CN111548510A - Dendritic UPy damping agent and preparation method and application thereof - Google Patents
Dendritic UPy damping agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a dendritic UPy damping agent, a preparation method and application thereof. The dendritic UPy damping agent is obtained by reacting terminal isocyanate group dendritic macromolecules and 6-methylisocytosine, the terminal isocyanate group dendritic macromolecules are obtained by reacting terminal amino group dendritic macromolecules and 1, 6-hexamethylene diisocyanate, the terminal amino group dendritic macromolecules are obtained by reacting terminal chlorine atom-containing dendritic macromolecules and 1, 6-hexamethylene diamine, and the terminal chlorine atom-containing dendritic macromolecules are obtained by alternately reacting products obtained by reacting hexachlorotriphosphazene and ethylene glycol with 1, 6-hexamethylene diamine and hexachlorotriphosphazene respectively. Experiments show that: the dendritic UPy damping agent can be uniformly dispersed in a chlorinated butyl rubber matrix, and can remarkably improve the damping performance, heat resistance, mechanical property, wear resistance and high-temperature damping temperature range of the obtained chlorinated butyl damping rubber composite material.
Description
Technical Field
The invention relates to a damping agent, a preparation method and application thereof, in particular to a dendritic UPy damping agent, a preparation method thereof and application thereof in chlorinated butyl damping rubber composite materials, belonging to the technical field of damping materials.
Background
With the rapid development of modern science and technology and modern industry, traffic tends to be high-speed and automatic, and a series of problems such as vibration, noise, fatigue fracture and the like are inevitably generated, so that the fatigue damage of a vehicle structure is accelerated, the service life of the vehicle is shortened, the environment is polluted, and the health of people is harmed. Therefore, the research and development of novel and efficient damping materials with excellent comprehensive performance, vibration reduction and noise reduction and improvement of the man-machine working environment are problems to be solved urgently.
The rubber damping material is one of the important types of polymer damping materials, and is a functional material which absorbs vibration mechanical energy and converts the vibration mechanical energy into heat energy for loss by utilizing a viscoelastic structure of rubber. The chlorinated butyl rubber chain segment has large relaxation resistance, strong internal friction force and better damping and vibration reduction performance, and has wide application in the fields of aerospace, rail transit, automobile manufacturing and the like. In the use process in the engineering field, in order to meet the requirements of different environmental conditions, the damping rubber is often required to have higher damping performance in a wider temperature range, and only then, the high damping performance of the rubber can be fully embodied. However, the chlorinated butyl rubber has a glass transition temperature (Tg) of about-40 ℃, the damping temperature range is concentrated in a low-temperature region, and the defects of insufficient wide high-temperature damping temperature range, insufficient damping performance and heat resistance meeting harsh damping vibration attenuation requirements, poor mechanical property and wear resistance and the like exist, so that the application field has certain limitation. For this reason, certain measures are required to modify chlorinated butyl rubber.
In order to overcome the defects of chlorinated butyl rubber, widen the damping temperature range and improve the damping performance of chlorinated butyl rubber, at present, scholars at home and abroad mainly modify chlorinated butyl rubber by adopting the following technologies: the preparation method comprises the steps of organic small molecular hindered phenol blending modification, organic clay intercalation modification, inorganic piezoelectric ceramic and carbon black blending modification and the like; secondly, high polymer blending modification, including rubber and rubber blending modification, rubber and plastic blending modification and the like; and modifying the high polymer structure by an interpenetrating polymer network method, a multilayer coextrusion method and the like. The modification technologies have respective damping mechanisms, wherein the small molecular hindered phenol endows the material with high-temperature damping characteristics through the destruction of hydrogen bonds and the formation of mechanical energy consuming the outside in the use process of the material, namely a hydrogen bond action mechanism; the interpenetrating polymer network converts mechanical energy into thermal energy through forced mutual compatibility and interface interpenetration of a porous network structure, namely an entanglement buffer mechanism. Although the above modification technology can improve the damping performance of chlorinated butyl rubber to a certain extent, the improvement on the whole aspects of the high-temperature damping temperature range, damping performance, heat resistance, mechanical property and wear resistance of chlorinated butyl rubber still cannot meet the actual requirements.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a dendritic UPy (namely 2-ureido-4[ 1H ] pyrimidinone, having an English name of 2-ureido-4[ lH ] pyreimidinone) damping agent, a preparation method thereof and application thereof in chlorinated butyl damping rubber composite materials, so as to overcome the defects of the existing materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
a dendritic UPy damping agent is obtained by reacting terminal isocyanate group dendritic macromolecules and 6-methylisocytosine, wherein the terminal isocyanate group dendritic macromolecules are obtained by reacting terminal amino group dendritic macromolecules and 1, 6-hexamethylene diisocyanate, the terminal amino group dendritic macromolecules are obtained by reacting terminal chlorine atom containing dendritic macromolecules and 1, 6-hexamethylene diamine, and the terminal chlorine atom containing dendritic macromolecules are obtained by alternately reacting products obtained by reacting hexachlorotriphosphazene and ethylene glycol with 1, 6-hexamethylene diamine and hexachlorotriphosphazene respectively.
A method for preparing the dendritic UPy damping agent comprises the following steps:
a) preparing a dendritic macromolecule containing chlorine atoms at the tail ends:
firstly, reacting hexachlorotriphosphazene with ethylene glycol in the presence of an acid catalyst to obtain a 1 st generation dendritic macromolecule; then the 1 st generation dendritic macromolecule reacts with 1, 6-hexamethylene diamine in the presence of an acid catalyst to obtain 1.5 th generation dendritic macromolecule; then reacting the 1.5 th generation dendritic macromolecule with hexachlorotriphosphazene in the presence of an acid catalyst to obtain a 2 nd generation dendritic macromolecule; performing alternate reaction to obtain n-th generation of dendritic macromolecules, namely the dendritic macromolecules with chlorine atoms at the tail ends, wherein n is an integer more than or equal to 3;
b) preparing an amino-terminated dendritic macromolecule:
dispersing D-n and 1, 6-hexanediamine in toluene, stirring and reacting for 1-2 hours at room temperature under the protection of inert gas, and collecting a solid product to obtain amino-terminated dendritic macromolecules, namely D-NH2；
c) Preparing the isocyanate-terminated dendritic macromolecule:
by reacting D-NH2Dispersing in deionized water to prepare 5-10 wt% of suspension, adding 1, 6-hexamethylene diisocyanate and an organic tin catalyst, stirring and reacting for 2-3 hours at room temperature under the protection of inert gas, and collecting a solid product to obtain isocyanate-terminated dendritic macromolecules, namely D-NCO;
d) preparing a dendritic UPy damping agent:
dispersing D-NCO and 6-methylisocytosine in dichloromethane, then stirring and reacting for 30-50 minutes at room temperature under the protection of inert gas, reacting for 3-5 hours at 20-40 ℃, and distilling under reduced pressure to remove a reaction solvent to obtain the dendritic UPy damping agent, namely D-UPy.
In one embodiment, in step a), the acidic catalyst is p-toluenesulfonic acid.
In a preferred embodiment, the preparation of the dendrimer having a chlorine atom at the terminal in step a) comprises the following steps:
dispersing hexachlorotriphosphazene and p-toluenesulfonic acid in ethylene glycol, stirring and reacting for 2-4 hours at 120-140 ℃ under the protection of inert gas, and collecting a solid product to obtain a 1 st generation dendritic macromolecule, which is abbreviated as D-1;
dispersing 1, 6-hexanediamine and p-toluenesulfonic acid in toluene, adding D-1, stirring and reacting for 2-4 hours at 130-150 ℃ under the protection of inert gas, and collecting a solid product to obtain a 1.5 generation dendritic macromolecule, which is abbreviated as D-1.5;
dispersing hexachlorotriphosphazene and p-toluenesulfonic acid in toluene, adding D-1.5, stirring and reacting at 120-140 ℃ for 2-4 under the protection of inert gas, and collecting a solid product to obtain a 2 nd generation dendritic macromolecule, which is abbreviated as D-2;
and performing alternate reaction to obtain the n-th generation of dendritic macromolecules, namely the dendritic macromolecules with the tail ends containing chlorine atoms, which are abbreviated as D-n, wherein n is an integer more than or equal to 3.
In a preferred embodiment, the step a) of preparing the dendrimer of generation 1, the collecting the solid product comprises the following steps:
firstly, vacuumizing to remove unreacted monomers, then washing residues with methanol, centrifuging and precipitating, and drying the obtained precipitate for 4-6 hours at 40-60 ℃ in vacuum.
In a preferred embodiment, the step a) of preparing the dendrimer of generation 1.5, the collecting the solid product comprises the following steps:
firstly, vacuumizing to remove unreacted monomers, then washing residues with methanol, centrifuging and precipitating, and drying the obtained precipitate for 4-6 hours at the temperature of 60-80 ℃ in vacuum.
In a preferred embodiment, the step a) of preparing the dendrimer of generation 2, the collecting the solid product comprises the following steps:
firstly, vacuumizing to remove unreacted monomers, then washing residues with methanol, centrifuging and precipitating, and drying the obtained precipitate for 4-6 hours at 80-100 ℃ in vacuum.
In a preferable embodiment, in the step a), when hexachlorotriphosphazene participates in the reaction, the mass ratio of p-toluenesulfonic acid to corresponding hexachlorotriphosphazene is 1: (100-200); when 1, 6-hexamethylene diamine participates in the reaction, the mass ratio of p-toluenesulfonic acid to the corresponding 1, 6-hexamethylene diamine is 1: (100-150).
In a preferable embodiment, in the step a), the mass ratio of the hexachlorotriphosphazene used in the previous step to the 1, 6-hexamethylenediamine used in the next adjacent step is 1: 1-1: 2.
In a preferable scheme, in the step a), n is any integer between 3 and 6.
In one embodiment, step b), the preparation of the amino-terminated dendrimer, the collection of the solid product comprises the following operations:
firstly, filtering, then drying a filter cake in vacuum at 120-140 ℃ for 12-16 hours, and grinding.
In one embodiment, step b), D-n: the mass ratio of the 1, 6-hexamethylene diamine is 1: 1-2: 1.
In one embodiment, step c), the preparation of the isocyanate-terminated dendrimer, the collection of the solid product comprises the following operations:
firstly, filtering, then drying a filter cake for 24-30 hours at 100-120 ℃, and grinding.
In one embodiment, step c), D-NH2: the mass ratio of the 1, 6-hexamethylene diisocyanate is 1: 1-2: 1.
In one embodiment, step c), the organotin catalyst is dibutyltin dilaurate and the amount of organotin catalyst added is D-NH2And 1 to 5 parts by weight of 1, 6-hexamethylene diisocyanatewt％。
In one embodiment, step D), D-NCO: the mass ratio of the 6-methylisocytosine is 1: 1-3: 1.
The chlorinated butyl damping rubber composite material prepared by applying the dendritic UPy damping agent is prepared by adding 5-15 parts by mass of the dendritic UPy damping agent into 100 parts by mass of a chlorinated butyl rubber matrix.
One embodiment of the chlorinated butyl damping rubber composite material comprises the following components in percentage by weight:
chlorinated butyl rubber matrix: 100 parts by mass;
vulcanizing agent: 2-4 parts by mass;
accelerator M (chemical name 2-mercaptobenzothiazole): 2-3 parts by mass;
accelerator TMTD (chemical name bis (dimethylthiocarbamoyl) disulfide): 1-2 parts by mass;
stearic acid: 1-3 parts by mass;
zinc oxide: 4-5 parts by mass;
antioxidant a (chemical name is diaryl secondary amine antioxidant): 2-4 parts by mass;
dendritic UPy damping agent: 5 to 15 parts by mass.
In one embodiment, the vulcanizing agent is sulfur.
A method for preparing the chlorinated butyl damping rubber composite material is to add the components in proportion into an open mill and mix at 30-50 ℃.
Compared with the prior art, the invention has the following remarkable beneficial effects:
the invention adopts the product obtained by the reaction of hexachlorotriphosphazene and ethylene glycol to respectively react with 1, 6-hexamethylene diamine and hexachlorotriphosphazene alternately to prepare the dendritic macromolecule with the chlorine atom at the tail end with controllable size and shape, and then the dendritic macromolecule with the chlorine atom at the tail end reacts with 1, 6-hexamethylene diamine, 1, 6-hexamethylene diisocyanate and 6-methylisocytosine in sequence to prepare the dendritic UPy damping agent, the prepared dendritic UPy damping agent has rich and various functional groups and multiple hydrogen bond characteristics, and can be uniformly dispersed into a chlorinated butyl rubber matrix after being added into the chlorinated butyl rubber matrix, so that the chlorinated butyl damping rubber composite material obtained by the invention has excellent damping performance, heat resistance, mechanical property and wear resistance, especially has wider high-temperature damping temperature range, the method achieves remarkable progress and unexpected effect and has industrial application value.
Detailed Description
The technical scheme of the invention is further detailed and completely explained by combining the embodiment, the application example and the comparative example.
Analyzing the functional group composition of the dendritic UPy damping agent by adopting infrared spectroscopy;
testing the molecular weight of the dendritic UPy damping agent by matrix-assisted laser desorption ionization time-of-flight mass spectrometry;
the damping performance of the rubber is tested by adopting a DMA-242 type dynamic mechanical analyzer produced by German Chinesota corporation;
the thermal weight loss method specified in the theory and practice of polymer/layered silicate nano composite materials (sumoni, Shang Wen Yu Shu, chemical industry Press, 2002) is adopted to test the thermal weight loss center temperature of the dendritic damping agent;
the tensile and abrasion properties of the rubber were tested using GB 528-83 and GB/T1689-1998.
Example 1
a) Preparing a dendritic macromolecule containing chlorine atoms at the tail ends:
dispersing 20g of hexachlorotriphosphazene and 0.1g of p-toluenesulfonic acid in 150g of ethylene glycol (the ethylene glycol serves as a reactant and a solvent at the same time), then stirring and reacting for 2 hours at 140 ℃ under the protection of nitrogen, finishing the reaction, firstly vacuumizing to remove unreacted monomers, then washing residues with methanol, centrifugally precipitating, and drying the obtained precipitate for 6 hours at 40 ℃ in vacuum to obtain a 1 st generation dendritic macromolecule, which is abbreviated as D-1;
dispersing 30g of 1, 6-hexanediamine and 0.2g of p-toluenesulfonic acid in 100g of toluene, adding D-1 prepared in the previous step, stirring and reacting for 4 hours at 130 ℃ under the protection of nitrogen, finishing the reaction, firstly vacuumizing to remove unreacted monomers, then washing residues with methanol, centrifugally precipitating, and drying the obtained precipitate for 6 hours at 60 ℃ in vacuum to obtain 1.5 generation dendritic macromolecules, namely D-1.5;
dispersing 40g of hexachlorotriphosphazene and 0.3g of p-toluenesulfonic acid in 120g of toluene, adding D-1.5 prepared in the previous step, stirring and reacting for 4 hours at 120 ℃ under the protection of nitrogen, finishing the reaction, firstly vacuumizing to remove unreacted monomers, then washing residues with methanol, centrifugally precipitating, and drying the obtained precipitate for 6 hours at 80 ℃ in vacuum to obtain 2 nd generation of dendritic macromolecules, which are abbreviated as D-2;
performing alternate reaction to obtain a 3 rd generation dendritic macromolecule, namely a dendritic macromolecule with a chlorine atom at the tail end, which is abbreviated as D-3;
b) preparing an amino-terminated dendritic macromolecule:
dispersing 20g D-3 and 10g of 1, 6-hexanediamine in 100g of toluene, stirring and reacting for 1 hour at room temperature under the protection of nitrogen, finishing the reaction, filtering, drying a filter cake for 12 hours at 120 ℃, and grinding to obtain the amino-terminated dendritic macromolecule, which is abbreviated as D-NH2；
c) Preparing the isocyanate-terminated dendritic macromolecule:
20g D-NH2Dispersing in deionized water to prepare 5 wt% of suspension, adding 10g of 1, 6-hexamethylene diisocyanate and 0.5g of dibutyltin dilaurate, stirring and reacting for 2 hours at room temperature under the protection of nitrogen, finishing the reaction, filtering, drying a filter cake for 28 hours at 100 ℃, and grinding to obtain an isocyanate-terminated dendritic macromolecule, which is abbreviated as D-NCO;
d) preparing a dendritic UPy damping agent:
dispersing 30g D-NCO and 10g 6-methylisocytosine in 100g dichloromethane, then stirring and reacting for 30 minutes at room temperature under the protection of nitrogen, reacting for 3 hours at 20 ℃, ending the reaction, and distilling under reduced pressure to remove the reaction solvent to obtain a white viscous substance, namely the dendritic UPy damping agent, which is abbreviated as D-UPy.
Data on the infrared spectra and molecular weights of the dendritic UPy damping agents prepared in this example are shown in table 1.
Application example 1
100g of chlorinated butyl rubber, 2g of sulfur, 2g of accelerator M, 1g of accelerator TMTD, 1g of stearic acid, 4g of zinc oxide, 2g of antioxidant A and 5g of dendritic UPy damping agent are put into an open mill and mixed at the temperature of 30 ℃ to obtain the chlorinated butyl damping rubber composite material.
The performance test data for the chlorinated butyl damping rubber composites prepared are shown in table 2.
Comparative example 1
100g of chlorinated butyl rubber, 2g of sulfur, 2g of accelerator M, 1g of accelerator TMTD, 1g of stearic acid, 4g of zinc oxide and 2g of antioxidant A are put into an open mill and mixed at the temperature of 30 ℃ to obtain a comparative chlorinated butyl damping rubber material.
The performance test data for the comparative chlorinated butyl damping rubber material prepared is shown in table 2.
Example 2
a) Preparing a dendritic macromolecule containing chlorine atoms at the tail ends:
dispersing 30g of hexachlorotriphosphazene and 0.2g of p-toluenesulfonic acid in 180g of ethylene glycol (the ethylene glycol is used as a reactant and a solvent at the same time), then stirring and reacting for 3 hours at 130 ℃ under the protection of nitrogen, finishing the reaction, firstly vacuumizing to remove unreacted monomers, then washing residues with methanol, centrifugally precipitating, and drying the obtained precipitate for 5 hours at 50 ℃ in vacuum to obtain a 1 st generation dendritic macromolecule, which is abbreviated as D-1;
dispersing 40g of 1, 6-hexanediamine and 0.3g of p-toluenesulfonic acid in 130g of toluene, adding D-1 prepared in the previous step, stirring and reacting at 140 ℃ for 3 hours under the protection of nitrogen, finishing the reaction, firstly vacuumizing to remove unreacted monomers, then washing residues with methanol, centrifugally precipitating, and drying the obtained precipitate at 70 ℃ for 5 hours in vacuum to obtain 1.5 generation dendritic macromolecules, namely D-1.5;
dispersing 50g of hexachlorotriphosphazene and 0.4g of p-toluenesulfonic acid in 150g of toluene, adding D-1.5 prepared in the previous step, stirring and reacting at 130 ℃ for 3 hours under the protection of nitrogen, finishing the reaction, firstly vacuumizing to remove unreacted monomers, then washing residues with methanol, centrifugally precipitating, and drying the obtained precipitate at 90 ℃ for 5 hours in vacuum to obtain 2 nd generation of dendritic macromolecules, which are abbreviated as D-2;
performing alternate reaction to obtain a 3 rd generation dendritic macromolecule, namely a dendritic macromolecule with a chlorine atom at the tail end, which is abbreviated as D-3;
b) preparing an amino-terminated dendritic macromolecule:
dispersing 30g D-3 and 20g of 1, 6-hexanediamine in 150g of toluene, stirring and reacting for 1.5 hours at room temperature under the protection of nitrogen, finishing the reaction, filtering, drying a filter cake for 14 hours at 130 ℃, and grinding to obtain the amino-terminated dendritic macromolecule, which is abbreviated as D-NH2；
c) Preparing the isocyanate-terminated dendritic macromolecule:
mixing 30g D-NH2Dispersing in deionized water to prepare 8 wt% of suspension, adding 20g of 1, 6-hexamethylene diisocyanate and 0.6g of dibutyltin dilaurate, stirring and reacting for 2.5 hours at room temperature under the protection of nitrogen, finishing the reaction, filtering, drying a filter cake for 30 hours at 110 ℃, and grinding to obtain isocyanate-terminated dendritic macromolecules, namely D-NCO;
d) preparing a dendritic UPy damping agent:
dispersing 40g D-NCO and 20g 6-methylisocytosine in 150g dichloromethane, then stirring and reacting for 40 minutes at room temperature under the protection of nitrogen, then reacting for 4 hours at 30 ℃, ending the reaction, and distilling under reduced pressure to remove the reaction solvent to obtain a white viscous substance, namely the dendritic UPy damping agent, which is abbreviated as D-UPy.
Data on the infrared spectra and molecular weights of the dendritic UPy damping agents prepared in this example are shown in table 1.
Application example 2
100g of chlorinated butyl rubber, 3g of sulfur, 2.5g of accelerator M, 1.5g of accelerator TMTD, 2g of stearic acid, 4.5g of zinc oxide, 3g of antioxidant A and 10g of dendritic UPy damping agent are put into an open mill and mixed at the temperature of 40 ℃ to obtain the chlorinated butyl damping rubber composite material.
The performance test data for the chlorinated butyl damping rubber composites prepared are shown in table 2.
Comparative example 2
100g of chlorinated butyl rubber, 3g of sulfur, 2.5g of accelerator M, 1.5g of accelerator TMTD, 2g of stearic acid, 4.5g of zinc oxide and 3g of antioxidant A are put into an open mill and mixed at the temperature of 40 ℃ to obtain the comparative chlorinated butyl damping rubber material.
The performance test data for the comparative chlorinated butyl damping rubber material prepared is shown in table 2.
Example 3
a) Preparing a dendritic macromolecule containing chlorine atoms at the tail ends:
dispersing 40g of hexachlorotriphosphazene and 0.3g of p-toluenesulfonic acid in 210g of ethylene glycol (the ethylene glycol is used as a reactant and a solvent at the same time), then stirring and reacting for 4 hours at 120 ℃ under the protection of nitrogen, finishing the reaction, firstly vacuumizing to remove unreacted monomers, then washing residues with methanol, centrifugally precipitating, and drying the obtained precipitate for 4 hours at 60 ℃ in vacuum to obtain a 1 st generation dendritic macromolecule, which is abbreviated as D-1;
dispersing 50g of 1, 6-hexanediamine and 0.4g of p-toluenesulfonic acid in 150g of toluene, adding D-1 prepared in the previous step, stirring and reacting for 2 hours at 150 ℃ under the protection of nitrogen, finishing the reaction, firstly vacuumizing to remove unreacted monomers, then washing residues with methanol, centrifugally precipitating, and drying the obtained precipitate for 4 hours at 80 ℃ in vacuum to obtain 1.5 generation dendritic macromolecules, namely D-1.5;
dispersing 60g of hexachlorotriphosphazene and 0.5g of p-toluenesulfonic acid in 170g of toluene, adding D-1.5 prepared in the previous step, stirring and reacting for 4 hours at 140 ℃ under the protection of nitrogen, finishing the reaction, firstly vacuumizing to remove unreacted monomers, then washing residues with methanol, centrifugally precipitating, and drying the obtained precipitate for 6 hours at 100 ℃ in vacuum to obtain 2 nd generation of dendritic macromolecules, which are abbreviated as D-2;
performing alternate reaction to obtain a 3 rd generation dendritic macromolecule, namely a dendritic macromolecule with a chlorine atom at the tail end, which is abbreviated as D-3;
b) preparing an amino-terminated dendritic macromolecule:
dispersing 40g D-3 and 30g of 1, 6-hexanediamine in 200g of toluene, stirring and reacting for 2 hours at room temperature under the protection of nitrogen, finishing the reaction, filtering, drying a filter cake for 12 hours at 140 ℃, and grinding to obtain the amino-terminated dendritic macromolecule, which is abbreviated as D-NH2；
c) Preparing the isocyanate-terminated dendritic macromolecule:
mixing 40g D-NH2Dispersing in deionized water to prepare 10 wt% of suspension, adding 30g of 1, 6-hexamethylene diisocyanate and 0.7g of dibutyltin dilaurate, stirring and reacting for 3 hours at room temperature under the protection of nitrogen, finishing the reaction, filtering, drying a filter cake for 28 hours at 120 ℃, and grinding to obtain an isocyanate-terminated dendritic macromolecule, which is abbreviated as D-NCO;
d) preparing a dendritic UPy damping agent:
dispersing 50g D-NCO and 30g 6-methylisocytosine in 200g dichloromethane, then stirring and reacting for 50 minutes at room temperature under the protection of nitrogen, then reacting for 3 hours at 40 ℃, ending the reaction, and distilling under reduced pressure to remove the reaction solvent to obtain a white viscous substance, namely the dendritic UPy damping agent, which is abbreviated as D-UPy.
Data on the infrared spectra and molecular weights of the dendritic UPy damping agents prepared in this example are shown in table 1.
Application example 3
100g of chlorinated butyl rubber, 4g of sulfur, 3g of accelerator M, 2g of accelerator TMTD, 3g of stearic acid, 5g of zinc oxide, 4g of antioxidant A and 15g of dendritic UPy damping agent are put into an open mill and mixed at the temperature of 50 ℃ to obtain the chlorinated butyl damping rubber composite material.
The performance test data for the chlorinated butyl damping rubber composites prepared are shown in table 2.
Comparative example 3
100g of chlorinated butyl rubber, 4g of sulfur, 3g of accelerator M, 2g of accelerator TMTD, 3g of stearic acid, 5g of zinc oxide and 4g of antioxidant A are put into an open mill and mixed at the temperature of 50 ℃ to obtain a comparative chlorinated butyl damping rubber material.
The performance test data for the comparative chlorinated butyl damping rubber material prepared is shown in table 2.
TABLE 1 Infrared Spectroscopy and molecular weight of dendritic UPy damping Agents
TABLE 2 Performance test data for rubber materials
As can be seen from table 3: the chlorinated butyl damping rubber composite material using the dendritic UPy damping agent disclosed by the invention has more excellent mechanical property, wear resistance and heat resistance, has more excellent damping performance, and has a wider high-temperature damping temperature range.
Finally, it should be pointed out here that: the above is only a part of the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention, and the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above description are intended to be covered by the present invention.
Claims (10)
1. A dendritic UPy damping agent, characterized by: the isocyanate-terminated dendritic macromolecule is obtained by reacting an isocyanate-terminated dendritic macromolecule with 6-methylisocytosine, the isocyanate-terminated dendritic macromolecule is obtained by reacting an amino-terminated dendritic macromolecule with 1, 6-hexamethylene diisocyanate, the amino-terminated dendritic macromolecule is obtained by reacting a dendritic macromolecule containing a chlorine atom at the terminal with 1, 6-hexamethylene diamine, and the dendritic macromolecule containing the chlorine atom at the terminal is obtained by alternately reacting a product obtained by reacting hexachlorotriphosphazene with ethylene glycol with 1, 6-hexamethylene diamine and hexachlorotriphosphazene respectively.
2. A method of making a dendritic UPy damping agent as claimed in claim 1, comprising the steps of:
a) preparing a dendritic macromolecule containing chlorine atoms at the tail ends:
firstly, reacting hexachlorotriphosphazene with ethylene glycol in the presence of an acid catalyst to obtain a 1 st generation dendritic macromolecule; then the 1 st generation dendritic macromolecule reacts with 1, 6-hexamethylene diamine in the presence of an acid catalyst to obtain 1.5 th generation dendritic macromolecule; then reacting the 1.5 th generation dendritic macromolecule with hexachlorotriphosphazene in the presence of an acid catalyst to obtain a 2 nd generation dendritic macromolecule; performing alternate reaction to obtain n-th generation of dendritic macromolecules, namely the dendritic macromolecules with chlorine atoms at the tail ends, wherein n is an integer more than or equal to 3;
b) preparing an amino-terminated dendritic macromolecule:
dispersing D-n and 1, 6-hexanediamine in toluene, stirring and reacting for 1-2 hours at room temperature under the protection of inert gas, and collecting a solid product to obtain amino-terminated dendritic macromolecules, namely D-NH2；
c) Preparing the isocyanate-terminated dendritic macromolecule:
by reacting D-NH2Dispersing in deionized water to prepare 5-10 wt% of suspension, adding 1, 6-hexamethylene diisocyanate and an organic tin catalyst, stirring and reacting for 2-3 hours at room temperature under the protection of inert gas, and collecting a solid product to obtain isocyanate-terminated dendritic macromolecules, namely D-NCO;
d) preparing a dendritic UPy damping agent:
dispersing D-NCO and 6-methylisocytosine in dichloromethane, then stirring and reacting for 30-50 minutes at room temperature under the protection of inert gas, reacting for 3-5 hours at 20-40 ℃, and distilling under reduced pressure to remove a reaction solvent to obtain the dendritic UPy damping agent, namely D-UPy.
3. The method of claim 2, wherein: in step a), the acidic catalyst is p-toluenesulfonic acid.
4. The method of claim 2, wherein: in the step a), n is any integer between 3 and 6.
5. The method of claim 2, wherein: in step b), D-n: the mass ratio of the 1, 6-hexamethylene diamine is 1: 1-2: 1.
6. The method of claim 2, wherein: in step c), D-NH2: the mass ratio of the 1, 6-hexamethylene diisocyanate is 1: 1-2: 1.
7. The method of claim 2, wherein: in step D), D-NCO: the mass ratio of the 6-methylisocytosine is 1: 1-3: 1.
8. A chlorinated butyl damping rubber composite material prepared by applying the dendritic UPy damping agent of claim 1, which is characterized in that: and 5-15 parts by mass of the dendritic UPy damping agent is added into 100 parts by mass of a chlorinated butyl rubber matrix.
9. The chlorinated butyl damping rubber composite material according to claim 8, wherein the chlorinated butyl damping rubber composite material comprises the following components in percentage by weight:
chlorinated butyl rubber matrix: 100 parts by mass;
vulcanizing agent: 2-4 parts by mass;
accelerator M: 2-3 parts by mass;
accelerator TMTD: 1-2 parts by mass;
stearic acid: 1-3 parts by mass;
zinc oxide: 4-5 parts by mass;
an anti-aging agent A: 2-4 parts by mass;
dendritic UPy damping agent: 5 to 15 parts by mass.
10. A method of preparing the chlorinated butyl damping rubber composite of claim 8 or 9, wherein: the components are added into an open mill according to the proportion and are mixed at the temperature of 30-50 ℃.
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