CN110951023B - High-molecular damping material capable of being repaired at room temperature and preparation method and application thereof - Google Patents
High-molecular damping material capable of being repaired at room temperature and preparation method and application thereof Download PDFInfo
- Publication number
- CN110951023B CN110951023B CN201911294050.4A CN201911294050A CN110951023B CN 110951023 B CN110951023 B CN 110951023B CN 201911294050 A CN201911294050 A CN 201911294050A CN 110951023 B CN110951023 B CN 110951023B
- Authority
- CN
- China
- Prior art keywords
- room temperature
- damping material
- repaired
- repairable
- molecular
- 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.)
- Active
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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
-
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
-
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
-
- 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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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
- C08G2350/00—Acoustic or vibration damping material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a high-molecular damping material capable of being repaired at room temperature, and a preparation method and application thereof, and belongs to the technical field of high-molecular materials. The invention provides a room temperature repairable polymer damping material, which comprises the following preparation raw materials: the adhesive comprises polymeric polyol, isocyanate, a chain-extending cross-linking agent and a solvent; the polymeric polyol comprises an amino-terminated polymeric polyol or a hydroxyl-terminated polymeric polyol; the molar ratio of the polyhydric alcohol to the isocyanate is (1.1-1.3): 1; the crosslinking degree of the high-molecular damping material capable of being repaired at room temperature is 5-30%. The room temperature repairable polymer damping material provided by the invention has high transparency and excellent mechanical property, can perform spontaneous wound repair under the room temperature condition after being mechanically damaged, greatly improves the safety, durability and service life of the material, and has a good damping effect under the room temperature condition. Meanwhile, the damping material can be subjected to remodeling and recycling when being seriously damaged.
Description
Technical Field
The invention relates to the technical field of high polymer materials capable of being repaired at room temperature, in particular to a high polymer damping material capable of being repaired at room temperature and a preparation method and application thereof.
Background
With the development of modern industry, vibration tools and powerful machines generating strong vibration are increasing, and the vibration hazard caused by various mechanical equipment in operation and working processes is also increasing: (1) in daily life, such vibration and noise can bring adverse effects to people's life, work and physical health, such as impaired hearing, sleep impairment, and disease induction; (2) in the engineering field, broadband random excitation caused by vibration and noise can cause multi-resonance peak response of a structure, directly influence the normal work of electronic devices, instruments and meters, and cause catastrophic consequences in severe cases; (3) in the military field, as the development of weaponry and aircrafts increasingly accelerates and powers, various aircrafts are excited by engines and high-speed airflows during flight, and structural fatigue caused by vibration and harmonic response is very serious.
In order to solve the above problems, it is a common and effective method to cover or coat the surface of a vibrating object or a space contaminated by vibration noise with a polymeric damping material. However, the existing polymer damping material generally has a huge damage risk in the process of vibration reduction and noise reduction: firstly, the surface and the interior of the polymer damping material are easy to crack in the using process (the functional polymer science, 1999, 12 (4): 503.J Appl Polym Sci,2000, 75, 604-; secondly, the polymer damping material is damaged by external impact in the using process. Therefore, the development of the high-molecular damping material capable of repairing mechanical damage has great significance for improving the operation accuracy and safety of various high-power machines and prolonging the service life of the high-power machines.
In addition, the intrinsic type repairable material receives more and more attention because the intrinsic type repairable material can repair multiple damages at the same wound position, thereby effectively improving the durability, safety and service life of the material. Intrinsic repairable materials are based on the opening and remodeling of dynamic covalent bonds or reversible non-covalent interactions at the wound site and the movement of polymer segments to effect wound repair. Therefore, the mechanical properties of intrinsically repairable materials are generally poor. Increasing the mechanical strength of a repairable material tends to result in a decrease in its repair performance, and thus, how to achieve the preparation of a high-strength repairable material becomes a challenge. In addition, the opening and reestablishment of dynamic covalent bonds or reversible non-covalent interactions of the crosslinked intrinsically repairable material often requires an external stimulus, such as light, heat, oxidation-reduction, etc. This cannot be achieved for repairing a micro crack generated inside the material, preventing the material from being finally damaged. At the same time, the need for light, heat, etc. stimuli also limits the use of materials in some extreme conditions. Therefore, it is important to develop an intrinsic type repairable material capable of repairing damage at room temperature and under mild conditions.
Disclosure of Invention
In view of this, the present invention provides a room temperature repairable polymer damping material, and a preparation method and applications thereof. The preparation method of the high-molecular damping material capable of being repaired at room temperature is simple and suitable for large-scale production; the prepared room temperature repairable polymer damping material has high transparency, good damping effect in a room temperature range, excellent mechanical properties and capability of performing damage repair and remodeling at room temperature.
In order to achieve the above object, the present invention provides the following technical solutions: a room temperature repairable polymer damping material comprises the following preparation raw materials: the adhesive comprises polymeric polyol, isocyanate, a chain-extending cross-linking agent and a solvent;
the polymeric polyol comprises an amino-terminated polymeric polyol or a hydroxyl-terminated polymeric polyol;
the molar ratio of the polyhydric alcohol to the isocyanate is (1.1-1.3): 1;
the crosslinking degree of the high-molecular damping material capable of being repaired at room temperature is 5-30%.
Preferably, the polymeric polyol comprises one or more of polypropylene glycol, polyethylene glycol and polytetrahydrofuran.
Preferably, the isocyanate includes one or more of isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, and hexamethylene diisocyanate.
Preferably, the chain-extending cross-linking agent comprises one or more of polypropylene glycol, polydimethylsiloxane, trimesic aldehyde, 4' -dithiodiphenylamine, ethylenediamine, glutaraldehyde and terephthalaldehyde.
The invention provides a preparation method of a high-molecular damping material capable of being repaired at room temperature, which comprises the following steps:
mixing the polyalcohol, isocyanate and a solvent, and carrying out polycondensation reaction to obtain polyurethane;
and mixing the polyurethane, the chain extension cross-linking agent and the solvent, and carrying out cross-linking reaction to obtain the high-molecular damping material capable of being repaired at room temperature.
Preferably, the temperature of the polycondensation reaction is 5-70 ℃ and the time is 12-36 h.
Preferably, the temperature of the crosslinking reaction is 10-80 ℃, and the time is 12-24 h.
The invention also provides the application of the high molecular damping material capable of being repaired at room temperature in the technical scheme or the high molecular damping material capable of being repaired at room temperature prepared by the preparation method in the technical scheme in the fields of automobiles, constructional engineering, machinery, weapons, aerospace or ships.
The invention provides a room temperature repairable polymer damping material, which comprises the following preparation raw materials: the adhesive comprises polymeric polyol, isocyanate, a chain-extending cross-linking agent and a solvent;the polymeric polyol comprises an amino-terminated polymeric polyol or a hydroxyl-terminated polymeric polyol; the molar ratio of the polyhydric alcohol to the isocyanate is (1.1-1.3) to 1; the crosslinking degree of the high-molecular damping material capable of being repaired at room temperature is 5-30%. The molecular chain of the high molecular damping material capable of being repaired at room temperature provided by the invention is not crystallized, and the gaps between the molecular chain and the molecular chain allow visible light wavelengths to penetrate, so that the transparency is good; a large amount of dynamic acting force such as hydrogen bonds and dynamic covalent bonds exist in the room-temperature repairable macromolecular damping material, meanwhile, the flexibility of the polyol is good, the rapid penetration of molecular chains is convenient to realize, and the glass transition temperature of the material is in the room-temperature range, so that the material has high-efficient repairable performance at room temperature; the dynamic acting force in the room temperature repairable macromolecular damping material can be dynamically opened after being heated to a certain temperature, molecular chains are in a viscous state, the dynamic acting force is rebuilt after the temperature is reduced to the room temperature, and the material can be remolded, so that the remolding performance is excellent; because the high molecular damping material which can be repaired at room temperature has more motion units, such as: the change of bond long bond angle, the movement of the polymeric polyol side group, the disconnection reconstruction of molecular chain segments and hydrogen bonds with different strengths, the opening reconstruction of dynamic covalent bonds and the like, so when the material is subjected to external mechanical and noise vibration, the vibration can be effectively converted into heat energy to be consumed, and the damping effect is further achieved; the preparation method provided by the invention is simple to operate and suitable for large-scale production. As shown in the results of the examples, the room temperature repairable polymer damping film material provided by the invention has the strength of 10-40 MPa, the tensile ratio of 700-1200% and the toughness of 40-160 MJ.m-3Loss factor of>The damping temperature range is 50-55 ℃ at 0.3, and the maximum loss factor is 0.78-0.81; after the polymer damping film material capable of being repaired at room temperature provided by the invention is subjected to solution casting remodeling for 3 times and hot pressing remodeling for 3 times, the mechanical strength of more than 94% and the stretching ratio of more than 96% of the original polymer damping film material capable of being repaired at room temperature are still maintained, and the film material has good plasticity; after the film material is completely cut off, the film material can still be spontaneously repaired at room temperature, and the repairing efficiency is as high as more than 97%. After repairWhen the loss factor of the material is more than 0.3, the damping temperature range is 40 ℃, and the maximum loss factor reaches 0.67, which shows that the film material has excellent performance of repairing mechanical damage and damping action at room temperature.
The preparation method of the high-molecular damping material capable of being repaired at room temperature is simple to operate and suitable for large-scale production. The room temperature repairable macromolecular damping material prepared by the invention can spontaneously repair wounds under room temperature conditions with the aid of water when being mechanically damaged, and recovers the mechanical property and damping effect of the material, thereby effectively improving the safety, durability and service life of the damping material in the using process. The material has important application in the fields of automobiles, constructional engineering, machinery, weapons, aerospace or ships.
Drawings
FIG. 1 is a schematic view of a molecular structure of a polymer damping material capable of being repaired at room temperature;
FIG. 2 is an IR spectrum of the room temperature repairable polymeric damping material prepared in example 1, wherein the right image is a partially enlarged IR spectrum within the range of the left elliptic dotted line;
FIG. 3 is a nuclear magnetic diagram of the room temperature repairable polymeric damping material prepared in example 1;
FIG. 4 is a diagram of a room temperature repairable polymer damping film material prepared in example 1;
FIG. 5 is a mechanical property diagram of the room temperature repairable polymer damping film material prepared in example 1;
FIG. 6 is a graph showing the mechanical properties of the room temperature repairable polymer damping film material prepared in example 1 after 1, 2 and 3 solution casting remodeling and hot-pressing remodeling, respectively; wherein, (1) is the mechanical property diagram of the material after the solution remolding, (2) is the mechanical property diagram of the material after the hot-pressing remolding;
FIG. 7 is a graph of the initial mechanical properties of the room temperature repairable polymeric damping film material prepared in example 1 and the mechanical properties of the material after spontaneous repair at room temperature after complete fracture;
FIG. 8 is a graph showing the relationship between the dissipation factor and the temperature of the polymer damping film material capable of being repaired at room temperature prepared in example 2;
FIG. 9 is a photomicrograph of the room temperature repairable polymeric damping film material prepared in example 3 before and after being cut and spontaneously repaired at room temperature, wherein a is the photomicrograph of the room temperature repairable polymeric damping film material cut, and b is the photomicrograph after being repaired;
in fig. 10, a is a graph of the initial mechanical properties of the room temperature repairable polymer damping film material prepared in example 3 and the mechanical properties of the material after being completely cut and spontaneously repaired at room temperature; in fig. 10, b is a graph of the relationship between the dissipation factor and the temperature of the polymer damping film material capable of being repaired at room temperature prepared in example 3;
fig. 11 is a process diagram of the solution casting and hot-pressing remodeling of the polymer damping film material capable of room temperature repairing prepared in example 4, wherein c is a photo of a solution obtained by dissolving the polymer damping material capable of room temperature repairing in ethanol, d is a photo of a solution obtained by casting the ethanol solution in c into a culture dish, e is a photo of the polymer damping material capable of room temperature repairing obtained after the solution casting film is remodeled, f is a fragment of the polymer damping material capable of room temperature repairing, and g is the polymer damping material capable of room temperature repairing obtained after the fragment in f is hot-pressed and remodeled;
FIG. 12 is a graph showing the relationship between the dissipation factor and the temperature of the polymer damping film material capable of being repaired at room temperature prepared in example 4;
FIG. 13 is a graph showing the mechanical properties of the polymeric film material prepared in comparative example 1;
FIG. 14 is a graph showing the relationship between the loss factor and the temperature of the polymeric damping film materials prepared in comparative examples 2 to 4;
FIG. 15 is a graph showing the relationship between the mechanical properties and the isocyanate index of the polymeric damping film materials prepared in comparative examples 2 to 4.
Detailed Description
The invention provides a room temperature repairable polymer damping material, which comprises the following preparation raw materials: the adhesive comprises polymeric polyol, isocyanate, a chain-extending cross-linking agent and a solvent;
the molar ratio of the polyhydric alcohol to the isocyanate is (1.1-1.3): 1, preferably (1.1-1.25): 1;
the crosslinking degree of the room-temperature repairable polymer damping material is 5-30%, preferably 10-30%, and more preferably 15-25%.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the present invention, the polymeric polyol preferably includes one or more of polypropylene glycol, polyethylene glycol and polytetrahydrofuran. In the present invention, the molecular weight of the polypropylene glycol is preferably 230 to 4000, more preferably 400 to 3500, and most preferably 400 to 3000. In the present invention, the molecular weight of the polyethylene glycol is preferably 800 to 3000, more preferably 1000 to 3000, and most preferably 2000 to 3000. In the present invention, the molecular weight of the polytetrahydrofuran is preferably 650 to 3000, more preferably 1000 to 3000, and most preferably 2500 to 3000.
In the present invention, the polymeric polyol preferably includes an amino-terminated polymeric polyol or a hydroxyl-terminated polymeric polyol, specifically, the amino-terminated polymeric polyol preferably includes one or more of an amino-terminated polypropylene glycol, an amino-terminated polyethylene glycol and an amino-terminated polytetrahydrofuran, and more preferably includes an amino-terminated polypropylene glycol, an amino-terminated polyethylene glycol or an amino-terminated polytetrahydrofuran; the hydroxyl-terminated polymeric polyol preferably comprises one or more of hydroxyl-terminated polypropylene glycol, hydroxyl-terminated polyethylene glycol and hydroxyl-terminated polytetrahydrofuran, and more preferably comprises hydroxyl-terminated polypropylene glycol, hydroxyl-terminated polyethylene glycol or hydroxyl-terminated polytetrahydrofuran.
In the present invention, when the two kinds of polymeric polyols with different molecular weights are used as the polymeric polyols, the mass ratio of the polymeric polyol with a small molecular weight to the polymeric polyol with a large molecular weight is preferably 4 (3-5), and specifically, the mass ratio of the polypropylene glycol with a molecular weight of 1000 to the polypropylene glycol with a molecular weight of 2000 is 4 (3-5).
In the present invention, the isocyanate preferably includes one or more of isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Toluene Diisocyanate (TDI), and Hexamethylene Diisocyanate (HDI), more preferably includes isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, or hexamethylene diisocyanate, and most preferably includes isophorone diisocyanate, diphenylmethane diisocyanate, or dicyclohexylmethane diisocyanate. In the present invention, when the isocyanate is a mixture of two isocyanates, the molar ratio of the two isocyanates is preferably (1-2.5): 1, and specifically, the molar ratio of MDI and IPDI is (1-2.5): 1.
According to the invention, the polyol polymer and the isocyanate with specific types and specific dosage ratios are adopted as raw materials, so that the damping effect, the mechanical property, the room temperature self-repairing capability, the remodeling property and the transparency of the obtained room temperature repairable polymer damping material can be improved.
In the present invention, the kind of the solvent is not particularly limited, and the polyhydric alcohol and the isocyanate may be dissolved, and specifically, the solvent is, for example, N '-dimethylacetamide (DMAc), N' -Dimethylformamide (DMF), or Dimethylsulfoxide (DMSO). In the invention, the solvent is preferably dried before use to obtain an ultra-dry solvent; in the present invention, the drying method of the solvent is not particularly limited, and a drying method known in the art may be used. The amount of the solvent is not particularly limited, and the polymeric polyol or isocyanate can be dissolved, specifically, the amount ratio of the polymeric polyol to the solvent is 1 g: (8-10) mL, wherein the dosage ratio of the isocyanate to the solvent is 1 mmol: (1.5-5) mL.
In the present invention, the chain-extending crosslinking agent preferably includes one or more of polypropylene glycol, polydimethylsiloxane, trimesic aldehyde, 4' -dithio diphenylamine, ethylene diamine, glutaraldehyde and terephthalaldehyde, more preferably includes polypropylene glycol, polydimethylsiloxane, trimesic aldehyde, 4' -dithio diphenylamine, ethylene diamine, glutaraldehyde or terephthalaldehyde, and most preferably includes trimesic aldehyde or 4,4' -dithio diphenylamine. The dosage of the chain extension crosslinking agent is not specially limited, and the crosslinking degree requirement (5-30%) of the high-molecular damping material capable of being repaired at room temperature can be ensured.
In the present invention, when the polymeric polyol is a hydroxyl-terminated polymeric polyol, the preparation raw material preferably further includes a catalyst. In the present invention, the catalyst is preferably an organotin catalyst, more preferably dibutyltin dilaurate. The amount of the catalyst used in the present invention is not particularly limited, and may be an amount well known in the art.
According to the invention, the polyol and the isocyanate with specific dosage are adopted, and the crosslinking degree of the high-molecular damping material capable of being repaired at room temperature is regulated and controlled by adding the crosslinking chain extender, so that the high-molecular chains of the obtained material are crosslinked by hydrogen bonds with different strengths, and the construction of a three-dimensional network is realized by the introduced dynamic covalent bond. The molecular chain of the high molecular damping material capable of being repaired at room temperature provided by the invention is not crystallized in the material, the gap between the molecular chain and the molecular chain allows visible light wavelength to penetrate, and the transparency is good; meanwhile, a large amount of dynamic acting forces which can be opened and reconstructed at room temperature, such as hydrogen bonds and dynamic covalent bonds, and a polymeric polyol chain segment with good motility at room temperature exist in the material, so that the material is ensured to have excellent repairing performance at room temperature; meanwhile, the dynamic acting force in the high-molecular damping material capable of being repaired at room temperature can be quickly opened after being heated to a certain temperature (90 ℃), molecular chains are in a viscous state, the dynamic acting force is reconstructed after the temperature is reduced to the room temperature, the material can be remolded, and the remoldability performance is excellent; when the polymer damping material capable of being repaired at room temperature is vibrated by external machinery and noise, more units can move inside the polymer damping material, such as: the change of bond length angle, the movement of polypropylene glycol side group-methyl, the disconnection reconstruction of molecular chain segment and hydrogen bond with different strength, the opening reconstruction of dynamic covalent bond and the like can consume a large amount of energy, effectively convert external vibration and noise into heat energy to be consumed, and thus, the damping effect is excellent.
The invention provides a preparation method of a high-molecular damping material capable of being repaired at room temperature, which comprises the following steps:
mixing the polyalcohol, isocyanate and a solvent, and carrying out polycondensation reaction to obtain polyurethane;
and mixing the polyurethane, the chain extension cross-linking agent and the solvent, and carrying out cross-linking reaction to obtain the high-molecular damping material capable of being repaired at room temperature.
The invention mixes the polyol, isocyanate and solvent to carry out polycondensation reaction to obtain the polyurethane.
In the present invention, the order of mixing the polymeric polyol, the isocyanate and the solvent is preferably that the polymeric polyol and the solvent are subjected to first mixing to obtain a polymeric polyol solution; carrying out second mixing on isocyanate and the solvent to obtain an isocyanate solution; and dropwise adding the isocyanate solution into the polymeric polyol solution under ice bath conditions. In the invention, the second mixing temperature is preferably that the mixture is stirred and mixed for 10-30 min at room temperature, and then stirred and mixed under the ice bath condition until the temperature of the system is less than 5 ℃. In the invention, the dripping speed of the isocyanate solution is preferably 1-2 drops/second. According to the invention, the mixing sequence is adopted, so that the phenomenon that the isocyanate and amino or hydroxyl in the polyol react too fast to form gel or implode can be avoided; the heat generated by the reaction of the isocyanate and the polymeric polyol can be fully removed, and the system is prevented from being overheated to generate oxidation reaction, so that the damping effect, the mechanical property, the room-temperature self-repairing capability, the remolding property and the transparency of the material are realized.
In the present invention, the molar ratio of the polyhydric alcohol to the isocyanate is preferably (1.1 to 1.3):1, and more preferably (1.1 to 1.25): 1. The amount of the solvent is not particularly limited, and the polymeric polyol or isocyanate can be dissolved, specifically, the amount ratio of the polymeric polyol to the solvent is 1 g: (8-10) mL, wherein the dosage ratio of the isocyanate to the solvent is 1 mmol: (1.5-5) mL.
In the present invention, when the polymeric polyol is a hydroxyl-terminated polymeric polyol, the polycondensation reaction is preferably carried out in the presence of a catalyst, that is, the polymeric polyol, an isocyanate, a catalyst and a solvent are mixed and subjected to a polycondensation reaction to obtain a polyurethane. In the present invention, the catalyst is preferably an organotin catalyst, more preferably dibutyltin dilaurate. The amount of the catalyst used in the present invention is not particularly limited, and may be an amount well known in the art.
In the invention, the temperature of the polycondensation reaction is preferably 5-70 ℃, more preferably 20-65 ℃, and most preferably 20-40 ℃; the time of the polycondensation reaction is preferably 12-36 h, more preferably 12-24 h, and most preferably 18-24 h.
In the invention, when the polymeric polyol is amino-terminated polymeric polyol, during the polycondensation reaction, the isocyanate reacts with amino in the amino-terminated polymeric polyol to generate urea groups; when the polyhydric alcohol is hydroxyl-terminated polyhydric alcohol, in the polycondensation reaction process, the isocyanate and the hydroxyl in the hydroxyl-terminated polyhydric alcohol react to generate a carbamate group.
In the invention, after the polycondensation reaction is finished, the subsequent crosslinking reaction is directly carried out without post-treatment, and the preparation method is simple to operate.
After the polyurethane is obtained, the polyurethane, the chain extension crosslinking agent and the solvent are mixed for crosslinking reaction to obtain the high molecular damping material capable of being repaired at room temperature.
In the invention, the temperature of the crosslinking reaction is preferably 10-80 ℃, more preferably 20-75 ℃, and most preferably 60-70 ℃; the time of the crosslinking reaction is preferably 12-24 hours, and more preferably 18-24 hours.
In the invention, a schematic molecular structure diagram of the room-temperature repairable polymeric damping material is shown in fig. 1. In the invention, when the polymeric polyol is amino-terminated polymeric polyol, amino and aldehyde group react to generate Schiff base in the crosslinking reaction process; the polyurethane polymer chains are crosslinked through hydrogen bonds with different strengths, the construction of a three-dimensional network is realized by introducing dynamic reversible covalent bonds (imine bonds, disulfide bonds or boron ester bonds and the like), and meanwhile, the polyatomic alcohol has good mobility in a room temperature range, so that the material has excellent repairing performance at room temperature; the dynamic acting force in the room-temperature repairable macromolecular damping material can be quickly opened after being heated to a certain temperature, and molecular chains are in a viscous state; after the temperature is reduced to room temperature, the dynamic acting force is rebuilt, and the material can be remolded, so that the material has excellent remolding performance; when the material is subjected to external mechanical and noise vibration, the number of units which can move in the prepared room-temperature repairable polymer damping material is more, such as: the change of bond long bond angle, the movement of the polymeric polyol side group, the disconnection reconstruction of molecular chain segments and hydrogen bonds with different strengths, the opening reconstruction of dynamic covalent bonds and the like can consume a large amount of energy, effectively convert mechanical energy into heat energy to be consumed, and further play a role in damping. In the present invention, when the polyol is a hydroxyl-terminated polyol, the isocyanate reacts with the hydroxyl groups in the hydroxyl-terminated polyol to form a formate group during the polycondensation reaction. In the invention, in the crosslinking reaction process, amino and aldehyde group react to generate Schiff base; the polyurethane polymer chains are crosslinked through hydrogen bonds with different strengths, the construction of a three-dimensional network is realized by introducing dynamic reversible covalent bonds (imine bonds, disulfide bonds or boron ester bonds and the like), and meanwhile, the polyatomic alcohol has good mobility in a room temperature range, so that the material has excellent repairing performance at room temperature; the dynamic acting force in the room-temperature repairable macromolecular damping material can be quickly opened after being heated to a certain temperature, and molecular chains are in a viscous state; when the temperature is reduced to room temperature, the dynamic acting force is rebuilt, and the material can be remolded, so that the material has excellent remolding performance; when the material is subjected to external mechanical and noise vibration, the number of units which can move inside the prepared room-temperature repairable polymer damping material is more, such as: the change of bond long bond angle, the movement of the polymeric polyol side group, the disconnection reconstruction of molecular chain segments and hydrogen bonds with different strengths, the opening reconstruction of dynamic covalent bonds and the like can consume a large amount of energy, effectively convert external mechanical energy into heat energy to be consumed, and further play a role in damping.
After the crosslinking reaction is completed, the present invention preferably further comprises subjecting the resulting system to a post-treatment; the post-treatment preferably comprises concentrating the system obtained after the crosslinking reaction, subjecting the resulting concentrate to precipitation, dissolution and precipitation in sequence, repeating the steps of precipitation, dissolution and precipitation, and then drying. The concentration method of the present invention is not particularly limited, and a concentration method known in the art may be used, specifically, distillation under reduced pressure. In the invention, the precipitating agent adopted for precipitation is preferably water, diethyl ether or n-hexane, more preferably water, and when water is used as the precipitating agent, the precipitating agent is safe, nontoxic and low in cost; the amount of the precipitant used in the present invention is not particularly limited, and may be those known in the art. In the invention, the dissolving agent adopted for dissolving is preferably ethanol, tetrahydrofuran, methanol, DMF, DMAc or DMSO, more preferably ethanol, and the ethanol has the advantages of low boiling point, low toxicity, safety and environmental protection. In the invention, the dosage ratio of the dissolving agent to the obtained precipitate is preferably (5-8) mL:1 g. In the present invention, the drying is preferably performed by vacuum drying; the temperature of the vacuum drying is preferably 50-77 ℃, and more preferably 55 ℃; the vacuum drying time is preferably 24-48 h, and more preferably 30 h.
In the invention, the room temperature repairable polymer damping material is preferably prepared into a film state, namely the room temperature repairable polymer damping film material, and then the performance of the room temperature repairable polymer damping film material is tested.
In the present invention, the preparation method of the polymer damping film material preferably includes the following steps: and (3) carrying out solution film casting on the high-molecular damping material capable of being repaired at room temperature to obtain the high-molecular damping film material capable of being repaired at room temperature.
In the invention, the condition of the solution casting film is preferably that a high molecular damping material which can be repaired at room temperature is mixed with a solvent, and the obtained solution is transferred into a mould and dried to obtain the high molecular damping film material. In the present invention, the solvent is preferably ethanol. In the present invention, the mixing is preferably performed under heating conditions, the heating temperature in the present invention is not particularly limited, and the heating temperature well known in the art can be adopted to ensure that the room temperature repairable polymeric damping material is dissolved in the solvent. In the invention, the dosage ratio of the room-temperature repairable polymer damping material to the solvent is preferably (0.2-0.4) g: 1 mL. The temperature and time for drying in the present invention are not particularly limited, and those known in the art can be used.
In the invention, the thickness of the polymer damping film material is 0.5-2 mm, and more preferably 0.5-1.5 mm.
The invention also provides the application of the room temperature repairable polymer damping material or the room temperature repairable polymer damping material prepared by the preparation method in automobiles, constructional engineering, machinery, weapons, aerospace or ships. The room temperature repairable macromolecular damping material provided by the invention can spontaneously repair wounds under room temperature conditions with the aid of water when being damaged by machinery, and recover the mechanical property and damping effect of the material, so that the safety, durability and service life of the damping material in the using process are effectively improved, and the material has important application in the fields of automobiles, constructional engineering, machinery, weapons, aerospace or ships.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the high-molecular damping material capable of being repaired at room temperature comprises the following preparation route:
wherein, the short wavy line in the formula I represents a polypropylene glycol molecular chain, and the long wavy line in the formula II represents a molecular chain with a knot structure shown in the formula I.
Dissolving amino-terminated polypropylene glycol (4g) with the molecular weight of 400 in 30mL of ultra-dry N, N' -dimethylacetamide (DMAc), stirring for 10min at room temperature (25 ℃), and then stirring under an ice bath condition until the system temperature is lower than 5 ℃ to obtain a polypropylene glycol solution; dissolving isophorone diisocyanate (IPDI, 6mmol) in DMAc (10mL) to obtain an isocyanate solution; dropwise adding the isocyanate solution into the polypropylene glycol solution at a constant speed of 2 drops/second, and reacting for 24 hours at room temperature to obtain polyurethane;
dissolving trimesic aldehyde (8mmol) in DMAc (10mL) solution, dropwise adding the obtained trimesic aldehyde solution into a polyurethane system, reacting for 24h at 80 ℃, then sequentially carrying out reduced pressure distillation, putting the obtained concentrated solution into distilled water for precipitation, dissolving the obtained precipitate in 45mL of ethanol, then adding distilled water for precipitation, repeating the precipitation-dissolution-precipitation steps for 3 times, and carrying out vacuum drying on the obtained solid material to obtain the room-temperature repairable macromolecular damping material.
The infrared spectrum of the prepared room temperature repairable polymer damping material is shown in FIG. 2, and the wave number is 3330cm as shown in FIG. 2-1Is an N-H stretching vibration peak; wave number of 2970-2870 cm-1is-CH3and-CH2-a stretching vibration peak; wave number 1690cm-1And 1660cm-1Is the stretching vibration peak of two carbonyl groups; wave number 1643cm-1Stretching vibration of C-N; wave number 1597cm-1～1452cm-1Vibration of the aromatic ring carbon skeleton. The invention successfully prepares the high molecular damping material which can be repaired at room temperature.
The nuclear magnetic spectrum of the prepared room temperature repairable polymer damping material is shown in fig. 3, and it can be seen from fig. 3 that the chemical shift is 8.12 for hydrogen in-CH-N-, the chemical shifts are two carbonyl hydrogens at 8.33 and 5.93, the chemical shifts are 7.25, and the chemical shift is two hydrogens on the aromatic ring skeleton, which indicates that the room temperature repairable polymer damping material is successfully prepared by the present invention.
Dissolving the obtained room-temperature repairable polymer damping material in ethanol, heating to dissolve, placing the obtained solution in a mold, and drying at room temperature to obtain a 0.56mm thick room-temperature repairable polymer damping film material, wherein the dosage ratio of the room-temperature repairable polymer damping material to the solvent is 0.2 g: 1mL, and then tested for performance.
The real object diagram of the high molecular damping film material capable of being repaired at room temperature is shown in fig. 4, and as can be seen from fig. 4, the high molecular damping film material capable of being repaired at room temperature prepared by the invention has good transparency.
The polymer damping film material capable of being repaired at room temperature is subjected to performance test, and the test method comprises the following steps: the tensile property and the mechanical strength are tested by using a universal material testing machine, the test result is shown in fig. 5, and as can be seen from fig. 5, the mechanical strength of the high-molecular damping film material capable of being repaired at room temperature, which is prepared by the invention, is 37.5MPa, and the tensile rate is 816%.
The remolding performance can be tested by two methods: firstly, solution remodeling, namely re-dissolving the high-molecular damping film material fragments capable of being repaired at room temperature into solvents such as ethanol, casting the high-molecular damping film material fragments into a film, drying the film at room temperature to obtain the high-molecular damping film material capable of being repaired at room temperature again, and testing the mechanical properties of the material before and after remodeling, wherein the test result is shown as (1) in figure 6; secondly, hot-pressing and remolding, namely obtaining the high-molecular damping film material which can be repaired at room temperature again by using a hot-pressing film-forming method of a hot press for the high-molecular damping film material fragments which can be repaired at room temperature, and testing the mechanical properties of the material before and after remolding, wherein the test result is shown as (2) in fig. 6. As can be seen from fig. 6, after the polymer damping film material capable of being repaired at room temperature is subjected to solution casting remodeling for 3 times and hot pressing remodeling for 3 times, the mechanical strength is 35MPa, the tensile rate is 800%, 94% of the initial mechanical strength and 98% of the tensile rate are still maintained, which indicates that the polymer damping film material capable of being repaired at room temperature has good plasticity.
After the high molecular damping film material capable of being repaired at room temperature is completely cut off, the material can still be spontaneously repaired at room temperature, the initial mechanical property and the mechanical property after the repair are shown in fig. 7, and as can be seen from fig. 7, the mechanical strength of the repaired material is 35.6MPa, the elongation at break is 820%, which is 95% of the initial mechanical strength and 103% of the tensile ratio, respectively, so that the high molecular damping film material capable of being repaired at room temperature, which is prepared by the method disclosed by the invention, has good room temperature self-repairing property.
The dynamic thermomechanical curve is adopted to test the damping effect, when the loss factor of the high-molecular damping film material capable of being repaired at room temperature is larger than 0.3, the material still has the damping range of 40 ℃, and the maximum loss factor reaches 0.67, which shows that the high-molecular damping film material capable of being repaired at room temperature prepared by the invention has excellent damping effect.
Example 2
Dissolving a polypropylene glycol (2g) with a molecular weight of 1000 hydroxyl end capping and a polypropylene glycol (8g) with a molecular weight of 800 hydroxyl end capping in 80mL of ultra-dry N, N' -dimethylacetamide (DMAc), stirring for 10min at room temperature (25 ℃), and then stirring under an ice bath condition until the system temperature is lower than 5 ℃ to obtain a polypropylene glycol solution; dissolving isophorone diisocyanate (IPDI, 3mmol) and diphenylmethane diisocyanate (MDI, 7mmol) in DMAc (10mL) to obtain an isocyanate solution; dropwise adding an isocyanate solution into a polypropylene glycol solution at a constant speed of 2 drops/second, dropwise adding 3 drops of dibutyltin dilaurate into the obtained reaction system, and reacting for 24 hours at the temperature of 60 ℃ to obtain polyurethane;
dissolving trimesic aldehyde (8mmol) in DMAc (10mL) solution, dropwise adding the obtained trimesic aldehyde solution into a polyurethane system, reacting for 24h at 80 ℃, then sequentially carrying out reduced pressure distillation, putting the obtained concentrated solution into distilled water for precipitation, dissolving the obtained precipitate in 50mL of ethanol, then adding distilled water for precipitation, repeating the precipitation-dissolution-precipitation steps for 3 times, and carrying out vacuum drying on the obtained solid material to obtain the room-temperature repairable macromolecular damping material.
Dissolving the high molecular damping material capable of being repaired at room temperature in ethanol, heating to dissolve the high molecular damping material, placing the obtained solution in a mold, and drying at room temperature to obtain the high molecular damping film material which is 0.83mm thick and capable of being repaired at room temperature, wherein the dosage ratio of the high molecular damping material capable of being repaired at room temperature to the solvent is 0.4 g: 1 mL.
The mechanical strength of the prepared polymer damping film material is 40MPa, the stretching ratio is 810%, after the polymer damping film material is subjected to solution casting film remodeling for 3 times and hot pressing remodeling for 3 times respectively, the mechanical strength of the material is 36MPa, the stretching ratio is 780%, 96% of the initial mechanical strength of the material and 95% of the stretching ratio are still maintained, and the polymer damping film material capable of being repaired at room temperature has good plasticity.
The relationship between the loss factor and the temperature of the high-molecular damping film material capable of being repaired at room temperature before and after the repair is shown in fig. 8, and it can be seen from fig. 8 that the loss factor of the material is greater than 0.3 in the temperature range of 15-70 ℃, and the maximum loss factor reaches 0.73, which shows that the high-molecular damping film material capable of being repaired at room temperature prepared by the invention has good damping effect in the temperature ranges of room temperature and 70 ℃.
Example 3
Dissolving polyethylene glycol (6g) with a molecular weight of 3000 hydroxyl end-capping and polypropylene glycol (8g) with a molecular weight of 800 hydroxyl end-capping in 60mL of ultra-dry N, N' -dimethylacetamide (DMAc), stirring for 10min at room temperature (25 ℃), and then stirring under an ice bath condition until the system temperature is lower than 5 ℃ to obtain a mixed solution of polypropylene glycol and polyethylene glycol; dissolving isophorone diisocyanate (IPDI, 3mmol) and dicyclohexylmethane diisocyanate (HMDI, 1mmol) in DMAc (10mL) to obtain an isocyanate solution; dropwise adding an isocyanate solution into a polypropylene glycol solution at a constant speed of 2 drops/second, dropwise adding 3 drops of dibutyltin dilaurate into the obtained reaction system, and reacting for 24 hours at the temperature of 60 ℃ to obtain polyurethane;
dissolving 4,4 '-dithiodiphenylamine (2mmol) in DMAc (10mL) solution, dropwise adding the obtained 4,4' -dithiodiphenylamine solution into a polyurethane system, reacting for 24 hours at room temperature, then sequentially carrying out reduced pressure distillation, placing the obtained concentrated solution into diethyl ether for precipitation, dissolving the obtained precipitate in 50mL ethanol, then adding diethyl ether for precipitation, repeating the precipitation-dissolution-precipitation steps for 3 times, and carrying out vacuum drying on the obtained solid material to obtain the room-temperature repairable macromolecular damping material.
Dissolving the obtained room-temperature repairable polymer damping material in ethanol, heating to dissolve the obtained solution, placing the obtained solution in a mold, and drying at room temperature to obtain a 0.75mm thick room-temperature repairable polymer damping film material, wherein the dosage ratio of the room-temperature repairable polymer damping material to the solvent is 0.3 g: 1 mL.
The mechanical strength of the high molecular damping film material capable of being repaired at room temperature is 25.5MPa, the stretching ratio is 920%, after 3 times of solution casting and remodeling and 3 times of hot pressing and remodeling, the mechanical strength of the material is 23.4MPa, the stretching ratio is 915%, 92% of the initial mechanical strength and 99% of the stretching ratio are still maintained, and the high molecular damping film material capable of being repaired at room temperature, which is prepared by the invention, has good plasticity.
After the high molecular damping film material capable of being repaired at room temperature is completely cut off, the material can still be repaired spontaneously at room temperature, and the real object images of the material before and after the repair are shown in fig. 9, wherein a is a surface microscopic photograph of a wound of the high molecular damping film material capable of being repaired at room temperature, b is a surface microscopic photograph of the material after the wound is subjected to room-temperature self-repair for 48 hours in the image a, and the comparison between a and b shows that the wound of the material is completely repaired.
The mechanical properties of the room-temperature-repairable polymer damping film material prepared in the embodiment 3 before being completely cut off and after being self-repaired are shown in a in fig. 10, and as can be seen from a in fig. 10, the mechanical strength of the repaired material is 24.2MPa, the elongation at break is 865%, which is 95% of the initial mechanical strength of the material and 94% of the tensile ratio, which indicates that the room-temperature-repairable polymer damping film material prepared in the invention has good room-temperature self-repairing property; the relationship graph of the loss factor and the temperature before and after the repair of the high molecular damping film material capable of being repaired at room temperature is shown as b in figure 10, and as can be seen from b in figure 10, the loss factors of the material are all larger than 0.3 within the temperature range of 15-65 ℃, and the maximum loss factor reaches 0.81, which shows that the high molecular damping film material prepared by the invention has excellent damping effect.
Example 4
Dissolving polytetrahydrofuran (5.8g) with the molecular weight of 2900 in 55mL of ultra-dry N, N' -dimethylacetamide (DMAc), stirring for 10min at room temperature (25 ℃), and then stirring until the system temperature is lower than 5 ℃ under the ice bath condition to obtain a polytetrahydrofuran solution; dissolving isophorone diisocyanate (IPDI, 4mmol) in DMAc (10mL) to obtain an isocyanate solution; dropwise adding an isocyanate solution into a polytetrahydrofuran solution at a constant speed of 2 drops/second, dropwise adding 3 drops of dibutyltin dilaurate into the obtained reaction system, and reacting for 12 hours at the temperature of 60 ℃ to obtain first polyurethane; respectively dissolving IPDI (1mmol) and ethylenediamine (2mmol) in DMAc, sequentially adding the mixture into the obtained first polyurethane system, reacting for 12h at 60 ℃ to obtain second polyurethane, dissolving 4,4 '-dithio diphenylamine (1mmol) in DMAc (5mL) solution, dropwise adding the obtained 4,4' -dithio diphenylamine solution into the obtained second polyurethane system, reacting for 12h at room temperature, sequentially distilling under reduced pressure, placing the obtained concentrated solution in diethyl ether for precipitation, dissolving the obtained precipitate in 25mL tetrahydrofuran, adding diethyl ether for precipitation, repeating the precipitation-dissolution-precipitation steps for 3 times, and vacuum drying the obtained solid material to obtain the room-temperature repairable macromolecular damping material.
Dissolving the high molecular damping material capable of being repaired at room temperature in ethanol, heating to dissolve the high molecular damping material, placing the obtained solution in a mold, and drying at room temperature to obtain the high molecular damping film material which is 0.64mm thick and capable of being repaired at room temperature, wherein the dosage ratio of the high molecular damping material capable of being repaired at room temperature to the solvent is 0.3 g: 1 mL.
The solution casting and hot-pressing remodeling process of the room-temperature-repairable polymer damping film material is shown in fig. 11, wherein c is a photo of a solution obtained by dissolving the room-temperature-repairable polymer damping material in ethanol, d is a photo of a solution cast in a culture dish, e is a photo of the room-temperature-repairable polymer damping material obtained after room-temperature drying remodeling, f is a fragment of the room-temperature-repairable polymer damping material, and g is a room-temperature-repairable polymer damping material obtained after hot-pressing remodeling of the fragment in f. As can be seen from fig. 12, the room temperature repairable polymeric damping material prepared by the present invention has excellent solution and thermal remodeling properties.
The initial mechanical strength of the high-molecular damping film material capable of being repaired at room temperature is 39.8MPa, the initial stretching ratio is 834%, after 3 times of solution casting and remodeling and 3 times of hot-pressing and remodeling, the mechanical strength is 39MPa, the stretching ratio is 800%, 98% of the initial mechanical strength and 96% of the stretching ratio are still maintained, and the high-molecular damping film material capable of being repaired at room temperature, which is prepared by the invention, has good plasticity.
The relationship between the loss factor and the temperature of the high molecular damping film material capable of being repaired at room temperature is shown in fig. 12, and it can be known from fig. 12 that the loss factors of the high molecular damping film material capable of being repaired at room temperature are all larger than 0.3 within the temperature range of 18-77 ℃, and the maximum loss factor reaches 0.76, which indicates that the high molecular damping film material prepared by the invention has excellent damping effect.
Comparative example 1
Dissolving amino-terminated polypropylene glycol (4g, 5mmol) with molecular weight of 800 in 20mL of ultra-dry N, N' -dimethylacetamide (DMAc), stirring for 10min at room temperature, and then stirring under an ice bath condition until the system temperature is lower than 5 ℃ to obtain a polypropylene glycol solution; dissolving diphenylmethane diisocyanate (MDI, 5mmol) in DMAc (10mL) to obtain an isocyanate solution; dropwise adding the isocyanate solution into the polypropylene glycol solution at a constant speed of 2 drops/second, reacting for 24 hours at room temperature, placing the obtained reaction system into a glass culture dish with the diameter of 10cm, and drying at 60 ℃ to obtain the colorless and transparent polymer film material.
The mechanical properties of the polymer film material are shown in fig. 13, and it can be seen from fig. 13 that the movement of the molecular chain segment is limited due to the increase of the hydrogen bond density and the hydrogen bond strength, so that the material is changed from elasticity to plasticity, and the material has an obvious yield point and a poor damping effect.
Comparative example 2
Adding hydroxyl-terminated polypropylene glycol (6g) with molecular weight of 800 into four-neck bottle equipped with thermometer, stirrer and vacuum connection tube, vacuum dehydrating at 110 deg.C and-0.095 MPa for 3 hr, and measuring water content<Stopping vacuum pumping at 0.1 wt%, and keeping N2Under the protection condition, reducing the temperature of a reaction system to 50 ℃, adding isophorone diisocyanate (IPDI, 3mmol), diphenylmethane diisocyanate (MDI, 7mmol) and DMAc (10mL), heating to 90 ℃ to react for 2.5h, stopping the reaction when the-NCO% in the system reaches a theoretical value, degassing by adopting negative pressure until no bubble exists, and preheating in a 50 ℃ oven for 30min to obtain a component A;
adding hydroxyl-terminated polypropylene glycol (2g) with the molecular weight of 800 into a four-neck flask provided with a thermometer, a stirrer and a vacuum tail pipe, dehydrating for 3h under the conditions of 110 ℃ and-0.095 MPa in vacuum, stopping vacuumizing when the moisture content is measured to be less than 0.1 wt%, cooling the temperature of a reaction system to room temperature, adding a chain-extending cross-linking agent and 3 drops of dibutyltin dilaurate, and preheating for 30min in a 50 ℃ oven to obtain a component B;
and (2) uniformly stirring and mixing the component A and the component B, then carrying out vacuum defoaming, pouring into a standard mould, vulcanizing at 90 ℃ and 10MPa for 1.5h, then demoulding to obtain a polyurethane sample with the thickness of 2mm, placing the obtained polyurethane sample in a 100 ℃ oven for curing for 24h, and then curing at room temperature for 7 days to obtain the polymer damping film material.
Comparative example 3
The polymeric damping material was prepared according to the method of comparative example 2, which is different from comparative example 2 in that dicyclohexylmethane diisocyanate (HMDI) was used instead of IPDI.
Comparative example 4
A polymeric damping material was prepared according to the method of comparative example 2, which differs from comparative example 2 in that Toluene Diisocyanate (TDI) was used instead of IPDI.
The relationship between the loss factor and the temperature of the polymeric damping film materials prepared in the comparative examples 2-4 is shown in FIG. 14, and it can be seen from FIG. 14 that the loss factor change trends of different isocyanate type PUEs are almost consistent within-100 ℃, are reduced firstly and then increased sharply, a damping peak value appears, then the damping peak value is reduced sharply and finally tends to be stable, and generally speaking, when the loss factor is more than or equal to 0.3, the polymeric damping film materials have obvious damping performance. The effective damping temperature range of different isocyanate type PUE with the loss factor more than or equal to 0.3 is greatly changed, but the range is within the range of 30-50 ℃.
The relationship between the mechanical property and the isocyanate index of the polymer damping film materials prepared in the comparative examples 2-4 is shown in FIG. 15, and it can be known from FIG. 15 that the tensile strength of three types of isocyanate PUE increases with the increase of the R value. The reason is that the content of hard segments in the PUE material is increased along with the increase of the R value, the acting force between hydrogen bonds and molecules is increased, the cohesive energy is increased, and the tensile strength is increased.
In conclusion, compared with the polymer damping material prepared by the traditional preparation method, the preparation method provided by the invention is simple, the final product can be obtained only by a one-step method, and the intermediate treatment process is omitted, so that the preparation method is suitable for large-scale production. The polymer damping material prepared by the invention has wider use temperature and excellent damping effect; can be spontaneously repaired after being damaged by machinery, and has the potential of recycling, thereby greatly saving resources and protecting the environment.
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 (7)
1. The high-molecular damping material capable of being repaired at room temperature is characterized by comprising the following preparation raw materials: the adhesive comprises polymeric polyol, isocyanate, a chain-extending cross-linking agent and a solvent;
the molar ratio of the polyhydric alcohol to the isocyanate is (1.1-1.3): 1;
the crosslinking degree of the high-molecular damping material capable of being repaired at room temperature is 5-30%;
the chain extension crosslinking agent comprises one or more of trimesic aldehyde, glutaraldehyde and terephthalaldehyde.
2. The room temperature repairable polymeric damping material of claim 1, wherein said polymeric polyol includes one or more of polypropylene glycol, polyethylene glycol and polytetrahydrofuran.
3. The room temperature repairable polymeric damping material of claim 1, wherein said isocyanate comprises one or more of isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate and hexamethylene diisocyanate.
4. The preparation method of the room temperature repairable polymer damping material according to any one of claims 1 to 3, characterized by comprising the following steps:
mixing the polyalcohol, isocyanate and a solvent, and carrying out polycondensation reaction to obtain polyurethane;
and mixing the polyurethane, the chain extension cross-linking agent and the solvent, and carrying out cross-linking reaction to obtain the high-molecular damping material capable of being repaired at room temperature.
5. The method according to claim 4, wherein the polycondensation reaction is carried out at a temperature of 5 to 70 ℃ for 12 to 36 hours.
6. The preparation method according to claim 4, wherein the temperature of the crosslinking reaction is 10-80 ℃ and the time is 12-24 h.
7. The room temperature repairable polymer damping material according to any one of claims 1 to 3 or the room temperature repairable polymer damping material prepared by the preparation method according to any one of claims 4 to 6 is applied to the fields of automobiles, construction engineering, machinery, weapons, aerospace or ships.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911294050.4A CN110951023B (en) | 2019-12-16 | 2019-12-16 | High-molecular damping material capable of being repaired at room temperature and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911294050.4A CN110951023B (en) | 2019-12-16 | 2019-12-16 | High-molecular damping material capable of being repaired at room temperature and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110951023A CN110951023A (en) | 2020-04-03 |
| CN110951023B true CN110951023B (en) | 2021-01-22 |
Family
ID=69981910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911294050.4A Active CN110951023B (en) | 2019-12-16 | 2019-12-16 | High-molecular damping material capable of being repaired at room temperature and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110951023B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11780951B2 (en) * | 2021-05-13 | 2023-10-10 | Lanzhou Institute Of Chemical Physics | Chain extender, preparation method and application thereof, recyclable thermosetting polyurethane and preparation method thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112126036A (en) * | 2020-09-11 | 2020-12-25 | 常州大学 | Disulfide bond-based biodegradable cross-linked self-repairing polyurethane and preparation method thereof |
| CN112940214B (en) * | 2021-01-22 | 2022-08-26 | 山东师范大学 | Preparation method and application of self-repairing polymer based on reversible imine bond |
| TWI784598B (en) * | 2021-06-23 | 2022-11-21 | 國立臺北科技大學 | Self-healing copolymerized polymer material and manufacturing method thereof as well as light-emitting material, white led backlight display, conductive electrode material, organic light-emitting diode, and flexible light-emitting electronic device containing the same |
| CN114369218B (en) * | 2021-12-16 | 2022-11-22 | 河南大学 | Polymer material based on dynamic cross-linked network, preparation method and application |
| 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 |
| CN115197393A (en) * | 2022-07-06 | 2022-10-18 | 辽宁大学 | Preparation method of self-repairing material with synergistic effect of multiple mechanisms |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107602790A (en) * | 2017-10-26 | 2018-01-19 | 西南大学 | A kind of high-performance and can reprocessabilty castor oil network polymer and preparation method thereof |
| CN107961747A (en) * | 2017-11-30 | 2018-04-27 | 青岛理工大学 | Inside repair outer curable type polyureas base double-walled self-repairing microcapsule and preparation method thereof |
| CN108659188A (en) * | 2018-06-01 | 2018-10-16 | 南京理工大学 | A kind of polyureas selfreparing thermoplastic elastomer (TPE) and preparation method thereof |
| CN109054057A (en) * | 2018-06-15 | 2018-12-21 | 盐城工学院 | A kind of preparation method based on schiff bases room temperature selfreparing polyurethane |
| KR20190002820A (en) * | 2017-06-30 | 2019-01-09 | 한국과학기술연구원 | Composition for self healing thermoplastic elastomers comprising disulfide bonds and methods of preparing the same |
| US10344139B1 (en) * | 2015-08-03 | 2019-07-09 | Cornerstone Research Group, Inc. | Electrically responsive variable stiffness polymers |
| KR20190083551A (en) * | 2018-01-04 | 2019-07-12 | 한국과학기술연구원 | Self healing elastomer, self healing complex and self healing film |
| CN110498895A (en) * | 2019-08-05 | 2019-11-26 | 南京理工大学 | Poly- (urea-urethane) selfreparing elastomer of tridimensional network and preparation method thereof |
-
2019
- 2019-12-16 CN CN201911294050.4A patent/CN110951023B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10344139B1 (en) * | 2015-08-03 | 2019-07-09 | Cornerstone Research Group, Inc. | Electrically responsive variable stiffness 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 |
| KR20190002820A (en) * | 2017-06-30 | 2019-01-09 | 한국과학기술연구원 | Composition for self healing thermoplastic elastomers comprising disulfide bonds and methods of preparing the same |
| CN107602790A (en) * | 2017-10-26 | 2018-01-19 | 西南大学 | A kind of high-performance and can reprocessabilty castor oil network polymer and preparation method thereof |
| CN107961747A (en) * | 2017-11-30 | 2018-04-27 | 青岛理工大学 | Inside repair outer curable type polyureas base double-walled self-repairing microcapsule and preparation method thereof |
| KR20190083551A (en) * | 2018-01-04 | 2019-07-12 | 한국과학기술연구원 | Self healing elastomer, self healing complex and self healing film |
| CN108659188A (en) * | 2018-06-01 | 2018-10-16 | 南京理工大学 | A kind of polyureas selfreparing thermoplastic elastomer (TPE) and preparation method thereof |
| CN109054057A (en) * | 2018-06-15 | 2018-12-21 | 盐城工学院 | A kind of preparation method based on schiff bases room temperature selfreparing polyurethane |
| CN110498895A (en) * | 2019-08-05 | 2019-11-26 | 南京理工大学 | Poly- (urea-urethane) selfreparing elastomer of tridimensional network and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| Castor oil derived poly(urethane urea) networks with reprocessibility and enhanced mechanical properties;Chen Jia-Hui et al.;《POLYMER》;20180403;第143卷;第79-86页 * |
| Castor oil-based high performance and reprocessable poly(urethane urea) network;Chen Jia-Hui et al.;《POLYMER TESTING》;20180709;第70卷;第174-179页 * |
| Stretchy and strong polyurethane-urea supramolecular (PUUS) hydrogels with various stimulus-responsive behaviours: the effect of chain-extenders;Xia Qianhui et al.;《Journal of Materials Chemistry B》;20181115;第7卷(第10期);第1734-1740页，第1737页右栏第2段，支持信息图S1 * |
| Synthesis and Properties of Reversible Disulfide Bond-based Self-healing Polyurethane with Triple Shape Memory Properties;Jia Han et al.;《CHINESE JOURNAL OF POLYMER SCIENCE》;20190521;第37卷(第11期);第1119-1129页 * |
| Water-Enabled Room-Temperature Self-Healing and Recyclable Polyurea Materials with Super-Strong Strength, Toughness, and Large Stretchability;Zhen Shi et al.;《ACS Applied Materials & Interfaces》;20200428;第12卷(第20期);第23484-23493页 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11780951B2 (en) * | 2021-05-13 | 2023-10-10 | Lanzhou Institute Of Chemical Physics | Chain extender, preparation method and application thereof, recyclable thermosetting polyurethane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110951023A (en) | 2020-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110951023B (en) | High-molecular damping material capable of being repaired at room temperature and preparation method and application thereof | |
| CN109897148B (en) | Stable borate ester bond based dynamically covalently crosslinked renewable polyurea-urethanes and their preparation and use | |
| CN109504368B (en) | Preparation method of CDs/TPU fluorescent nano composite material | |
| Xia et al. | Castor‐oil‐based waterborne polyurethane dispersions cured with an aziridine‐based crosslinker | |
| Li et al. | Feasible self-healing CL-20 based PBX: employing a novel polyurethane-urea containing disulfide bonds as polymer binder | |
| CN113801294B (en) | High-strength, wide-temperature-range and high-damping polyurethane elastomer material and preparation method thereof | |
| CN114685756B (en) | High-performance self-repairing polyurea and preparation method thereof | |
| CN109749049B (en) | Reversible chain extender, preparation thereof and method for preparing crosslinked polyurethane by using reversible chain extender | |
| CN112062926A (en) | Cross-linking type fusible casting energetic polymer adhesive material | |
| CN110563922A (en) | Chemical crosslinking type high-performance room-temperature rapid self-repairing flexible material and preparation method and application thereof | |
| CN114195972B (en) | PDMS material containing benzimidazolyl dynamic covalent bond, preparation method and application thereof | |
| Deng et al. | Mechanically strong and stretchable polyurethane–urea supramolecular hydrogel using water as an additional in situ chain extender | |
| CN111019076A (en) | Rapid UV-cured hyperbranched polyurethane acrylate and preparation method thereof | |
| CN110551269A (en) | Heat-resistant room-temperature rapid self-repairing elastomer and preparation method and application thereof | |
| Wang et al. | Insertion of supramolecular segments into covalently crosslinked polyurethane networks towards the fabrication of recyclable elastomers | |
| CN115353609A (en) | Repairable and reinforced high-performance polyurethane elastomer and preparation method thereof | |
| CN111333807B (en) | Phenolic-based renewable high polymer material, and preparation method and regeneration application thereof | |
| CN115232465A (en) | Preparation method of tough self-repairing material capable of realizing self-repairing in seawater | |
| CN113881014B (en) | High-toughness self-repairing reprocessable polyurethane elastomer modified by 1, 8-menthane diamine and preparation method thereof | |
| CN110591043A (en) | Crosslinking type azide adhesive with self-repairability and preparation method thereof | |
| CN107849289B (en) | Method for recycling benzoxazine resin-containing materials, in particular benzoxazine resin-containing fiber composite plastics | |
| CN111875793A (en) | Phthalonitrile resin for composite material and preparation method thereof | |
| CN109694476B (en) | Method for preparing ureido-containing autocatalytic poly (phthalonitrile) resin | |
| CN115558074B (en) | Polyurethane elastomer and preparation method thereof | |
| CN115894841A (en) | Chemical crosslinking polyurea and preparation method thereof |
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 | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhang Ling Inventor after: Shi Zhen Inventor after: Kang Jing Inventor before: Shi Zhen Inventor before: Zhang Ling Inventor before: Kang Jing |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |