepare an isocyanate-terminated semi-prepolymer A with the relative mass percent of isocyanate groups of 15-25%; stirring and mixing the isocyanate-terminated semi-prepolymer A and an amino-terminated compound uniformly, and pouring to prepare a polysiloxane-polyurea-polyurethane gel material; wherein the isocyanate-terminated semi-prepolymer A30-60 parts by mass, and the amino-terminated compound 100-400 parts by mass. In this patent document, a hydroxyl-terminated polysiloxane is used, and the reactivity is low, so that the temperature required for the reaction is too high and the reaction time is also long. And the amino-terminated compounds used contain amino-terminated polyethers, the disadvantages of conventional polysiloxane-polyether-polyureas remain.
At present, no method can avoid sharp phase separation and cannot influence the exertion of excellent performance of polysiloxane, so that the mechanical property of the polysiloxane polyurea elastomer is improved.
The invention is therefore proposed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a polyurea elastomer with polysiloxane completely replacing polyether and a preparation method thereof. The mixed solvent is used as a reaction solvent for preparing the polyurea elastomer, and the mixed use of the two solvents can ensure that the soft segment and the hard segment are better dissolved in a system, avoid macroscopic phase separation during reaction, and ensure the generation of a polymer with large molecular weight. Meanwhile, the amine propyl terminated polydimethylsiloxane with proper molecular weight is selected as the soft segment to be used for synthesizing the polyurea elastomer, and the sharp micro-phase separation between the soft segment and the hard segment is reduced by regulating and controlling the molecular weight, so that the mechanical property of the elastomer is greatly improved.
The technical scheme of the invention is as follows:
a polyurea elastomer having a polysiloxane completely substituted for a polyether, the elastomer having the general formula shown in formula (I):
wherein n and m are integers greater than or equal to 1;
x is
Or
CH2CH2CH2CH2CH2CH2；
Y is CH2CH2、CH2CH(CH3)CH2CH2CH2、CH2CH2CH2CH2CH2CH2Or
According to the invention, it is preferred that 1. ltoreq. n.ltoreq.150 and 1. ltoreq. m.ltoreq.50.
According to the present invention, the preparation method of the polyurea elastomer completely replacing the polyether with the polysiloxane comprises the following steps:
(1) respectively adding aminopropyl terminated polydimethylsiloxane C and a diisocyanate compound into a mixed solvent of an organic solvent A and an organic solvent B, and stirring and reacting for 10-80min at the temperature of 0-50 ℃ to generate an isocyanate group terminated prepolymer D with low molecular weight;
(2) reacting the prepolymer D generated in the step (1) with an amino-terminated compound at 0-30 ℃ for 10-500min to obtain a mixed solution containing a polysiloxane-polyurea polymer; then volatilizing to remove the solvent, and obtaining the polyurea elastomer which completely replaces the polyether with the polysiloxane.
According to the preparation method of the present invention, preferably, the organic solvent a in step (1) is xylene, tetrahydrofuran, dimethyl sulfoxide, toluene, acetone, cyclohexane or dioxane;
preferably, the organic solvent B is diethyl ether, dichloromethane, ethyl acetate, isopropanol or n-hexane;
preferably, the volume ratio of the organic solvent A, B is (5-15): 1.
According to the preparation method of the present invention, preferably, the aminopropyl terminated polydimethylsiloxane C in the step (1) has a general formula shown in formula (ii):
in the formula (II), the value of n is the same as that of the formula (I);
further preferably, the relative molecular weight of the aminopropyl terminated polydimethylsiloxane C is in the range of 1000-10000 g/mol.
According to the preparation method of the present invention, preferably, the diisocyanate compound in the step (1) is toluene diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, hexamethylene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate or tetramethylphenylene diisocyanate;
further preferred is diphenylmethane diisocyanate, hexamethylene diisocyanate, methylcyclohexyl diisocyanate, or dicyclohexylmethane diisocyanate.
According to the preparation method of the present invention, the molar ratio of the terminal amino group of the aminopropyl terminated polydimethylsiloxane C in the step (1) to the isocyanate group of the diisocyanate compound is preferably 1 (2-15), and more preferably 1 (3-8).
The molar ratio of the aminopropyl terminated polydimethylsiloxane C to the isocyanate group in the diisocyanate compound has an important influence on the mechanical property of the final elastomer, and the mechanical property of the elastomer is obviously reduced when the molar ratio is beyond the range of the invention.
According to the preparation method of the invention, the reaction temperature in the step (1) is preferably 5-40 ℃ and the reaction time is 10-50 min. The structural general formula of the isocyanate group-terminated low molecular weight prepolymer D prepared in the step (1) of the invention is shown as the formula (III):
according to the preparation method of the present invention, preferably, the amine-terminated compound in step (2) is ethylenediamine, hexamethylenediamine, propylene glycol bis (p-aminobenzoate), 1, 2-bis (2-aminophenylthio) ethane, 2-methyl-1, 5-pentanediamine, 3, 5-diamino-4-trifluoromethylphenetole or 4, 4' -methylenebis (2-ethyl-6-methylcyclohexylamine).
According to the preparation method of the invention, preferably, the reaction temperature in the step (2) is 0-15 ℃, and the reaction time is 5-20 min.
According to the preparation method of the present invention, preferably, the solvent is volatilized at room temperature in the step (2), and the time for volatilizing the solvent is 2-48 h.
The invention has not been described in detail as being prior art in the field.
The invention has the beneficial effects that:
1. the invention adopts the aminopropyl terminated polydimethylsiloxane C as the polyurea elastomer prepared by the soft segment under the condition of the mixed solvent of A and B, and adopts the mixed solvent to better dissolve the soft segment and the hard segment in the system, so that the reaction is faster and more thorough, and the reaction rate is greatly improved.
2. The invention selects the aminopropyl terminated polydimethylsiloxane C with proper molecular weight as the soft segment to synthesize the polyurea elastomer, reduces sharp microcosmic phase separation between the soft segment and the hard segment, thereby greatly improving the mechanical property of the elastomer, having higher mechanical strength and having the tensile strength of 21 MPa.
3. The reaction process of the invention is simpler, and the elastomer with excellent tensile property can be obtained by adopting the least raw materials.
Drawings
FIG. 1 is an infrared spectrum of a polyurea elastomer prepared in example 1 of the present invention, in which a polyether is completely replaced with a polysiloxane.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be illustrative, not limiting and are not intended to limit the scope of the invention.
The raw materials used in the examples are all conventional commercial products.
The aminopropyl terminated polydimethylsiloxane C described in the examples was prepared as follows:
a four-necked flask equipped with a thermometer, a bulb-shaped condenser, mechanical stirring and nitrogen inlet was charged with the calculated amount of D4Alpha, omega-aminopropyldisiloxane and traces of KOH solid powder. And heating the system to 80-120 ℃ in an oil bath under the mechanical stirring, and carrying out equilibrium reaction for 8 hours. After the reaction is finished, stopping heating, adding glacial acetic acid with the molar quantity equal to that of the added KOH for neutralization reaction, and performing reduced pressure distillation operation to evaporate low-boiling-point substances. The product was filtered to give aminopropyl terminated polydimethylsiloxane.
Examples 1,
A preparation method of polyurea elastomer with polysiloxane completely replacing polyether comprises the following steps:
30g of dicyclohexylmethane diisocyanate was added to a four-neck flask equipped with a constant pressure dropping funnel, a drying tube, mechanical stirring and a nitrogen-introducing device, and completely dissolved in a mixed solvent of xylene and isopropanol (volume ratio 6: 1), 70g of aminopropyl terminated polydimethylsiloxane C having a molecular weight of 4000 was completely dissolved with vigorous stirring, and then dropwise added to the above solution through the dropping funnel, and reacted at 40 ℃ for 30min to prepare prepolymer D, and finally 20g of 2-methyl-1, 5-pentanediamine was dissolved in the mixed solution, and finally dropwise added to a reactor through the dropping funnel, reacted at 5 ℃ for 10min, and the product was poured into a mold, and the solvent was removed by volatilization at room temperature to obtain an elastomer.
The resulting elastomer structure was as follows:
the tensile strength of the material is 21MPa, and the elongation at break is 100 percent.
The IR spectrum of the polyurea elastomer prepared by this example, which completely replaced the polyether with polysiloxane, is shown in FIG. 1.
Examples 2,
A preparation method of polyurea elastomer with polysiloxane completely replacing polyether comprises the following steps:
20g of diphenylmethane diisocyanate was added into a four-neck flask equipped with a constant pressure dropping funnel, a drying tube, mechanical stirring and a nitrogen-introducing device, and dissolved completely in a mixed solvent of tetrahydrofuran and dichloromethane (volume ratio: 8: 1), 60g of aminopropyl terminated polydimethylsiloxane C having a molecular weight of 2000 was dissolved completely under vigorous stirring, and then added dropwise into the above solution through the dropping funnel, reacted at 30 ℃ for 10min to prepare a prepolymer D, and finally 20g of hexamethylenediamine was dissolved in the mixed solution, added dropwise into a reactor through the dropping funnel, reacted at 10 ℃ for 15min, and the product was poured into a mold, and evaporated at room temperature to remove the solvent, thereby obtaining an elastomer.
The resulting elastomer structure was as follows:
the tensile strength of the material is 20MPa, and the elongation at break is 110%.
Examples 3,
A preparation method of polyurea elastomer with polysiloxane completely replacing polyether comprises the following steps:
30g of dicyclohexylmethane diisocyanate is added into a four-neck flask provided with a constant-pressure dropping funnel, a drying tube, mechanical stirring and a nitrogen introducing device, a mixed solvent of dimethyl sulfoxide and n-hexane (the volume ratio is 8: 1) is used for completely dissolving, 70g of block copolymer A with the molecular weight of 3000 is dropwise added into the solution through the dropping funnel under strong stirring, the solution reacts for 20min at the temperature of 40 ℃ to prepare prepolymer D, 20g of 4, 4' -methylenebis (2-ethyl-6-methylcyclohexylamine) is dissolved into the mixed solution, the solution is dropwise added into a reactor through the dropping funnel, the reaction is carried out for 20min at the temperature of 10 ℃, the product is poured into a mold, and the solvent is volatilized at the room temperature to remove the solvent, so that the elastomer is obtained.
The tensile strength of the material is 18MPa, and the elongation at break is 120 percent.
Examples 4,
A preparation method of polyurea elastomer with polysiloxane completely replacing polyether comprises the following steps:
20g of diphenylmethane diisocyanate was added into a four-neck flask equipped with a constant pressure dropping funnel, a drying tube, mechanical stirring and a nitrogen-introducing device, and dissolved completely in a mixed solvent of toluene and n-hexane (volume ratio 5: 1), 60g of aminopropyl terminated polydimethylsiloxane C having a molecular weight of 5000 was dissolved completely under vigorous stirring, and then added dropwise into the above solution through the dropping funnel, reacted at 40 ℃ for 30min to prepare a prepolymer D, and finally 20g of ethylenediamine was dissolved in the mixed solution, added dropwise into a reactor through the dropping funnel, reacted at 10 ℃ for 10min, and the product was poured into a mold, and evaporated at room temperature to remove the solvent, thereby obtaining an elastomer.
The mechanical property test is carried out on the alloy, and the tensile strength is 19 MPa. The elongation at break was 120%.
Examples 5,
A preparation method of polyurea elastomer with polysiloxane completely replacing polyether comprises the following steps:
30g of dicyclohexylmethane diisocyanate is added into a four-neck flask provided with a constant-pressure dropping funnel, a drying tube, mechanical stirring and a nitrogen introducing device, and is completely dissolved by a mixed solvent of toluene and isopropanol (volume ratio is 5: 1), 60g of aminopropyl terminated polydimethylsiloxane C with molecular weight of 2000 is completely dissolved under strong stirring, and then is dropwise added into the solution through the dropping funnel, and reacts for 30min at 30 ℃ to prepare prepolymer D, and finally 20g of hexamethylenediamine is dissolved in the mixed solution and is dropwise added into a reactor through the dropping funnel, reacts for 10min at 20 ℃, and the product is poured into a mold, and is volatilized at room temperature to remove the solvent, so that the elastomer is obtained.
The tensile strength of the material is 20MPa, and the elongation at break is 100 percent.
Comparative examples 1,
A preparation method of polyurea elastomer with polysiloxane completely replacing polyether comprises the following steps:
30g of dicyclohexylmethane diisocyanate is added into a four-neck flask provided with a constant-pressure dropping funnel, a drying tube, mechanical stirring and a nitrogen introducing device, 70g of aminopropyl terminated polydimethylsiloxane C with the molecular weight of 4000 is completely dissolved by using a toluene solvent under strong stirring, then the mixture is dropwise added into the solution through the dropping funnel, a reaction is carried out for 30min at 40 ℃, a prepolymer D is prepared, finally 20g of 2-methyl-1, 5-pentanediamine is dissolved into the mixed solution, the mixture is dropwise added into a reactor through the dropping funnel, a reaction is carried out for 10min at 5 ℃, the product is poured into a mold, and the solvent is removed through volatilization at room temperature, so that the elastomer is obtained.
The tensile strength of the material is 4MPa, and the elongation at break is 110%.
The comparative example adopts a single solvent, and because the soft segment and the hard segment can not be fully dissolved by the single solvent, macroscopic phase separation is generated in the reaction, so that the reaction can not be carried out completely, and the mechanical property of the product is influenced.
Comparative examples 2,
A preparation method of polyurea elastomer with polysiloxane completely replacing polyether comprises the following steps:
40g of diphenylmethane diisocyanate was added into a four-neck flask equipped with a constant pressure dropping funnel, a drying tube, mechanical stirring and a nitrogen-introducing device, and dissolved completely in a mixed solvent of tetrahydrofuran and dichloromethane (volume ratio: 8: 1), 60g of aminopropyl terminated polydimethylsiloxane C having a molecular weight of 2000 was dissolved completely under vigorous stirring, and then added dropwise into the above solution through the dropping funnel, reacted at 30 ℃ for 10min to prepare a prepolymer D, and finally 20g of hexamethylenediamine was dissolved in the mixed solution, added dropwise into a reactor through the dropping funnel, reacted at 10 ℃ for 15min, and the product was poured into a mold, and evaporated at room temperature to remove the solvent, thereby obtaining an elastomer.
The mechanical property test is carried out on the alloy, and the tensile strength is 3 MPa. The elongation at break was 90%.
In the comparative example, the ratio of the terminal amino group of the aminopropyl terminated polydimethylsiloxane C to the isocyanate group in the diisocyanate compound was too low (the amount of diphenylmethane diisocyanate added was too large), resulting in poor mechanical properties of the elastomer.
Comparative examples 3,
A preparation method of polyurea elastomer with polysiloxane completely replacing polyether comprises the following steps:
30g of dicyclohexylmethane diisocyanate is added into a four-neck flask provided with a constant-pressure dropping funnel, a drying tube, mechanical stirring and a nitrogen introducing device, and is completely dissolved by a mixed solvent of dimethyl sulfoxide and n-hexane (the volume ratio is 8: 1), 70g of aminopropyl terminated polydimethylsiloxane C with the molecular weight of 20000 is completely dissolved under strong stirring, and then is dropwise added into the solution through the dropping funnel, the reaction is carried out for 20min at 40 ℃, a prepolymer D is prepared, finally 20g of 4, 4' -methylenebis (2-ethyl-6-methylcyclohexylamine) is dissolved into the mixed solution, is dropwise added into a reactor through the dropping funnel, the reaction is carried out for 20min at 10 ℃, the product is poured into a mold, and the solvent is removed through volatilization at room temperature, so that the elastomer is obtained.
The tensile strength of the material is 3MPa, and the elongation at break is 230 percent.
In this comparative example, the aminopropyl terminated polydimethylsiloxane C had too high a molecular weight, resulting in too significant phase separation of the soft and hard segments, and the sharp microphase separation reduced the mechanical properties of the elastomer.
Comparative examples 4,
A preparation method of polyurea elastomer with polysiloxane completely replacing polyether comprises the following steps:
20g of diphenylmethane diisocyanate was added into a four-neck flask equipped with a constant pressure dropping funnel, a drying tube, mechanical stirring and a nitrogen-introducing device, and dissolved completely in a mixed solvent of toluene and n-hexane (volume ratio 5: 1), 60g of aminopropyl terminated polydimethylsiloxane C having a molecular weight of 5000 was dissolved completely under vigorous stirring, and then added dropwise into the above solution through the dropping funnel, reacted at 40 ℃ for 30min to prepare a prepolymer D, and finally 20g of ethylenediamine was dissolved in the mixed solution, added dropwise into a reactor through the dropping funnel, reacted at 50 ℃ for 10min, and the product was poured into a mold, and evaporated at room temperature to remove the solvent, thereby obtaining an elastomer.
The tensile strength of the material is 3MPa, and the elongation at break is 300 percent.
In the comparative example, the reaction temperature is too high during the chain extension reaction, so that the reaction is too violent, the product is precipitated in advance, the reaction is not thorough, the reaction is also not easy to control, and the mechanical property of the product is lower.
Claims (5)
1. A preparation method of polyurea elastomer with polysiloxane completely replacing polyether comprises the following steps:
in a four-necked flask equipped with a constant pressure dropping funnel, a drying tube, mechanical stirring and a nitrogen gas introducing device, 30g of dicyclohexylmethane diisocyanate was charged, and the mixture was purified by adding xylene and isopropanol in a volume ratio of 6: 1, completely dissolving, under strong stirring, completely dissolving 70g of aminopropyl terminated polydimethylsiloxane with the molecular weight of 4000, dropwise adding the mixture into the obtained solution through a dropping funnel, reacting at 40 ℃ for 30min to prepare a prepolymer, finally dissolving 20g of 2-methyl-1, 5-pentanediamine in the mixed solution, dropwise adding the mixture into a reactor through the dropping funnel, reacting at 5 ℃ for 10min, pouring the product into a mold, and volatilizing at room temperature to remove the solvent to obtain the elastomer.
2. A preparation method of polyurea elastomer with polysiloxane completely replacing polyether comprises the following steps:
in a four-necked flask equipped with a constant pressure dropping funnel, a drying tube, mechanical stirring and a nitrogen gas introducing device, 20g of diphenylmethane diisocyanate was charged, and the mixture was cooled in a volume ratio of tetrahydrofuran to dichloromethane of 8: 1, completely dissolving, under strong stirring, completely dissolving 60g of aminopropyl terminated polydimethylsiloxane with molecular weight of 2000, dropwise adding the mixture into the obtained solution through a dropping funnel, reacting at 30 ℃ for 10min to prepare a prepolymer, finally dissolving 20g of hexamethylenediamine in the mixed solution, dropwise adding the mixture into a reactor through the dropping funnel, reacting at 10 ℃ for 15min, pouring the product into a mold, and volatilizing at room temperature to remove the solvent to obtain the elastomer.
3. A preparation method of polyurea elastomer with polysiloxane completely replacing polyether comprises the following steps:
in a four-necked flask equipped with a constant pressure dropping funnel, a drying tube, mechanical stirring and a nitrogen gas introducing device, 30g of dicyclohexylmethane diisocyanate was charged, and the mixture was cooled in a volume ratio of dimethyl sulfoxide to n-hexane of 8: 1, completely dissolving, under strong stirring, completely dissolving 70g of aminopropyl terminated polydimethylsiloxane with the molecular weight of 3000, dropwise adding the mixture into the obtained solution through a dropping funnel, reacting at 40 ℃ for 20min to prepare a prepolymer, finally dissolving 20g of 4, 4' -methylenebis (2-ethyl-6-methylcyclohexylamine) into the mixed solution, dropwise adding the mixture into a reactor through the dropping funnel, reacting at 10 ℃ for 20min, pouring the product into a mold, and volatilizing at room temperature to remove the solvent to obtain the elastomer.
4. A preparation method of polyurea elastomer with polysiloxane completely replacing polyether comprises the following steps:
in a four-necked flask equipped with a constant pressure dropping funnel, a drying tube, mechanical stirring and a nitrogen gas introducing device, 20g of diphenylmethane diisocyanate was charged, and the mixture was cooled in a volume ratio of toluene to n-hexane of 5: 1, completely dissolving, under strong stirring, completely dissolving 60g of aminopropyl terminated polydimethylsiloxane with the molecular weight of 5000, dropwise adding the mixture into the obtained solution through a dropping funnel, reacting at 40 ℃ for 30min to prepare a prepolymer, finally dissolving 20g of ethylenediamine into the mixed solution, dropwise adding the mixture into a reactor through the dropping funnel, reacting at 10 ℃ for 10min, pouring the product into a mold, and volatilizing at room temperature to remove the solvent to obtain the elastomer.
5. A preparation method of polyurea elastomer with polysiloxane completely replacing polyether comprises the following steps:
in a four-necked flask equipped with a constant pressure dropping funnel, a drying tube, mechanical stirring and a nitrogen gas introducing device, 30g of dicyclohexylmethane diisocyanate was charged, and the mixture was dissolved in toluene and isopropyl alcohol at a volume ratio of 5: 1, completely dissolving, under strong stirring, completely dissolving 60g of aminopropyl terminated polydimethylsiloxane with molecular weight of 2000, dropwise adding the mixture into the obtained solution through a dropping funnel, reacting at 30 ℃ for 30min to prepare a prepolymer, finally dissolving 20g of hexamethylenediamine in the mixed solution, dropwise adding the mixture into a reactor through the dropping funnel, reacting at 20 ℃ for 10min, pouring the product into a mold, and volatilizing at room temperature to remove the solvent to obtain the elastomer.
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| CN115819711B (en) * | 2022-11-24 | 2024-04-05 | 四川大学 | Reactive extrusion 3D printing silicone rubber-polyurea material and application thereof |
| CN116285618B (en) * | 2022-12-20 | 2023-11-07 | 蔚湃建筑科技(上海)有限公司 | Organosilicon waterproofing agent and preparation method thereof |
| CN116082644A (en) * | 2023-01-10 | 2023-05-09 | 粤芯半导体技术股份有限公司 | Organic silicon elastomer and preparation method thereof, flexible sensor and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5512650A (en) * | 1986-06-20 | 1996-04-30 | Minnesota Mining And Manufacturing Company | Block copolymer, method of making the same, diamine precursors of the same, method of making such diamines and end products comprising the block copolymer |
| EP0250248B1 (en) * | 1986-06-20 | 1997-11-05 | Minnesota Mining And Manufacturing Company | Block copolymer, method of making the same, diamine precursors of the same method, method of making such diamines and end products comprising the block copolymer |
| WO2000067812A1 (en) * | 1999-05-07 | 2000-11-16 | Salviac Limited | Biostability of polymeric structures |
| CN101058640A (en) * | 2006-04-18 | 2007-10-24 | 汉高股份两合公司 | Organic silicon polyurea base polymer, elastic body prepared by the same, preparation method and application thereof |
| WO2008065039A1 (en) * | 2006-11-29 | 2008-06-05 | Wacker Chemie Ag | Siloxane-urea copolymers |
| CN102140157A (en) * | 2010-12-23 | 2011-08-03 | 上海凯众聚氨酯有限公司 | Preparation method of high-temperature-resistant MDI (Diphenyl Methane Diisocyanate)-based polyurethane elastomer |
| CN102942667A (en) * | 2012-10-22 | 2013-02-27 | 青岛海洋新材料科技有限公司 | Polysiloxane-polyurethane gel material and preparation method thereof |
| CN105949422A (en) * | 2016-05-10 | 2016-09-21 | 四川大学 | Polysiloxane-carbamate elastomer containing Diels-Alder bond and preparation method of polysiloxane-carbamate elastomer |
| CN108003317A (en) * | 2017-12-22 | 2018-05-08 | 四川大学 | A kind of silicone elastomer and its preparation method and application |
-
2018
- 2018-05-17 CN CN201810470625.2A patent/CN108610466B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5512650A (en) * | 1986-06-20 | 1996-04-30 | Minnesota Mining And Manufacturing Company | Block copolymer, method of making the same, diamine precursors of the same, method of making such diamines and end products comprising the block copolymer |
| EP0250248B1 (en) * | 1986-06-20 | 1997-11-05 | Minnesota Mining And Manufacturing Company | Block copolymer, method of making the same, diamine precursors of the same method, method of making such diamines and end products comprising the block copolymer |
| WO2000067812A1 (en) * | 1999-05-07 | 2000-11-16 | Salviac Limited | Biostability of polymeric structures |
| CN101058640A (en) * | 2006-04-18 | 2007-10-24 | 汉高股份两合公司 | Organic silicon polyurea base polymer, elastic body prepared by the same, preparation method and application thereof |
| WO2008065039A1 (en) * | 2006-11-29 | 2008-06-05 | Wacker Chemie Ag | Siloxane-urea copolymers |
| CN102140157A (en) * | 2010-12-23 | 2011-08-03 | 上海凯众聚氨酯有限公司 | Preparation method of high-temperature-resistant MDI (Diphenyl Methane Diisocyanate)-based polyurethane elastomer |
| CN102942667A (en) * | 2012-10-22 | 2013-02-27 | 青岛海洋新材料科技有限公司 | Polysiloxane-polyurethane gel material and preparation method thereof |
| CN105949422A (en) * | 2016-05-10 | 2016-09-21 | 四川大学 | Polysiloxane-carbamate elastomer containing Diels-Alder bond and preparation method of polysiloxane-carbamate elastomer |
| CN108003317A (en) * | 2017-12-22 | 2018-05-08 | 四川大学 | A kind of silicone elastomer and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| Design and preparation of a new polyurea–polysiloxane–polyether copolymer with a block soft segment prepared by utilizing aza-Michael addition reaction;Bo Pang et.al;《Polymer Chemistry》;20180116(第9期);第869-877页 * |
| Influence of system variables on the morphological and dynamic mechanical behavior of polydimethylsiloxane based segmented polyurethane and polyurea copolymers: a comparative perspective;Jignesh P. Sheth et.al;《polymer》;20040820;第45卷;Fig.1以及第6921页右栏第2段，table 1 * |
| 聚脲-聚硅氧烷嵌段共聚物的合成及性能;万士明等;《高分子材料科学与工程》;19881031(第5期);第24页，第25页（2）嵌段共聚合 * |
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