CN113801288A - High-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action and preparation method thereof - Google Patents
High-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action and preparation method thereof Download PDFInfo
- Publication number
- CN113801288A CN113801288A CN202110916375.2A CN202110916375A CN113801288A CN 113801288 A CN113801288 A CN 113801288A CN 202110916375 A CN202110916375 A CN 202110916375A CN 113801288 A CN113801288 A CN 113801288A
- Authority
- CN
- China
- Prior art keywords
- chain extender
- disulfide
- damping material
- pyridine
- polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
Abstract
The invention belongs to the technical field of polyurethane damping materials, and discloses a high-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action and a preparation method thereof. The polyurethane damping material is mainly prepared from the following components: 11-25 parts of polyurethane prepolymer, 0.9-3 parts of disulfide chain extender and 0.2-1.1 part of pyridine chain extender; the disulfide chain extender is an aromatic disulfide chain extender; the pyridine chain extender is more than one of 2, 6-diaminopyridine and pyridine-2, 6-dicarboxylic acid. The invention also discloses a preparation method of the polyurethane damping material. The material disclosed by the invention has good mechanical property and damping property and has self-repairing property. The material has the advantages of effective damping temperature range (tan delta is more than or equal to 0.3) width of about 120 ℃, excellent mechanical property (tensile strength can reach 15MPa, elongation at break exceeds 700%) and self-repairing efficiency of more than 70%.
Description
Technical Field
The invention belongs to the field of functional polyurethane materials, and particularly relates to a high-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond effects and a preparation method thereof.
Background
With the development and progress of industry and science and technology, noise and vibration bring more and more influence to the production and life of people. On one hand, vibration and noise greatly harm physical and psychological health of people; on the other hand, reliability, stability and accuracy of the equipment machinery are also greatly affected, and fatigue failure occurs. The damping material is one of effective measures for vibration reduction and noise reduction, and can effectively absorb vibration mechanical energy, convert the vibration mechanical energy into heat energy and dissipate the heat energy, thereby reducing various adverse effects brought by vibration noise.
Polymer-based materials, particularly elastomer materials, have excellent damping performance due to the characteristic viscoelasticity, and are an important damping material. The wide temperature range high damping material requires that the damping factor tan delta is more than or equal to 0.3 at least in the temperature range of 60-80 ℃. The elastic damping material has the defects that the glass transition temperature range is generally narrow, about 20-40 ℃, most of the elastic damping material is below room temperature, the damping performance above the room temperature is not good, and the requirements of practical application are difficult to meet. Patent application CN106146799A discloses a polyurethane damping material with a cross-linked structure containing dynamic disulfide bonds, wherein the effective damping temperature range exceeds 220 ℃, but the mechanical property is poor, which is not beneficial to the application of the polyurethane damping material, and the polyurethane damping material adopts polyester diol, so the self-repairing performance of the material is poor; the patent CN110894277A discloses a wide temperature range polyurethane material based on a disulfide bond and a suspension chain structure, the introduction of the suspension chain can effectively widen the damping temperature range (more than or equal to 170 ℃) of polyurethane, but the mechanical property of the material is greatly reduced; patent application CN112126034A discloses a mixed soft segment type polyurethane damping material, wherein polyether, polyester polyol and micromolecular diol chain extender are introduced to synthesize and prepare polyurethane with tensile strength of 9.7MPa, but the damping temperature range is only 49 ℃. It can be seen that the damping performance and the mechanical property of the polymer damping material are difficult to balance, and the application requirements in reality cannot be met at the same time, so that the application of the polyurethane damping material is limited.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a high-performance polyurethane damping material based on the action of dynamic disulfide bonds and hydrogen bonds and a preparation method thereof. According to the invention, mixed chain extenders (such as carboxyl disulfide and aminopyridine) are introduced into the polyurethane prepolymer and react to form the polyurethane elastomer containing different functional groups such as anhydride groups, urea groups, carbamate groups and the like, so that hydrogen bonds with different strengths are formed and disulfide bonds are introduced. The distance between the carbamido groups is regulated and controlled by changing the proportion of the chain extender, so that the system is endowed with the optimal hydrogen bond function, and the polyurethane has positive effects of improving the damping and mechanical properties of polyurethane; the aromatic disulfide bond can spontaneously perform dynamic exchange of disulfide bonds at room temperature or above, improve the mobility of molecular chain segments, increase the intermolecular friction force and consume energy. The invention regulates and controls the hydrogen bonding action, the microphase mixing degree and the crystallinity of the polyurethane from multiple scales such as molecules, mesoscopic scales and the like by depending on the disulfide bonds and the hydrogen bonding action with different strengths, thereby widening the damping temperature range of the polyurethane and simultaneously improving the mechanical property of the polyurethane. The polyurethane damping material has a damping temperature range of more than 110 ℃ and a strength of more than 10 MPa. The polyurethane damping material has good damping and mechanical properties, and can effectively solve the problem that the damping property and the mechanical property of the conventional polyurethane damping material are difficult to balance. In addition, the damping material also has self-repairing performance.
The purpose of the invention is realized by the following technical scheme:
a high-performance polyurethane damping material based on the action of dynamic disulfide bonds and hydrogen bonds with different strengths is mainly prepared from the following components: 11-25 parts of polyurethane prepolymer, 0.9-3 parts of disulfide chain extender and 0.2-1.1 parts of pyridine chain extender.
The polyurethane prepolymer is obtained by the reaction of polyether polyol and diisocyanate under the action of a catalyst; in the polyurethane prepolymer, the weight ratio of polyether polyol to polyisocyanate is (6-20) to (3-5).
The disulfide chain extender is an aromatic disulfide chain extender, and specifically is more than one of 2, 2 '-dithiodibenzoic acid (DTSA), 4' -diaminodiphenyl disulfide (4-DTDA), 2 '-diaminodiphenyl disulfide (2-DTDA), 3' -dihydroxy diphenyl disulfide (3-DDPS) and bis (4-hydroxyphenyl) disulfide (4-DDPS);
the pyridine chain extender is more than one of 2, 6-diaminopyridine and pyridine-2, 6-dicarboxylic acid.
The diisocyanate is more than one of toluene diisocyanate, diphenyl methylene diisocyanate, 3-isocyanato methylene-3, 5, 5-trimethyl cyclohexyl isocyanate (isophorone diisocyanate) and hexamethylene diisocyanate.
The weight ratio of the disulfide chain extender to the pyridine chain extender is preferably 0.9 to (0.5-1), and more preferably 0.9 to (0.6-0.9).
The molecular weight of the polyether polyol is 650-2000.
In the polyurethane prepolymer, the reaction temperature is 80-85 ℃, and the reaction time is 3-4 h.
The polyether polyol is preferably polyether glycol, and is subjected to dehydration treatment before use, such as: and (5) performing vacuum dehydration treatment.
The preparation method of the high-performance polyurethane damping material based on the action of the dynamic disulfide bond and the hydrogen bonds with different strengths comprises the following steps:
1) under the protective atmosphere, polyether glycol reacts with diisocyanate under the action of a catalyst to obtain a polyurethane prepolymer; dehydrating the polyether polyol before reaction; the dehydration treatment is vacuum dehydration, and the vacuum dehydration condition is that the vacuum pumping is carried out at the temperature of 110-120 ℃ for dehydration for 1.5-3 h; the reaction temperature is 80-85 ℃, and the reaction time is 3-4 h;
2) carrying out chain extension reaction on the polyurethane prepolymer and a disulfide chain extender, and then carrying out secondary chain extension on the reaction product and a pyridine chain extender; or, carrying out chain extension reaction on the polyurethane prepolymer and a pyridine chain extender, and then carrying out secondary chain extension on the reaction product and a disulfide chain extender; and (4) molding and curing to obtain the high-performance polyurethane damping material based on the action of the dynamic disulfide bonds and the hydrogen bonds with different strengths.
In the step 2), secondary chain extension and molding curing are carried out step by step or simultaneously; the step-by-step representation is that firstly, the chain extension is carried out for the second time, and then the molding and the curing are carried out; and simultaneously, the secondary chain extension is completed in the molding and curing process.
Reaction conditions of the disulfide chain extender in the step 2): reacting for 5-8 h at 60-85 ℃; the reaction condition of the pyridine chain extender is that the pyridine chain extender reacts for 1 to 3 hours at the temperature of 55 to 65 ℃;
the molding and curing conditions in the step 2) are heat preservation for 6-15 hours at 55-80 ℃ under a vacuum condition.
The temperature range of the molding and curing is the same as that of the secondary chain extension.
When the secondary chain extension and the molding and curing are carried out simultaneously, the molding and curing time is not less than the secondary chain extension time, the molding and curing conditions comprise the secondary chain extension conditions, and only the molding and curing conditions are considered at the moment.
When the reaction product and the chain extender carry out secondary chain extension, the molding curing and the secondary chain extension can be carried out simultaneously, namely the secondary chain extension is completed in the molding curing process; at the moment, the reaction product and the chain extender are mixed uniformly, then molding and curing are carried out, and secondary chain extension is completed, wherein the mixing is carried out by rapidly stirring for 5-15 min. The temperature of uniform mixing is the same as the temperature of secondary chain extension, and the temperature of molding and curing is the same as the temperature of secondary chain extension; and the molding and curing conditions are heat preservation for 6-15 hours under vacuum conditions.
Preferably, the step 2) is specifically to perform chain extension reaction on the polyurethane prepolymer and a disulfide chain extender, then perform secondary chain extension on the reaction product and a pyridine chain extender, and then perform molding and curing; or uniformly mixing the reaction product with a pyridine chain extender, molding and curing, and carrying out secondary chain extension. Chain extension reaction conditions: reacting for 5-8 h at 60-85 ℃; and carrying out secondary chain extension reaction for 1-3 h at 55-65 ℃. The mixing is stirring for 5-15 min at 55-65 ℃.
The disulfide chain extender is added in a form of solution, and the solution of the disulfide chain extender is obtained by dissolving the disulfide chain extender in an organic solvent; before reaction, the disulfide chain extender is dissolved by an organic solvent to prepare a solution; the organic solvent is more than one of toluene, N '-Dimethylformamide (DMF) and N, N' -dimethylacetamide (DMAc); the weight ratio of the disulfide chain extender to the organic solvent is (0.9-3) to (4-5);
the pyridine chain extender is added in the form of solution, and the solution of the pyridine chain extender is obtained by dissolving the pyridine chain extender in an organic solvent; dissolving a pyridine chain extender by using an organic solvent to prepare a solution before reaction; the organic solvent is more than one of toluene, N '-Dimethylformamide (DMF) and N, N' -dimethylacetamide (DMAc). The weight ratio of the pyridine chain extender to the organic solvent is (0.2-1.1) to (4-5).
The diisocyanate in the step 1) is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate (IPDI, isophorone diisocyanate) and Hexamethylene Diisocyanate (HDI).
The polyether polyol in the step 1) is polytetrahydrofuran, polypropylene glycol and the like, such as: one or more of molecular weight 650 polytetrahydrofuran (PTMEG650), molecular weight 1000 polytetrahydrofuran (PTMEG1000), molecular weight 2000 polytetrahydrofuran (PTMEG 2000).
The catalyst in the step 1) is more than one of dibutyltin dilaurate, stannous octoate, zinc isooctanoate, zinc neodecanoate, bismuth isooctanoate and bismuth neodecanoate.
The dosage of the catalyst in the step 1) is 0.1-2% of the mass of the polyether polyol.
Adding a good solvent in the reaction process of the step 1), and adjusting the viscosity of the reactant, wherein the good solvent is more than one of N, N' -Dimethylformamide (DMF), toluene and DMAc. The weight ratio of the good solvent to the polyether polyol is (1-4): (6-20).
The special molecular structure of the pyridine chain extender selected by the invention can enhance the intermolecular hydrogen bond action, thereby improving the mechanical strength of the system and the intermolecular internal friction.
When the high-performance polyurethane damping material is subjected to self-repairing, a heavy object is pressed on a sample, and then heating treatment is carried out; self-repairing conditions are as follows: and (3) 50-200 g of weight at the temperature of 60-80 ℃.
The disulfide chain extender and the pyridine chain extender are combined to form hydrogen bonds with different strengths, so that the mechanical property of the polyurethane is improved; meanwhile, the energy can be consumed in the processes of bond breaking and recombination of hydrogen bonds and dynamic exchange of disulfide bonds, and the damping performance of the polyurethane is improved. The disulfide bond and the hydrogen bond have combined action to obtain the polyurethane elastomer with good mechanical property and damping property, and endow the polyurethane with certain self-repairing property.
The invention focuses on the defects of the traditional polyurethane damping material, namely the improvement of the damping performance is usually accompanied with the great reduction of the mechanical performance, and the mechanical performance and the damping performance cannot be compatible, so that the use value of the polyurethane damping material is limited. In order to overcome the difficulties, the invention introduces an aromatic dynamic disulfide bond capable of reversible exchange at room temperature based on the designability of a polyurethane structure, and then is assisted with different types of second chain extenders to form hydrogen bonds with different strengths so as to improve the damping performance and the mechanical performance of the polyurethane. Meanwhile, the polyurethane damping material also has self-repairing performance, and the application value of the material is improved.
Compared with the prior art, the invention has the following advantages:
1. according to the polyurethane damping material, the dynamic reversible disulfide bonds are introduced into the polyether system polyurethane, the dynamic exchange of the disulfide bonds can be spontaneously carried out at room temperature due to the aromatic disulfide bonds, the disulfide bond exchange rate is accelerated along with the rise of the temperature, the mutual diffusion and entanglement among molecular chains are promoted, the friction among the molecular chains is increased, the mechanical energy of the molecular chain motion is converted into heat energy, and the damping performance of the polyurethane at the room temperature is improved. Meanwhile, the polyether system polyurethane has good damping performance at low temperature, so that the damping temperature range of the material is greatly widened.
2. According to the polyurethane damping material, isocyanate groups in the prepolymer can react with carboxyl groups or amino groups of the mixed chain extender to generate a certain number of urea bonds, acid anhydride bonds and urethane bonds, so that hydrogen bonds with different strengths are formed. The hydrogen bond effects with different strengths in the system are adjusted by changing the proportion of the mixed chain extender, so that the mechanical property of the polyurethane damping material is improved. Meanwhile, the dissociation and recombination of the hydrogen bond can dissipate energy, and the polyurethane damping material has a positive effect on the improvement of the polyurethane damping performance.
3. The effective damping temperature range (tan delta is more than or equal to 0.3) of the polyurethane damping material reaches 117 ℃ (-17 ℃ -100 ℃), and the existing polyurethane damping material has a narrow effective damping temperature range of about 60-80 ℃.
4. The polyurethane damping material provided by the invention has the mechanical strength of 14.98MPa, solves the problem that the mechanical property and the damping property of the polyurethane cannot be considered simultaneously, and can greatly widen the application field of the polyurethane.
5. The system of the invention has simple structure, good damping performance and mechanical property, and can repair for 24 hours at 60 ℃, and the self-repairing efficiency can reach 70% or more.
Drawings
FIG. 1 is a graph showing the dynamic mechanical properties at 10Hz of the damping materials prepared in examples 1, 7 and 8.
Detailed Description
The invention will be further illustrated with reference to specific examples, without however being limited thereto.
Example 1
A high-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action comprises the following synthetic steps:
(1) vacuumizing 10 weight parts of polytetrahydrofuran (PTMEG1000) with molecular weight of 1000 (number average molecular weight) at 110 ℃, removing water for 2h, turning off heating, and introducing N2Protection is carried out; after the temperature is reduced to 80 ℃, 4.5 weight portions of 3-isocyanatomethylene-3, 5, 5-trimethyl cyclohexyl isocyanate (IPDI) are added, and 0.02 weight portion of catalyst dibutyltin dilaurate (DBTDL) and 2 weight portions of catalyst are simultaneously addedAdjusting the viscosity of the reactant by N, N' -Dimethylformamide (DMF) in parts by weight, and reacting at 85 ℃ for 4 hours to obtain a prepolymer.
(2) 0.9 part by weight of 2, 2' -dithiodibenzoic acid (DTSA) was weighed out, dissolved completely in 4 parts by weight of DMF and added to the prepolymer obtained in step (1) (the parts by weight of the prepolymer correspond to 14.5), N2And (4) protecting, reacting at 80 ℃ for 6 hours, and then stopping heating to obtain a primary chain extension product.
(3) Weighing 0.7 weight part of 2, 6-Diaminopyridine (DAP), completely dissolving with 4 weight parts of DMF, adding into the product obtained in step (2), and adding N2And (3) protecting, quickly stirring for 10min at 60 ℃, pouring into a polytetrafluoroethylene mold, molding and taking out a plate, and keeping the temperature at 60 ℃ for 6h under a vacuum condition for molding and curing to obtain the polyurethane damping material.
Example 2
A high-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action comprises the following synthetic steps:
(1) vacuumizing 10 weight parts of polytetrahydrofuran (PTMEG1000) with molecular weight of 1000 at 110 ℃, removing water for 2h, turning off heating, and introducing N2Protection is carried out; and after the temperature is reduced to 80 ℃, 4.5 parts by weight of 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate (IPDI) is added, 0.02 part by weight of catalyst dibutyltin dilaurate (DBTDL) and 2 parts by weight of N, N' -Dimethylformamide (DMF) are added to adjust the viscosity of the reactant, and the prepolymer is obtained after reaction for 3 hours at 85 ℃.
(2) Weighing 1.2 parts by weight of 2, 2' -dithiodibenzoic acid (DTSA), completely dissolving with 4 parts by weight of DMF, adding into the prepolymer obtained in the step (1), and adding N2And (4) protecting, reacting at 80 ℃ for 6 hours, and then stopping heating to obtain a primary chain extension product.
(3) 0.6 part by weight of 2, 6-Diaminopyridine (DAP) was weighed out and added to the product obtained in step (2) after complete dissolution with 4 parts by weight of DMF, N2And (3) protecting, quickly stirring for 10min at 60 ℃, pouring into a polytetrafluoroethylene mold, molding and taking out a plate, and keeping the temperature at 60 ℃ for 6h under a vacuum condition for molding and curing to obtain the polyurethane damping material.
Example 3
A high-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action comprises the following synthetic steps:
(1) vacuumizing 10 weight parts of polytetrahydrofuran (PTMEG1000) with molecular weight of 1000 at 110 ℃, removing water for 2h, turning off heating, and introducing N2Protection is carried out; and after the temperature is reduced to 80 ℃, 4.5 parts by weight of 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate (IPDI) is added, 0.02 part by weight of catalyst dibutyltin dilaurate (DBTDL) and 2 parts by weight of N, N' -Dimethylformamide (DMF) are added to adjust the viscosity of the reactant, and the prepolymer is obtained after reaction for 3 hours at 85 ℃.
(2) Weighing 1.5 parts by weight of 2, 2' -dithiodibenzoic acid (DTSA), completely dissolving with 4 parts by weight of DMF, adding into the prepolymer obtained in the step (1), and adding N2And (4) protecting, reacting at 80 ℃ for 6 hours, and then stopping heating to obtain a primary chain extension product.
(3) Weighing 0.5 weight part of 2, 6-Diaminopyridine (DAP), completely dissolving with 4 weight parts of DMF, adding into the product obtained in step (2), and adding N2And (3) protecting, quickly stirring for 10min at 60 ℃, pouring into a polytetrafluoroethylene mold, molding and taking out a plate, and keeping the temperature at 60 ℃ for 6h under a vacuum condition for molding and curing to obtain the polyurethane damping material.
Example 4
A high-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action comprises the following synthetic steps:
(1) vacuumizing 10 weight parts of polytetrahydrofuran (PTMEG1000) with molecular weight of 1000 at 110 ℃, removing water for 2h, turning off heating, and introducing N2And (6) protecting. And after the temperature is reduced to 80 ℃, 4.5 parts by weight of 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate (IPDI) is added, 0.02 part by weight of catalyst dibutyltin dilaurate (DBTDL) and 2 parts by weight of N, N' -Dimethylformamide (DMF) are added to adjust the viscosity of the reactant, and the prepolymer is obtained after reaction for 3 hours at 85 ℃.
(2) Weighing 1.8 parts by weight of 2, 2' -dithiodibenzoic acid (DTSA), completely dissolving with 4 parts by weight of DMF, adding into the prepolymer obtained in the step (1), and adding N2And (4) protecting, reacting at 80 ℃ for 6 hours, and then stopping heating to obtain a primary chain extension product.
(3) Weighing 0.4 weight part of 2, 6-diaminopyridine(DAP) dissolved completely in 4 parts by weight of DMF and added to the product obtained in step (2), N2And (3) protecting, quickly stirring for 10min at 60 ℃, pouring into a polytetrafluoroethylene mold, molding and taking out a plate, and keeping the temperature at 60 ℃ for 6h under a vacuum condition for molding and curing to obtain the polyurethane damping material.
Example 5
A high-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action comprises the following synthetic steps:
(1) vacuumizing 10 weight parts of polytetrahydrofuran (PTMEG1000) with molecular weight of 1000 at 110 ℃, removing water for 2h, turning off heating, and introducing N2Protection is carried out; and after the temperature is reduced to 80 ℃, 4.5 parts by weight of 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate (IPDI) is added, 0.02 part by weight of catalyst dibutyltin dilaurate (DBTDL) and 2 parts by weight of N, N' -Dimethylformamide (DMF) are added to adjust the viscosity of the reactant, and the prepolymer is obtained after reaction for 3 hours at 85 ℃.
(2) Weighing 2.1 parts by weight of 2, 2' -dithiodibenzoic acid (DTSA), completely dissolving with 4 parts by weight of DMF, adding into the prepolymer obtained in the step (1), and adding N2And (4) protecting, reacting at 80 ℃ for 6 hours, and then stopping heating to obtain a primary chain extension product.
(3) Weighing 0.3 part by weight of 2, 6-Diaminopyridine (DAP), completely dissolving with 4 parts by weight of DMF, adding into the product obtained in step (2), N2And (3) protecting, quickly stirring for 10min at 60 ℃, pouring into a polytetrafluoroethylene mold, molding and taking out a plate, and keeping the temperature at 60 ℃ for 6h under a vacuum condition for molding and curing to obtain the polyurethane damping material.
Example 6
A high-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action comprises the following synthetic steps:
(1) vacuumizing 10 weight parts of polytetrahydrofuran (PTMEG1000) with molecular weight of 1000 at 110 ℃, removing water for 2h, turning off heating, and introducing N2Protection is carried out; after the temperature is reduced to 80 ℃, 4.5 weight parts of 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate (IPDI) is added, and 0.02 weight part of catalyst dibutyltin dilaurate (DBTDL) and 2 weight parts of N, N' -Dimethylformamide (DMF) are added for regulationThe viscosity of the reactant is reacted for 3 hours at 85 ℃ to obtain the prepolymer.
(2) Weighing 2.5 parts by weight of 2, 2' -dithiodibenzoic acid (DTSA), completely dissolving with 4 parts by weight of DMF, adding into the prepolymer obtained in the step (1), and adding N2And (4) protecting, reacting at 80 ℃ for 6 hours, and then stopping heating to obtain a primary chain extension product.
(3) Weighing 0.2 weight part of 2, 6-Diaminopyridine (DAP), completely dissolving with 4 weight parts of DMF, adding into the product obtained in step (2), and adding N2And (3) protecting, quickly stirring for 10min at 60 ℃, pouring into a polytetrafluoroethylene mold, molding and taking out a plate, and keeping the temperature at 60 ℃ for 6h under a vacuum condition for molding and curing to obtain the polyurethane damping material.
Example 7
A high-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action comprises the following synthetic steps:
(1) vacuumizing 10 weight parts of polytetrahydrofuran (PTMEG1000) with molecular weight of 1000 at 110 ℃, removing water for 2h, turning off heating, and introducing N2Protection is carried out; and after the temperature is reduced to 80 ℃, 4.5 parts by weight of 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate (IPDI) is added, 0.02 part by weight of catalyst dibutyltin dilaurate (DBTDL) and 2 parts by weight of N, N' -Dimethylformamide (DMF) are added to adjust the viscosity of the reactant, and the prepolymer is obtained after reaction for 3 hours at 85 ℃.
(2) Weighing 3 parts by weight of 2, 2' -dithiodibenzoic acid (DTSA), completely dissolving with 4 parts by weight of DMF, adding into the prepolymer obtained in the step (1), and adding N2And (3) protecting, reacting at 80 ℃ for 6h, stopping heating, pouring into a polytetrafluoroethylene mold, molding, taking out a plate, keeping the temperature at 60 ℃ under a vacuum condition for 6h, molding and curing to obtain the polyurethane elastomer.
Example 8
A high-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action comprises the following synthetic steps:
(1) vacuumizing 10 weight parts of polytetrahydrofuran (PTMEG1000) with molecular weight of 1000 at 110 ℃, removing water for 2h, turning off heating, and introducing N2Protection is carried out; after the temperature is reduced to 80 ℃, 4.5 weight parts of 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexane are addedAdding 0.02 weight part of catalyst dibutyltin dilaurate (DBTDL) and 2 weight parts of N, N' -Dimethylformamide (DMF) into isocyanate (IPDI) to adjust the viscosity of the reactant, and reacting at 85 ℃ for 3 hours to obtain the prepolymer.
(2) Weighing 1.1 weight parts of 2, 6-Diaminopyridine (DAP), completely dissolving with 4 weight parts of DMF, adding into the product obtained in step (1), and adding N2Protecting, quickly stirring at 60 ℃ for 10min, pouring into a polytetrafluoroethylene mold, molding and taking out a plate, and keeping the temperature at 60 ℃ under a vacuum condition for 6h, molding and curing to obtain the polyurethane elastomer.
Example 9
A high-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action comprises the following synthetic steps:
(1) vacuumizing 6.5 weight parts of polytetrahydrofuran (PTMEG650) with molecular weight of 650 at 110 ℃, removing water for 2h, turning off heating, and introducing N2Protection is carried out; and after the temperature is reduced to 80 ℃, 4.5 parts by weight of 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate (IPDI) is added, 0.02 part by weight of catalyst dibutyltin dilaurate (DBTDL) and 2 parts by weight of N, N' -Dimethylformamide (DMF) are added to adjust the viscosity of the reactant, and the prepolymer is obtained after reaction for 3 hours at 85 ℃.
(2) Weighing 0.9 part by weight of 2, 2' -dithiodibenzoic acid (DTSA), completely dissolving with 4 parts by weight of DMF, adding into the prepolymer obtained in the step (1), and adding N2And (4) protecting, reacting at 80 ℃ for 6 hours, and then stopping heating to obtain a primary chain extension product.
(3) Weighing 0.7 weight part of 2, 6-Diaminopyridine (DAP), completely dissolving with 4 weight parts of DMF, adding into the product obtained in step (2), and adding N2And (3) protecting, quickly stirring for 10min at 60 ℃, pouring into a polytetrafluoroethylene mold, molding and taking out a plate, and keeping the temperature at 60 ℃ for 6h under a vacuum condition for molding and curing to obtain the polyurethane elastic damping material.
Example 10
A high-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action comprises the following synthetic steps:
(1) vacuumizing 20 weight parts of polytetrahydrofuran (PTMEG2000) with molecular weight of 2000 at 110 ℃, removing water for 2h, and turning off heatingIntroduction of N2Protection is carried out; and after the temperature is reduced to 80 ℃, 4.5 parts by weight of 3-isocyanatomethylene-3, 5, 5-trimethylcyclohexyl isocyanate (IPDI) is added, 0.02 part by weight of catalyst dibutyltin dilaurate (DBTDL) and 2 parts by weight of N, N' -Dimethylformamide (DMF) are added to adjust the viscosity of the reactant, and the prepolymer is obtained after reaction for 3 hours at 85 ℃.
(2) Weighing 0.9 part by weight of 2, 2' -dithiodibenzoic acid (DTSA), completely dissolving with 4 parts by weight of DMF, adding into the prepolymer obtained in the step (1), and adding N2And (4) protecting, reacting at 80 ℃ for 6 hours, and then stopping heating to obtain a primary chain extension product.
(3) Weighing 0.7 weight part of 2, 6-Diaminopyridine (DAP), completely dissolving with 4 weight parts of DMF, adding into the product obtained in step (2), and adding N2And (3) protecting, quickly stirring for 10min at 60 ℃, pouring into a polytetrafluoroethylene mold, molding and taking out a plate, and keeping the temperature at 60 ℃ for 6h under a vacuum condition for molding and curing to obtain the polyurethane damping material.
And (3) performance testing:
the mechanical tensile strength test and the self-repair test were performed on the above examples, respectively, and the results are shown in table 1.
Through comparison, the mechanical property of the embodiment 1 with the mass ratio of the disulfide chain extender to the aminopyridine being 0.9: 0.7 is the best, and the mechanical property of a pure disulfide chain extender system is the worst and is 3.65 MPa. The chain extenders have different proportions, the strength of hydrogen bonds formed among molecules is different, the acting force among molecules is different, and the mechanical strength of different embodiments is greatly different. On the other hand, the existence of the aromatic dynamic disulfide bond endows the polyurethane damping material with good self-repairing performance, and the self-repairing efficiency of the embodiment 1 with the optimal mechanical performance at 80 ℃ reaches 70 percent, so that the self-repairing performance is good.
Meanwhile, in order to test and compare the damping performance of different systems, dynamic mechanical analysis tests were respectively performed on example 1, example 7 and example 8. The testing temperature is-90-100 ℃, and the testing frequency is 10 Hz. The results obtained are shown in FIG. 1.
As can be seen from FIG. 1, compared with the narrower damping temperature range of the single chain extender in examples 7 and 8, the effective damping temperature range (tan delta is greater than or equal to 0.3) of the chain extender system in example 1 reaches 117 ℃ (-17 ℃ -100 ℃) and the damping performance is better.
By combining the mechanical properties in table 1 and the damping properties in fig. 1, the balance between the damping properties and the mechanical properties can be realized by adjusting different proportions of the mixed chain extender, and meanwhile, the polyurethane damping material has excellent self-repairing properties, so that the high-performance polyurethane damping material is obtained.
TABLE 1 mechanical Properties and self-repair efficiencies of the examples
The above examples are examples of the present invention for preparing high performance polyurethane damping materials based on the dynamic disulfide bond and hydrogen bond interactions, but the present invention is not limited to the above examples, and the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention are all equivalent substitutions and are included in the protection scope of the present invention.
Claims (10)
1. A high-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action with different strengths is characterized in that: the composition is mainly prepared from the following components: 11-25 parts of polyurethane prepolymer, 0.9-3 parts of disulfide chain extender and 0.2-1.1 part of pyridine chain extender;
the polyurethane prepolymer is obtained by the reaction of polyether polyol and diisocyanate under the action of a catalyst;
the disulfide chain extender is an aromatic disulfide chain extender, and specifically is more than one of 2, 2 '-dithiodibenzoic acid, 4' -diaminodiphenyl disulfide, 2 '-diaminodiphenyl disulfide, 3' -dihydroxy diphenyl disulfide and bis (4-hydroxyphenyl) disulfide;
the pyridine chain extender is more than one of 2, 6-diaminopyridine and pyridine-2, 6-dicarboxylic acid.
2. The high-performance polyurethane damping material based on the dynamic disulfide bond and hydrogen bond interaction with different strengths as claimed in claim 1, wherein:
the weight ratio of the disulfide chain extender to the pyridine chain extender is 0.9: 0.5-1;
in the polyurethane prepolymer, the weight ratio of polyether polyol to diisocyanate is (6-20) to (3-5).
3. The high-performance polyurethane damping material based on the dynamic disulfide bond and hydrogen bond interaction with different strengths as claimed in claim 1, wherein: the diisocyanate is more than one of toluene diisocyanate, diphenyl methylene diisocyanate, 3-isocyanato methylene-3, 5, 5-trimethyl cyclohexyl isocyanate and hexamethylene diisocyanate;
the molecular weight of the polyether polyol is 650-2000.
4. The high-performance polyurethane damping material based on the dynamic disulfide bond and hydrogen bond interaction with different strengths as claimed in claim 1, wherein: in the polyurethane prepolymer, the reaction temperature is 80-85 ℃, and the reaction time is 3-4 h;
the polyether polyol is polyether glycol.
5. The high-performance polyurethane damping material based on the dynamic disulfide bond and hydrogen bond interaction with different strengths as claimed in claim 1, wherein: the catalyst is more than one of dibutyltin dilaurate, stannous octoate, zinc isooctanoate, zinc neodecanoate, bismuth isooctanoate and bismuth neodecanoate;
the dosage of the catalyst is 0.1-2% of the mass of the polyether polyol.
6. The preparation method of the high-performance polyurethane damping material based on the dynamic disulfide bond and hydrogen bond effects with different strengths as claimed in any one of claims 1 to 5, is characterized in that: the method comprises the following steps:
1) under the protective atmosphere, polyether glycol reacts with diisocyanate under the action of a catalyst to obtain a polyurethane prepolymer;
2) carrying out chain extension reaction on the polyurethane prepolymer and a disulfide chain extender, and then carrying out secondary chain extension on the reaction product and a pyridine chain extender; or, carrying out chain extension reaction on the polyurethane prepolymer and a pyridine chain extender, and then carrying out secondary chain extension on the reaction product and a disulfide chain extender; and (4) molding and curing to obtain the high-performance polyurethane damping material based on the action of the dynamic disulfide bonds and the hydrogen bonds with different strengths.
7. The preparation method of the high-performance polyurethane damping material based on the dynamic disulfide bond and hydrogen bond action with different strengths as claimed in claim 6, wherein:
the disulfide chain extender in the step 2) is reacted for 5-8 hours at the temperature of 60-85 ℃; the reaction condition of the pyridine chain extender is that the pyridine chain extender reacts for 1-3 hours at the temperature of 55-65 ℃;
in the step 2), secondary chain extension and molding curing are carried out step by step or simultaneously; the step-by-step representation is that firstly, the chain extension is carried out for the second time, and then the molding and the curing are carried out; and simultaneously, the secondary chain extension is completed in the molding and curing process.
8. The preparation method of the high-performance polyurethane damping material based on the dynamic disulfide bond and hydrogen bond action with different strengths as claimed in claim 6, wherein:
the molding and curing conditions in the step 2) are heat preservation for 6-15 h at 55-80 ℃ under a vacuum condition;
the disulfide chain extender is added in a form of solution, and the solution of the disulfide chain extender is obtained by dissolving the disulfide chain extender in an organic solvent;
the pyridine chain extender is added in the form of solution, and the solution of the pyridine chain extender is obtained by dissolving the pyridine chain extender in an organic solvent.
9. The preparation method of the high-performance polyurethane damping material based on the dynamic disulfide bond and hydrogen bond interaction with different strengths as claimed in claim 8, wherein: in the solution of the disulfide chain extender, the organic solvent is more than one of toluene, N '-dimethylformamide and N, N' -dimethylacetamide; the weight ratio of the disulfide chain extender to the organic solvent is (0.9-3): (4-5);
in the solution of the pyridine chain extender, the organic solvent is more than one of toluene, N '-dimethylformamide and N, N' -dimethylacetamide; the weight ratio of the pyridine chain extender to the organic solvent is (0.2-1.1) to (4-5).
10. The preparation method of the high-performance polyurethane damping material based on the dynamic disulfide bond and hydrogen bond action with different strengths as claimed in claim 6, wherein:
when the molding curing and the secondary chain extension in the step 2) meet the following conditions: the molding and curing and the secondary chain extension are carried out simultaneously, namely the secondary chain extension is completed in the molding and curing process; at the moment, the reaction product and the chain extender are mixed uniformly, and then molding and curing are carried out to complete secondary chain extension;
dehydrating the polyether polyol in the step 1) before reaction; the reaction temperature is 80-85 ℃, and the reaction time is 3-4 h;
the polyether polyol in the step 1) is more than one of polytetrahydrofuran and polypropylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110916375.2A CN113801288B (en) | 2021-08-10 | 2021-08-10 | High-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110916375.2A CN113801288B (en) | 2021-08-10 | 2021-08-10 | High-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113801288A true CN113801288A (en) | 2021-12-17 |
| CN113801288B CN113801288B (en) | 2023-03-21 |
Family
ID=78893486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110916375.2A Active CN113801288B (en) | 2021-08-10 | 2021-08-10 | High-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113801288B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114634609A (en) * | 2022-04-29 | 2022-06-17 | 山东科技大学 | Disulfide bond-containing single-component polyurethane damping material and preparation method thereof |
| CN114773570A (en) * | 2022-03-16 | 2022-07-22 | 华南理工大学 | Polyurethane elastomer containing metal coordination and disulfide bond, preparation method and self-repairing method thereof |
| CN116554430A (en) * | 2023-05-11 | 2023-08-08 | 青岛格林沃德新材料科技有限公司 | High-performance polyurethane damping material containing dynamic disulfide bonds and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4017939A1 (en) * | 1990-06-05 | 1991-12-12 | Univ Schiller Jena | Prepn. of di:functional prepolymers contg. two isocyanate end gps. - by reacting di:isocyanate and di:thiol to form prepolymer |
| WO2010128007A1 (en) * | 2009-05-06 | 2010-11-11 | Technische Universiteit Eindhoven | Self-healing polymers |
| CN106146799A (en) * | 2016-07-01 | 2016-11-23 | 华南理工大学 | A kind of wide temperature zone high damping polyurethane elastomer material and preparation method thereof |
| CN107383304A (en) * | 2017-06-19 | 2017-11-24 | 福州大学 | A kind of preparation method of high temperature damping polyurethane curing agent |
| CN108034344A (en) * | 2017-11-30 | 2018-05-15 | 中国船舶重工集团公司第七二五研究所 | A kind of medium temperature wide temperature range polyurethane damping paint and preparation method thereof |
| CN110105534A (en) * | 2019-04-30 | 2019-08-09 | 郑州大学 | A kind of transparent high-intensity and high-tenacity room temperature selfreparing thermoplastic polyurethane urea elastomer and preparation method |
| CN110790888A (en) * | 2019-11-07 | 2020-02-14 | 华南理工大学 | High-strength room-temperature self-repairing polyurethane elastomer based on multiple dynamic reversible effects and preparation and application thereof |
| CN110894277A (en) * | 2019-11-15 | 2020-03-20 | 华南理工大学 | High-temperature-resistant wide-temperature-range high-damping polyurethane elastomer material and preparation method thereof |
| CN111285988A (en) * | 2020-02-26 | 2020-06-16 | 天津大学 | Self-repairing elastomer with high tensile property and preparation method and application thereof |
| CN112048047A (en) * | 2020-08-24 | 2020-12-08 | 郑州大学 | Transparent yellowing-resistant high-toughness self-repairing polyurethane elastomer based on hydrogen bonding pyridine |
-
2021
- 2021-08-10 CN CN202110916375.2A patent/CN113801288B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4017939A1 (en) * | 1990-06-05 | 1991-12-12 | Univ Schiller Jena | Prepn. of di:functional prepolymers contg. two isocyanate end gps. - by reacting di:isocyanate and di:thiol to form prepolymer |
| WO2010128007A1 (en) * | 2009-05-06 | 2010-11-11 | Technische Universiteit Eindhoven | Self-healing polymers |
| CN106146799A (en) * | 2016-07-01 | 2016-11-23 | 华南理工大学 | A kind of wide temperature zone high damping polyurethane elastomer material and preparation method thereof |
| CN107383304A (en) * | 2017-06-19 | 2017-11-24 | 福州大学 | A kind of preparation method of high temperature damping polyurethane curing agent |
| CN108034344A (en) * | 2017-11-30 | 2018-05-15 | 中国船舶重工集团公司第七二五研究所 | A kind of medium temperature wide temperature range polyurethane damping paint and preparation method thereof |
| CN110105534A (en) * | 2019-04-30 | 2019-08-09 | 郑州大学 | A kind of transparent high-intensity and high-tenacity room temperature selfreparing thermoplastic polyurethane urea elastomer and preparation method |
| CN110790888A (en) * | 2019-11-07 | 2020-02-14 | 华南理工大学 | High-strength room-temperature self-repairing polyurethane elastomer based on multiple dynamic reversible effects and preparation and application thereof |
| CN110894277A (en) * | 2019-11-15 | 2020-03-20 | 华南理工大学 | High-temperature-resistant wide-temperature-range high-damping polyurethane elastomer material and preparation method thereof |
| CN111285988A (en) * | 2020-02-26 | 2020-06-16 | 天津大学 | Self-repairing elastomer with high tensile property and preparation method and application thereof |
| CN112048047A (en) * | 2020-08-24 | 2020-12-08 | 郑州大学 | Transparent yellowing-resistant high-toughness self-repairing polyurethane elastomer based on hydrogen bonding pyridine |
Non-Patent Citations (5)
| Title |
|---|
| J. XIAOLIN ET AL.: "Preparation and molecular dynamics study of polyurethane damping elastomer containing dynamic disulfide bond and multiple hydrogen bond", 《EUROPEAN POLYMERJOURNAL》 * |
| STEFAN OPREA ET AL.: "Synthesis and characterization of photoactive polyurethane elastomers with 2,3-dihydroxypyridine in the main chain", 《J MATER SCI》 * |
| 李建军: "《塑料配方设计》", 30 September 2019, 中国轻工业出版社 * |
| 杨加明: "《黏弹性复合材料结构及其优化设计》", 31 July 2018, 国防工业出版社 * |
| 汪东等: "聚合物基阻尼材料的结构设计及功能化研究进展", 《中国科学:化学》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773570A (en) * | 2022-03-16 | 2022-07-22 | 华南理工大学 | Polyurethane elastomer containing metal coordination and disulfide bond, preparation method and self-repairing method thereof |
| CN114634609A (en) * | 2022-04-29 | 2022-06-17 | 山东科技大学 | Disulfide bond-containing single-component polyurethane damping material and preparation method thereof |
| CN114634609B (en) * | 2022-04-29 | 2023-12-15 | 山东科技大学 | Single-component polyurethane damping material containing disulfide bonds and preparation method thereof |
| CN116554430A (en) * | 2023-05-11 | 2023-08-08 | 青岛格林沃德新材料科技有限公司 | High-performance polyurethane damping material containing dynamic disulfide bonds and preparation method thereof |
| CN116554430B (en) * | 2023-05-11 | 2024-04-19 | 青岛格林沃德新材料科技有限公司 | High-performance polyurethane damping material containing dynamic disulfide bonds and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113801288B (en) | 2023-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113801288B (en) | High-performance polyurethane damping material based on dynamic disulfide bond and hydrogen bond action and preparation method thereof | |
| CN105399917B (en) | Organic silicon modified thermoplastic polyurethane elastomer and preparation method thereof | |
| CN103265685B (en) | Microporous polyether urethane elastomer composite material and preparation method thereof | |
| CN105367736B (en) | A kind of preparation method for reprocessing polyurethane hot melt of good performance | |
| CN114940740B (en) | High-performance transparent room-temperature self-repairing polyurethane elastomer based on multiple reversible actions and preparation method thereof | |
| CN105038684A (en) | Method for preparing environment-friendly polyurethane adhesive for plastic track | |
| CN102250308A (en) | Polyurethane elastomer composite and preparation method of transparent elastomer thereof | |
| JPWO2011125540A1 (en) | Thermoplastic polyurethane resins and molded products | |
| CN101698695B (en) | Method for synthesizing heat-resistance epoxy resin modified thermoplastic linear polyurethane elastomer | |
| CN109536112B (en) | Hot-melt polyurethane adhesive for attaching waterproof fabric and preparation method thereof | |
| CN108164991B (en) | Polyurethane elastomer composite material for tire filling and preparation method and application thereof | |
| EP2687552A1 (en) | Use of polyurea nanoparticles as performance modifiers in polyurethane materials | |
| CN113817119A (en) | Preparation method of self-healing waterborne polyurethane with synergistic effect of disulfide bond and multiple hydrogen bonds | |
| CN106380570B (en) | A kind of TPU film and preparation method thereof | |
| CN109535374B (en) | Polyurethane elastomer and preparation method thereof | |
| CN113061229B (en) | Weather-resistant heat-resistant high-toughness room-temperature self-repairing polyurethane urea elastomer | |
| JP2024055880A (en) | Telechelic polyurethanes, methods for their preparation and use | |
| US20230407025A1 (en) | Self-healing polyurethane (pu) material, double-layer self-healing pu film, and preparation method and use thereof | |
| CN112011029A (en) | Polycarbonate-based end-capped polyurethane prepolymer, preparation method and application | |
| CN101255619B (en) | Preparation method of melt-spun spandex containing nano-powder | |
| Minoura et al. | Crosslinking and mechanical property of liquid rubber. II. Curative effect of aromatic diols | |
| CN113307941B (en) | Acrylate oligomer and preparation method and application method thereof | |
| CN109096460B (en) | Polyurethane elastomer for manufacturing foamed shoe material and preparation method thereof | |
| CN112538149B (en) | Preparation process of casting polyurethane elastomer | |
| TWI841462B (en) | Modified polyurethane material and method for manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |