CN113603885A - Modified dendritic polyamide-amine, preparation method thereof and application thereof in damping chlorinated butyl rubber - Google Patents
Modified dendritic polyamide-amine, preparation method thereof and application thereof in damping chlorinated butyl rubber Download PDFInfo
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- CN113603885A CN113603885A CN202110836853.9A CN202110836853A CN113603885A CN 113603885 A CN113603885 A CN 113603885A CN 202110836853 A CN202110836853 A CN 202110836853A CN 113603885 A CN113603885 A CN 113603885A
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- pamam
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- methyl acrylate
- ethylenediamine
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- 238000013016 damping Methods 0.000 title claims abstract description 61
- 229920005556 chlorobutyl Polymers 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229920001971 elastomer Polymers 0.000 claims abstract description 37
- 239000005060 rubber Substances 0.000 claims abstract description 35
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 22
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011787 zinc oxide Substances 0.000 claims abstract description 17
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 14
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 14
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008117 stearic acid Substances 0.000 claims abstract description 14
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 85
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 70
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 64
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 37
- 239000005457 ice water Substances 0.000 claims description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 230000015572 biosynthetic process Effects 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- VKOUCJUTMGHNOR-UHFFFAOYSA-N Diphenolic acid Chemical compound C=1C=C(O)C=CC=1C(CCC(O)=O)(C)C1=CC=C(O)C=C1 VKOUCJUTMGHNOR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- RGKUKMROHWBUNQ-UHFFFAOYSA-N methanol;methyl prop-2-enoate Chemical compound OC.COC(=O)C=C RGKUKMROHWBUNQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 15
- 239000000412 dendrimer Substances 0.000 description 12
- 229920000736 dendritic polymer Polymers 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000009826 distribution Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- SENLDUJVTGGYIH-UHFFFAOYSA-N n-(2-aminoethyl)-3-[[3-(2-aminoethylamino)-3-oxopropyl]-[2-[bis[3-(2-aminoethylamino)-3-oxopropyl]amino]ethyl]amino]propanamide Chemical compound NCCNC(=O)CCN(CCC(=O)NCCN)CCN(CCC(=O)NCCN)CCC(=O)NCCN SENLDUJVTGGYIH-UHFFFAOYSA-N 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to modified dendritic polyamide-amine, a preparation method thereof and application thereof in damping chlorinated butyl rubber, wherein the modified dendritic polyamide-amine is applied to damping chlorinated butyl rubber materials, and the rubber materials comprise the following components in parts by mass: 100 parts of chlorinated butyl rubber, 1-3 parts of vulcanizing agent, 1-3 parts of accelerator M, 2-4 parts of stearic acid, 1-2 parts of nano zinc oxide, 2-4 parts of anti-aging agent A, 1-3 parts of light magnesium oxide and 15-30 parts of modified dendritic polyamide-amine. Compared with the prior art, the modified G3.0 dendritic polyamide-amine is applied to the chlorinated butyl rubber, so that the damping performance, the mechanical property, the heat-conducting property and the like of the product are remarkably improved, the damping performance of the rubber is greatly improved, the use limitation of the chlorinated butyl rubber is improved, and the application prospect is very wide.
Description
Technical Field
The invention relates to the field of damping materials, in particular to modified dendritic polyamide-amine, a preparation method thereof and application thereof in damping chlorinated butyl rubber.
Background
Along with the development of society, mechanical equipment has all played important role in daily life and production, has greatly improved production efficiency and product precision, but the vibration of machine in the operation process has also brought a lot of problems simultaneously, the noise that machine vibration sent can seriously influence people's production and living environment at first, can influence people's health and physical and mental health under being in this kind of noise for a long time, the vibration of equipment can lead to the fact the influence to equipment itself secondly, can influence the precision of equipment on the one hand, stability and reliability, on the other hand, the vibration can lead to the fact fatigue damage to the mechanical part of equipment, can make the design and manufacture level reduce in some high-level manufacturing fields, even become technical bottleneck. At present, damping materials are mostly adopted to effectively control mechanical vibration, so that damping and noise reduction are realized. The polymer damping material is used as a novel material and is widely applied to various fields such as military, civil use and the like.
The chlorinated butyl rubber has wide application in the fields of shock absorption, damping and the like. With the development of advanced high-tech technologies in the automobile industry, the aerospace industry and the like, the chlorinated butyl rubber has a very wide application prospect as an excellent damping base material. The chlorinated butyl rubber is an isobutylene-isoprene copolymer elastomer with active chlorine. In a common vulcanization system of rubber, the isobutylene-isoprene copolymer elastomer can be crosslinked with one or two of carbon-carbon double bonds or active chlorine of isoprene, so that the vulcanized rubber of chlorinated butyl rubber has good thermal stability and corrosion resistance, and can be used in extreme environments such as strong corrosion or high temperature. Chlorinated butyl rubber cures faster than butyl rubber and can be used in combination with other elastomers for vulcanization. China once depends on import of chlorinated butyl rubber completely, the domestic demand for chlorinated butyl rubber continuously increases at a growth rate of 15-20% per year, and the growth rate reaches 44.4% in 2005. However, chlorinated butyl rubber has the defects that the high-temperature effective damping functional area is not wide enough, the low-temperature damping stability is not good, the damping effect and the heat-conducting property cannot meet the rigorous requirements of damping vibration attenuation, and the like, so the application field of the chlorinated butyl rubber has certain limitation.
The inventor finds that the small molecular hindered phenol can enhance the damping performance of the rubber material to a certain extent, for example, the hindered phenol AO-60 is added into the chlorinated butyl rubber to improve the damping performance. Or adding the hindered phenol AO-80 into the chlorinated butyl rubber/nitrile rubber to improve the mechanical property and the damping property of the chlorinated butyl rubber/nitrile rubber. Although the small molecular hindered phenol can improve the mechanical property or damping property of the chlorinated butyl rubber to a certain extent, the whole aspects of the effective damping temperature range, the damping property and the mechanical property of the chlorinated butyl rubber still cannot meet the actual requirement, and the small molecular hindered phenol is easy to migrate and influences the long-term maintenance of the damping effect of the chlorinated butyl rubber.
In addition, Chinese patent CN105801947A discloses a high molecular weight hindered phenol damping agent, a preparation method and application thereof. The preparation process of the high molecular weight hindered phenol comprises the steps of hydroxyl protection of the hindered phenol, catalytic dehydrogenation of the methylated hindered phenol, addition polymerization of the methylated hindered phenol containing double bonds, hydroxyl deprotection of the methylated high molecular weight hindered phenol and the like. However, the damping agent has a low hydrogen bond proportion and an uncertain hydrogen bond position, is not easy to form a hydrogen bond with a chlorinated butyl rubber chain, and is not ideal enough in the aspects of improving damping performance and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide modified dendritic polyamidoamine which enables damping performance to be more excellent and stable and prolongs the service life of a damping material, a preparation method thereof and application thereof in damping chlorinated butyl rubber.
The purpose of the invention can be realized by the following technical scheme:
in the invention, certain technology is needed to improve the stability of the rubber material in hydroxyl, and the damping agent with high hydroxyl content is prepared at the same time, so as to further improve the hydrogen bond effect between the damping agent and the rubber matrix and enhance the damping vibration attenuation effect of the rubber material.
According to the invention, the micromolecular compound containing phenolic hydroxyl is used for modifying the dendritic polyamide-amine, so that the hindered phenol dendritic polymer with larger relative molecular mass is obtained, the mobility of the hindered phenol dendritic polymer is reduced relative to that of micromolecular hindered phenol, the damping performance is more excellent and stable, and the service life of the damping material is prolonged.
The invention prepares high molecular weight dendritic hindered phenol, the damping agent contains more hydroxyl, and the phenolic hydroxyl is positioned on the surface of the dendritic polymer due to the spherical space structure and the determined molecular structure of the dendritic polymer, so that the speed, the quantity and the firmness of hydrogen bonds formed by the phenolic hydroxyl and chlorinated butyl rubber are greatly improved, the damping performance of the chlorinated butyl rubber can be effectively improved, and the specific scheme is as follows:
a method for preparing a modified dendritic polyamidoamine, comprising the steps of:
(1) synthesis of G0.5 PAMAM: introducing nitrogen into a methyl acrylate solution for deoxidation and stirring; then putting the ethylenediamine-methanol solution in ice-water bath, and adding N2Under the protection condition, dropwise adding the mixture into a methyl acrylate solution, reacting, removing excessive methyl acrylate, and drying to obtain a colorless viscous transparent liquid G0.5PAMAM;
(2) g1.0 Synthesis of PAMAM: preparing G0.5PAMAM into solution, and performing ice-water bath and N2Under the protection and stirring conditions, dropwise adding the mixture into an ethylenediamine solution, then stirring for reaction, and removing ethylenediamine after the reaction is finished; drying the product to obtain yellowish viscous oily G1.0PAMAM dendrimer, wherein the product G1.0PAMAM is yellowish viscous liquid;
(3) g1.5 Synthesis of PAMAM: introducing nitrogen gas into methyl acrylate solution, deoxidizing and stirring, preparing G1.0PAMAM into solution, and placing in ice-water bath, N2Under the protection condition, dropwise adding into methyl acrylate solution, reacting, removing excessive methyl acrylate, oven drying to obtain yellowish viscous transparent liquid G1.5 PAMAM with viscosity higher than G1.0PThe AMAM is reduced;
(4) g2.0 synthesis of PAMAM: preparing G1.5 PAMAM into solution, and performing ice-water bath and N2Under the protection and stirring conditions, dropwise adding the mixture into an ethylenediamine solution, then stirring for reaction, and removing ethylenediamine after the reaction is finished; drying the product to obtain yellowish viscous oily G2.0 PAMAM dendrimer, wherein the product G2.0 PAMAM is yellow viscous liquid with viscosity higher than that of G1.0 and G1.5;
(5) synthesis of G2.5 PAMAM: introducing nitrogen gas into methyl acrylate solution, deoxidizing, stirring, preparing G2.0 PAMAM into solution, and placing in ice-water bath, N2Under the protection condition, dropwise adding the mixture into a methyl acrylate solution, reacting, removing excessive methyl acrylate, and drying to obtain a yellow brown viscous oily G2.5 PAMAM dendrimer, wherein the viscosity of the dendrimer is reduced compared with that of the G2.0 PAMAM dendrimer;
(6) g3.0 Synthesis of PAMAM: preparing G2.5 PAMAM into solution, and performing ice-water bath and N2Under the protection and stirring conditions, dropwise adding the mixture into an ethylenediamine solution, then stirring for reaction, and removing ethylenediamine after the reaction is finished; drying the product to obtain yellowish viscous oily G3.0PAMAM dendrimer, wherein the product G3.0PAMAM is a tawny viscous liquid with viscosity higher than that of G2.0 and G2.5;
(7) synthesis of modified G3.0 PAMAM: preparing the G3.0PAMAM into a solution, and adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) into the bisphenol acid solution; then the mixture is dropped into the solution of G3.0PAMAM, then reaction is carried out, after dialysis and drying of the reaction mixture, the light yellow powdery product modified dendritic polyamidoamine is obtained, which is stored at-20 ℃ for later use.
Further, the methyl acrylate solution is methyl acrylate methanol solution, wherein the ratio of methyl acrylate to methanol is (0.4-0.5) mol:40 ml;
the ethylene diamine solution is an ethylene diamine methanol solution, wherein the ratio of ethylene diamine to methanol is (0.05-0.5) mol (20-50) ml;
the bisphenol acid solution is diphenolic acid DMSO solution, wherein the ratio of diphenolic acid to DMSO is (0.02-0.05) mol:200 ml.
Further, in the step (2), the molar ratio of G0.5PAMAM to ethylenediamine is 0.01 (0.4-0.5);
in the step (3), the molar ratio of the G1.0PAMAM to the methyl acrylate is 0.04 (0.4-0.5);
in the step (4), the molar ratio of the G1.5 PAMAM to the ethylenediamine is 0.01 (0.2-0.3);
in the step (5), the molar ratio of the G2.0 PAMAM to the methyl acrylate is 0.01 (0.4-0.5);
in the step (6), the molar ratio of the G2.5 PAMAM to the ethylenediamine is 0.01 (0.2-0.3);
in the step (7), the molar ratio of diphenolic acid, EDC, N-hydroxysuccinimide and G3.0PAMAM is 0.03 (0.2-0.4) to (1.5-1.6).
Further, in the step (1), the reaction time is 20-30h, and the temperature is 20-30 ℃; in the step (2), the reaction time is 40-50h, and the temperature is 20-30 ℃; in the step (3), the reaction time is 40-50h, and the temperature is 20-30 ℃; in the step (4), the reaction time is 40-50h, and the temperature is 20-30 ℃; in the step (5), the reaction time is 40-50h, and the temperature is 20-30 ℃; in the step (6), the reaction time is 40-50h, and the temperature is 20-30 ℃; in the step (7), the reaction time is 2-4 days.
Further, the drying includes one or more of vacuum drying, heat drying or freeze drying.
A modified dendritic polyamidoamine prepared as described above.
The application of the modified dendritic polyamide-amine in damping chlorinated butyl rubber material comprises the following components in parts by mass:
100 parts of chlorinated butyl rubber, 1-3 parts of vulcanizing agent, 3-3 parts of accelerator M1, 2-4 parts of stearic acid, 1-2 parts of nano zinc oxide, 2-4 parts of anti-aging agent A, 1-3 parts of light magnesium oxide and 15-30 parts of modified dendritic polyamide-amine, wherein the preferred part of modified dendritic polyamide-amine is 21-29 parts.
Further, the vulcanizing agent comprises sulfur; the promoter M comprises 2-mercaptobenzothiazole; the particle size of the nano zinc oxide is 50-70 nm; the particle size of the light magnesium oxide is 2-5 μm; the anti-aging agent comprises N-phenyl-1-naphthylamine.
Further, the preparation method of the rubber material comprises the following steps: according to the mass parts, putting the chlorinated butyl rubber, a vulcanizing agent, an accelerator M, stearic acid, nano zinc oxide, an anti-aging agent A, light magnesium oxide and modified dendritic polyamide-amine into an open mill, and mixing to obtain the damping chlorinated butyl rubber material.
Further, the mixing temperature is 30-50 ℃.
Compared with the prior art, the modified G3.0 dendritic polyamide-amine prepared by the invention has larger difference between the glass transition temperature and chlorinated butyl rubber, and can effectively improve the loss factor of rubber after being blended with chloroprene rubber
The temperature range of the high damping area of the rubber is widened, so that the damping area of the rubber approaches to the room temperature. In addition, the modified G3.0 dendritic polyamide-amine is in a three-dimensional spherical structure in space, and the surface of the modified G3.0 dendritic polyamide-amine contains a large number of phenolic hydroxyl polar groups, so that the modified G3.0 dendritic polyamide-amine can generate hydrogen bond action with polar groups on a rubber molecular chain. In addition, the addition of the modified G3.0 dendritic polyamide-amine can improve the crosslinking density of molecular chains of the rubber material, so that heat is more easily conducted and diffused in molecular chain links, and the mechanical property of the rubber material is improved. Therefore, when the modified G3.0 dendritic polyamide-amine is applied to chlorinated butyl rubber, the damping performance, the mechanical property, the heat conductivity and the like of the product are obviously improved, the damping performance of the rubber is greatly improved, the use limitation of the chlorinated butyl rubber is improved, and the application prospect is very wide.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
The preparation method of the modified dendritic polyamide-amine comprises the following steps:
(1) synthesis of G0.5 PAMAM: 35.00g (about 0.4100mol) of methyl acrylate was weighed and dissolved in 40mL of methanol solution to obtain a methyl acrylate solution, which was placed in a 250mL three-necked flask and stirred for 1 hour under deoxygenation with nitrogen. 3.00g (about 0.0500mol) of ethylenediamine was weighed out and dissolved in 20mL of methanol to obtain an ethylenediamine-methanol solution, which was placed in a dropping funnel. In an ice water bath, N2Under the protection condition, the ethylenediamine-methanol solution is slowly added into a three-neck flask, the dropping speed is kept to be 1 drop per second, the reaction is carried out for 24 hours at the temperature of 25 ℃, and the excessive methyl acrylate is removed by rotary evaporation and azeotropy at the temperature of 40 ℃. Drying in a vacuum oven at 50 ℃ to obtain colorless viscous transparent liquid.
(2) G1.0 Synthesis of PAMAM: ice water bath, N2Under the protection and magnetic stirring conditions, 25.00g of ethylenediamine (about 0.4200mol) was slowly added to 50mL of methanol solution, mixed well and placed in a three-necked flask, the previously prepared 4.00g G0.5.5 PAMAM (0.0100mol) was dissolved well in 20mL of methanol, placed in a dropping funnel, and subjected to ice-water bath and N-ray tube chromatography2And (3) protecting, dropwise adding the mixture into a three-neck flask under the magnetic stirring condition, keeping the dropwise adding speed at 1 drop per second, stirring for 1 hour under the ice-water bath condition, and stirring for reacting for 48 hours at 25 ℃ after dropwise adding. After the reaction was complete, the solution was rotary evaporated at 40 ℃ to remove methanol and excess ethylenediamine. After most of ethylenediamine was removed, a mixed solution of toluene and methanol (9:1) was added to azeotropically remove the remaining ethylenediamine, and methanol was added to remove toluene. And finally, placing the product in a vacuum drying oven to be dried for 24 hours in vacuum at the temperature of 40 ℃ to obtain the light yellow and viscous oily G1.0PAMAM dendrimer. The product G1.0PAMAM is a pale yellow viscous liquid.
(3) G1.5 Synthesis of PAMAM: 35.00g (about 0.4100mol) of methyl acrylate was weighed and dissolved in 40mL of methanol solution to obtain a methyl acrylate solution, which was placed in a 250mL three-necked flask and stirred for 1 hour under deoxygenation with nitrogen. G1.0PAMAM 2.42.42 g (ca. 0.0400mol) was weighed out and dissolved in 20mL of methanol solution and placed in the dropping funnel. In an ice-water bath、N2Under the protection condition, slowly adding the G1.0 PAMAM-methanol solution into a three-neck flask, keeping the dropping speed at 1 drop per second, stirring for 1h under the condition of ice-water bath, reacting for 48h under the condition of 25 ℃, performing rotary evaporation and azeotropy at 40 ℃, and removing excessive methyl acrylate. Drying in a vacuum oven at 50 deg.C for 48 hr to obtain yellowish viscous transparent liquid with viscosity lower than that of G1.0 PAMAM.
(4) G2.0 synthesis of PAMAM: ice water bath, N2Under the protection and magnetic stirring conditions, 15.00g of ethylenediamine (about 0.2500mol) was slowly added to 50mL of methanol solution, mixed thoroughly and placed in a three-necked flask, the previously prepared 12.00g G1.5.5 PAMAM (about 0.0100mol) was dissolved sufficiently in 10mL of methanol, placed in a dropping funnel, and subjected to ice-water bath and N-ray tube filtration2Adding the mixture into a three-neck flask drop by drop under the protection and magnetic stirring conditions, keeping the dropping speed at 1 drop per second, stirring the mixture for 1 hour under the ice-water bath condition, and then stirring the mixture for reaction for 48 hours at 25 ℃. After the reaction was complete, the solution was rotary evaporated at 40 ℃ to remove methanol and excess ethylenediamine. After most of ethylenediamine was removed, a mixed solution of toluene and methanol (9:1) was added to azeotropically remove the remaining ethylenediamine, and then methanol was added to remove toluene. And finally, placing the product in a vacuum drying oven to be dried in vacuum for 48 hours at the temperature of 50 ℃, thus obtaining the 1.0G PAMAM dendrimer which is light yellow and viscous oily. The product G2.0 PAMAM is a yellow viscous liquid, and the viscosity is increased compared with G1.0 and G1.5.
(5) Synthesis of G2.5 PAMAM: 35.00g (about 0.4100mol) of methyl acrylate was weighed and dissolved in 40mL of methanol solution to obtain a methyl acrylate solution, which was placed in a 250mL three-necked flask and stirred for 1 hour under deoxygenation with nitrogen. 14.29G (ca. 0.0100mol) of G2.0 PAMAM was weighed into 40mL of methanol solution and placed in the dropping funnel. In an ice water bath, N2Under the protection condition, slowly adding the G2.0 PAMAM-methanol solution into a three-neck flask, keeping the dropping speed at 1 drop per second, stirring for 1h under the condition of ice-water bath, reacting for 48h under the condition of 25 ℃, performing rotary evaporation and azeotropy at 40 ℃, and removing excessive methyl acrylate. Drying in a vacuum oven at 50 deg.C for 48 hr to obtain brown viscous oily G2.5 PAMAM dendrimer with viscosity lower than that of G2.0 PAMAM.
(6) Of G3.0PAMAMSynthesizing: ice water bath, N2Under the protection and magnetic stirring conditions, 15.00g of ethylenediamine (0.2500mol) was slowly added to 50mL of methanol solution, mixed well and placed in a three-necked flask, 28.00g G2.5 PAMAM (0.0100mol) prepared previously was dissolved well in 40mL of methanol, placed in a dropping funnel, and subjected to ice-water bath and N-ray tube chromatography2The mixture is added into a three-neck flask drop by drop under the protection condition, the dropping speed is kept to be 1 drop per second, the mixture is stirred for 1 hour under the condition of ice-water bath, and then the reaction is stirred for 48 hours at 25 ℃. After the reaction was complete, the solution was rotary evaporated at 40 ℃ to remove methanol and excess ethylenediamine. After most of ethylenediamine was removed, a mixed solution of toluene and methanol (9:1) was added to azeotropically remove the remaining ethylenediamine, and then methanol was added to remove toluene. And finally, placing the product in a vacuum drying oven for vacuum drying for 48 hours at the temperature of 50 ℃, thus obtaining the yellowish and viscous oily G3.0PAMAM dendrimer. The product G3.0PAMAM is a yellow brown viscous liquid, and has viscosity increased compared with G2.0 and G2.5.
(7) Synthesis of modified G3.0 PAMAM: diphenolic acid (8.45g, 0.03mol) was dissolved in DMSO (200mL) and EDC (57.11g, 0.30mol) and N-hydroxysuccinimide (NHS) (34.28g, 0.30mol) were added to the Diphenolic acid in DMSO solution. Ice water bath, N2The mixture was added dropwise to a DMSO solution of G3.0PAMAM (5.00G, 1.54mmol) under protecting, magnetic stirring. Then allowed to react at room temperature for 3 days, then molecular chains that could not pass through the dialysis membrane were trapped using a dialysis membrane with a molecular weight cut-off (MWCO) of 3,500, and the reaction mixture that was not trapped was dialyzed against DMSO (9 times, 2L) for 2 days, with water being removed from the lyophilizer to give a pale yellow powdered product, which was stored at-20 ℃ for later use. The final product is the added filler.
The damping rubber composite material comprises the following components in parts by weight: chlorinated butyl rubber: 100, respectively; vulcanizing agent: 1-3; accelerator M: 1-3; stearic acid: 2-4; nano zinc oxide: 1-2; an anti-aging agent A: 2-4; light magnesium oxide: 1-3; modified G3.0 PAMAM-H: 15-30, wherein the vulcanizing agent is sulfur; the chemical name of the accelerator M is 2-mercaptobenzothiazole; the grain size of the nano zinc oxide is 50-70 nm; the grain diameter of the light magnesium oxide is 2-5 μm; the chemical name of the anti-aging agent A is N-phenyl-1-naphthylamine.
The following examples were prepared by the method reported in materials Structure and characterization (Wu-chemical industry Press 2004) using an IR spectrophotometer to perform IR analysis on dendrimers G1.0-G3.0 of different generations, using a Nicolet AVATAR 370 model FTIR IR spectrophotometer from Thermo Fisher, USA; the molecular weight of the dendrimer G3.0 was determined by laser flight mass spectrometry using a testing instrument, Voyager DE-STR MALDI-TOF-MS from Applied Biosystems, USA; performing 1HNMR test on the dendritic polymers G1.0-G3.0 by using a nuclear magnetic resonance apparatus, wherein the test apparatus is a Biospin Gmb model of Bruker company; the damping performance of the rubber is tested by adopting a DMA-242 type dynamic mechanical analyzer produced by German Chinesota corporation; the mechanical properties of the chlorinated butyl rubber are tested by GB 528-83.
Comparative example 1
100g of chlorinated butyl rubber, 2g of stearic acid, 1g of nano zinc oxide, 1g of accelerator M1g, 1g of anti-aging agent A2g, 1g of light magnesium oxide and 1g of sulfur are put into an open mill according to the proportion and are mixed under the condition that the roller temperature is 30 ℃, and the common chlorinated butyl rubber is obtained.
The loss factor, tensile strength, elongation at break and thermal conductivity of the common chlorinated butyl damping rubber are shown in Table 2.
Comparative example 2
100g of chlorinated butyl rubber, 3g of stearic acid, 1.5g of nano zinc oxide, 2g of accelerator M, 3g of anti-aging agent A, 3g, 2g of light magnesium oxide and 2g of sulfur are put into an open mill according to the proportion and are mixed under the condition that the roller temperature is 40 ℃, and the common chlorinated butyl rubber is obtained.
The loss factor, tensile strength, elongation at break and thermal conductivity of the common chlorinated butyl damping rubber are shown in Table 2.
Comparative example 3
100g of chlorinated butyl rubber, 4g of stearic acid, 2g of nano zinc oxide, 3g of accelerator M, 3g of anti-aging agent A4g, 3g of light magnesium oxide and 3g of sulfur are put into an open mill according to the proportion and are mixed under the condition that the roller temperature is 50 ℃, and then the common chlorinated butyl rubber is obtained.
The loss factor, tensile strength, elongation at break and thermal conductivity of the common chlorinated butyl damping rubber are shown in Table 2.
Comparative example 4
100g of chlorinated butyl rubber, 4g of stearic acid, 2g of nano zinc oxide, 3g of accelerator M, 3g of anti-aging agent A4g, 3g of light magnesium oxide and 3g of 25g G3.0.0 PAMAM sulfur are put into an open mill according to the proportion and are mixed under the condition that the roller temperature is 50 ℃, and the common chlorinated butyl rubber is obtained.
The nuclear magnetic spectrum, molecular weight and molecular weight distribution index of G3.0PAMAM are shown in Table 1. G3.0PAMAM loss factor, tensile strength, elongation at break and thermal conductivity of the modified damping rubber are shown in Table 2.
Example 1
100G of chlorinated butyl rubber, 2G of stearic acid, 1G of nano zinc oxide, 1G of accelerator M1G, antioxidant A2G, 1G of light magnesium oxide, 15G of modified G3.0PAMAM and 1G of sulfur are put into an open mill according to the proportion and are mixed under the condition that the roller temperature is 30 ℃, and the damping rubber is obtained.
The nuclear magnetic spectrum, infrared spectrum, molecular weight and molecular weight distribution index of the modified G3.0PAMAM are shown in Table 1. The loss factor, tensile strength, elongation at break and thermal conductivity of the modified G3.0PAMAM damping rubber are shown in table 2.
Example 2
100G of chlorinated butyl rubber, 2G of stearic acid, 1G of nano zinc oxide, 1G of accelerator M1G, antioxidant A2G, 1G of light magnesium oxide, 20G of modified G3.0PAMAM and 1G of sulfur are put into an open mill according to the proportion and are mixed under the condition that the roller temperature is 30 ℃, and the damping rubber is obtained.
The modified G3.0PAMAM has the nuclear magnetic spectrum, infrared spectrum, molecular weight and molecular weight distribution index shown in Table 1. The loss factor, tensile strength, elongation at break and thermal conductivity of the modified G3.0PAMAM damping rubber are shown in table 2.
Example 3
100G of chlorinated butyl rubber, 2G of stearic acid, 1G of nano zinc oxide, 1G of accelerator M1G, antioxidant A2G, 1G of light magnesium oxide, 25G of modified G3.0PAMAM and 1G of sulfur are put into an open mill according to the proportion and are mixed under the condition that the roller temperature is 30 ℃, and the damping rubber is obtained.
The nuclear magnetic spectrum, infrared spectrum, molecular weight and molecular weight distribution index of the modified G3.0PAMAM are shown in Table 1. The loss factor, tensile strength, elongation at break and thermal conductivity of the modified G3.0PAMAM damping rubber are shown in table 2.
Example 4
100G of chlorinated butyl rubber, 2G of stearic acid, 1G of nano zinc oxide, 1G of accelerator M1G, antioxidant A2G, 1G of light magnesium oxide, 30G of modified G3.0PAMAM and 1G of sulfur are put into an open mill according to the proportion and are mixed under the condition that the roller temperature is 30 ℃, and the damping rubber is obtained.
The nuclear magnetic spectrum, infrared spectrum, molecular weight and molecular weight distribution index of the modified G3.0PAMAM are shown in Table 1. The loss factor, tensile strength, elongation at break and thermal conductivity of the modified G3.0PAMAM damping rubber are shown in table 2.
TABLE 1 NMR spectra, IR spectra, molecular weights, molecular weight distribution indices of modified G3.0PAMAM and G3.0PAMAM
TABLE 2 loss factor, tensile strength, elongation at break and thermal conductivity of damping rubbers
| Examples | tanδ | Tensile strength/MPa | Elongation at break/% | Thermal conductivity/W/m.K |
| Comparative example 1 | 1.3～1.4 | 5.7～5.8 | 580～590 | 0.13～0.14 |
| Comparative example 2 | 1.4～1.5 | 5.9～6.0 | 600～610 | 0.14～0.15 |
| Comparative example 3 | 1.5～1.6 | 6.2～6.3 | 630～640 | 0.15～0.16 |
| Comparative example 4 | 2.0～2.5 | 8.2～9.3 | 650～680 | 0.16～0.17 |
| Example 1 | 3.5～3.6 | 15.1～1.5 | 680～690 | 0.18～0.19 |
| Example 2 | 3.8～3.9 | 18.3～18.8 | 720～740 | 0.19～0.22 |
| Example 3 | 4.2～4.3 | 19.8～20.9 | 880～900 | 0.22～0.25 |
| Example 4 | 4.0～4.2 | 17.4～17.9 | 760～780 | 0.20～0.21 |
As can be seen from Table 2, in the present invention, the loss factor, tensile strength, elongation at break and thermal conductivity of the damping rubber are improved with the addition of the modified G3.0PAMAM, and the improvement is beyond the improvement of the unmodified G3.0PAMAM, and the molecular structure of the modified G3.0PAMAM is greatly changed from Table 1.
In addition, with the increase of the modified G3.0PAMAM, the initial improvement is obvious, the improvement is not obvious, and even adverse effect occurs, because when the modified G3.0PAMAM is added to reach 30 parts, the particles are seriously agglomerated, so that the internal structure of the rubber is provided with holes, and the related physical properties are reduced.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for preparing modified dendritic polyamidoamine, which is characterized by comprising the following steps:
(1) synthesis of G0.5 PAMAM: introducing nitrogen into a methyl acrylate solution for deoxidation and stirring; then putting the ethylenediamine-methanol solution in ice-water bath, and adding N2Under the protection condition, dropwise adding the mixture into a methyl acrylate solution, reacting, removing excessive methyl acrylate, and drying to obtain G0.5 PAMAM;
(2) g1.0 Synthesis of PAMAM: preparing G0.5PAMAM into solution, and performing ice-water bath and N2Under the protection and stirring conditions, dropwise adding the mixture into an ethylenediamine solution, then stirring for reaction, and removing ethylenediamine after the reaction is finished; drying the product to obtain a product G1.0 PAMAM;
(3) g1.5 Synthesis of PAMAM: introducing nitrogen gas into methyl acrylate solution, deoxidizing and stirring, preparing G1.0PAMAM into solution, and placing in ice-water bath, N2Under the protection condition, dropwise adding the mixture into a methyl acrylate solution, reacting, removing excessive methyl acrylate, and drying to obtain G1.5 PAMAM;
(4) g2.0 synthesis of PAMAM: preparing G1.5 PAMAM into solution, and performing ice-water bath and N2Under the protection and stirring conditions, dropwise adding the mixture into an ethylenediamine solution, then stirring for reaction, and removing ethylenediamine after the reaction is finished; drying the product to obtain G2.0 PAMAM;
(5) synthesis of G2.5 PAMAM: introducing nitrogen to remove methyl acrylate solutionStirring with oxygen, preparing G2.0 PAMAM into solution, and performing ice-water bath and N2Under the protection condition, dropwise adding the mixture into a methyl acrylate solution, reacting, removing excessive methyl acrylate, and drying to obtain G2.5 PAMAM;
(6) g3.0 Synthesis of PAMAM: preparing G2.5 PAMAM into solution, and performing ice-water bath and N2Under the protection and stirring conditions, dropwise adding the mixture into an ethylenediamine solution, then stirring for reaction, and removing ethylenediamine after the reaction is finished; drying the product to obtain G3.0 PAMAM;
(7) synthesis of modified G3.0 PAMAM: preparing the G3.0PAMAM into a solution, and adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) into the bisphenol acid solution; and then dropwise adding the mixture into a solution of G3.0PAMAM, reacting, dialyzing the reaction mixture, and drying to obtain the modified dendritic polyamide-amine.
2. The method for preparing modified dendritic polyamide-amine according to claim 1, characterized in that said methyl acrylate solution is methyl acrylate methanol solution, wherein the ratio of methyl acrylate to methanol is (0.4-0.5) mol:40 ml;
the ethylene diamine solution is an ethylene diamine methanol solution, wherein the ratio of ethylene diamine to methanol is (0.05-0.5) mol (20-50) ml;
the bisphenol acid solution is diphenolic acid DMSO solution, wherein the ratio of diphenolic acid to DMSO is (0.02-0.05) mol:200 ml.
3. The method for preparing modified dendritic polyamide-amine according to claim 1, wherein in the step (2), the molar ratio of G0.5PAMAM to ethylenediamine is 0.01 (0.4-0.5);
in the step (3), the molar ratio of the G1.0PAMAM to the methyl acrylate is 0.04 (0.4-0.5);
in the step (4), the molar ratio of the G1.5 PAMAM to the ethylenediamine is 0.01 (0.2-0.3);
in the step (5), the molar ratio of the G2.0 PAMAM to the methyl acrylate is 0.01 (0.4-0.5);
in the step (6), the molar ratio of the G2.5 PAMAM to the ethylenediamine is 0.01 (0.2-0.3);
in the step (7), the molar ratio of diphenolic acid, EDC, N-hydroxysuccinimide and G3.0PAMAM is 0.03 (0.2-0.4) to (1.5-1.6).
4. The method for preparing modified dendritic polyamide-amine according to claim 1, wherein in the step (1), the reaction time is 20-30h and the temperature is 20-30 ℃; in the step (2), the reaction time is 40-50h, and the temperature is 20-30 ℃; in the step (3), the reaction time is 40-50h, and the temperature is 20-30 ℃; in the step (4), the reaction time is 40-50h, and the temperature is 20-30 ℃; in the step (5), the reaction time is 40-50h, and the temperature is 20-30 ℃; in the step (6), the reaction time is 40-50h, and the temperature is 20-30 ℃; in the step (7), the reaction time is 2-4 days.
5. The method of claim 1, wherein the drying comprises one or more of vacuum drying, heat drying, or freeze drying.
6. A modified dendritic polyamidoamine prepared according to the process of any one of claims 1 to 5.
7. The use of the modified dendritic polyamidoamine according to claim 6, wherein the modified dendritic polyamidoamine is used for damping chlorinated butyl rubber material, and the rubber material comprises the following components in parts by mass:
100 parts of chlorinated butyl rubber, 1-3 parts of vulcanizing agent, 3-3 parts of accelerator M1, 2-4 parts of stearic acid, 1-2 parts of nano zinc oxide, 3-4 parts of anti-aging agent A2, 1-3 parts of light magnesium oxide and 15-30 parts of modified dendritic polyamide-amine.
8. The use of a modified dendritic polyamidoamine according to claim 7, wherein said vulcanizing agent comprises sulfur; the promoter M comprises 2-mercaptobenzothiazole; the particle size of the nano zinc oxide is 50-70 nm; the particle size of the light magnesium oxide is 2-5 μm; the anti-aging agent comprises N-phenyl-1-naphthylamine.
9. The use of a modified dendritic polyamidoamine according to claim 7, characterized in that the rubber material is prepared by the following steps: according to the mass parts, putting the chlorinated butyl rubber, a vulcanizing agent, an accelerator M, stearic acid, nano zinc oxide, an anti-aging agent A, light magnesium oxide and modified dendritic polyamide-amine into an open mill, and mixing to obtain the damping chlorinated butyl rubber material.
10. The use of a modified dendritic polyamidoamine according to claim 9, characterized in that the mixing temperature is 30-50 ℃.
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