CN116656017B - Damping composite system, damping composite material and preparation method of damping composite material - Google Patents
Damping composite system, damping composite material and preparation method of damping composite material Download PDFInfo
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- 238000013016 damping Methods 0.000 title claims abstract description 169
- 239000002131 composite material Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title abstract description 8
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- 229920000459 Nitrile rubber Polymers 0.000 claims description 21
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- 238000000034 method Methods 0.000 claims description 10
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- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000010059 sulfur vulcanization Methods 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
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- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
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- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 2
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- HNWAHFPYJHAAJE-UHFFFAOYSA-N n-tert-butyl-1,3-benzothiazole-2-sulfonamide Chemical compound C1=CC=C2SC(S(=O)(=O)NC(C)(C)C)=NC2=C1 HNWAHFPYJHAAJE-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of rubber materials, and discloses a damping composite system, a damping composite material and a preparation method of the damping composite material. The damping composite system comprises a crosslinkable polymer and a non-crosslinkable polymer, wherein the crosslinkable polymer is a polymer with the content of unsaturated double bonds being 1-10wt%, and the non-crosslinkable polymer is a fully saturated polymer with the content of double bonds being less than 1wt%. The damping composite system provided by the invention is composed of polymers which are completely compatible and have different crosslinking mechanisms, so that the corresponding damping composite material has the characteristics of high damping, high strength and wide material selection range. The damping composite material provided by the invention contains the damping composite system. The damping composite material has the characteristics of high damping, high strength and wide material selection range. The preparation method can be used for efficiently preparing the damping composite material with high damping factor or damping modulus and ensuring high mechanical property.
Description
Technical Field
The invention relates to the technical field of rubber materials, in particular to a damping composite system, a damping composite material and a preparation method thereof.
Background
The polymer damping material has the functional characteristics of shock absorption, noise reduction and the like, and is widely applied to the fields of automobiles, household appliances, traffic and the like. The damping characteristics of the polymer damping material mainly depend on the combination of the molecular structure and the formula of the polymer, and especially the molecular structure of the polymer plays a decisive role in damping performance. The damping mechanism mainly comprises energy dissipation, such as energy dissipation of molecular chain segment movement, intermolecular friction, filler network destruction, recombination and the like.
The method expands the selection range of the damping material, improves the damping factor or damping modulus of the damping material, realizes the application of the damping material in different environments, is a main problem of development of the damping material, and is a main way for realizing the development of novel damping material.
At present, the common polymer damping material is mainly a highly crosslinked rubber composite material, high energy consumption is realized by mainly applying segmental motion of rubber polymers in glass transition, and only polymers with specific molecular structures can achieve expected high damping effect, so that the damping material has a narrow selection range, and the damping effect is not easy to meet the requirements.
The polymer damping material mainly converts the kinetic energy of vibration into heat energy through the movement of polymer molecular chain segments to dissipate, and the molecular structure design of the polymer damping material plays a decisive role in the quality of damping performance of the material. However, due to the problems of dynamics, thermodynamics, steric hindrance effect and the like of polymer polymerization, it is often difficult to obtain an ideal single damping high polymer material.
Thus, composite damping materials have become the primary method of developing damping materials, including blends of different polymers, polymer-object material blends, and the like. In general, due to the different molecular structures, different polymers cannot achieve complete compatibility at the molecular level, and the mixed polymer has a phase separation structure (0.1-100 um) on a microscopic scale; the filler can also improve the damping performance of the polymer by the mechanism of the destruction and recombination of a filler network and the friction action of the filler and the polymer, but the application of the filler and the polymer is limited due to poor compatibility of the filler and the polymer. In addition, the non-crosslinked polymer molecules can slip under the external force to consume energy, so that the damping effect is realized, but the non-crosslinked polymer molecules can only be used as colloid due to the poor mechanical properties of the non-crosslinked elastomer, and cannot be applied as a single mechanical material. In addition, if the polymer composite system is completely crosslinked, the elasticity of the polymer system increases and the damping performance decreases; and in general, the polymer has lower compatibility and microscopic phase separation, so that the crosslinking uniformity is poor and the mechanical property of the material is lower due to non-uniformity.
Disclosure of Invention
The invention aims to solve the problems that the existing polymer damping material is poor in damping effect, single damping high polymer material is difficult to obtain and the conventional composite damping material is incompatible in molecules, and provides a damping composite system. The damping composite system is composed of polymers which are completely compatible and have different crosslinking mechanisms, so that the corresponding damping composite material has the characteristics of high damping, high strength and wide material selection range.
The invention also aims to provide a damping composite material. The damping composite material is specifically a molecular-level gel-unrestricted entangled uniform interpenetrating network damping composite material, is based on the damping composite system with molecular-level complete compatibility, and is characterized in that cross-linked polymers in the damping composite system generate cross-linking action to form interpenetrating network polymers with cross-linked networks and uncrosslinkable polymers to form unrestricted entangled networks, so that the uncrosslinked polymers can realize energy consumption in the cross-linked polymer networks in modes of entanglement-disentanglement, crawling movement and the like, generate damping action, and have the characteristics of high damping, high strength and wide material application temperature range.
It is another object of the present invention to provide a method of preparing the damping composite. According to the preparation method, the cross-linking density of the cross-linkable polymer in the damping composite system is adjusted through mixing processing, and the damping factor or damping modulus of the damping material is greatly improved through polymer combination, filler application and cooperation of the cross-linking system, and meanwhile, the damping composite material is obtained while the higher mechanical property is ensured.
The aim of the invention is achieved by the following technical scheme.
A damping composite system comprising a crosslinkable polymer which is a polymer having a content of unsaturated double bonds of from 1 to 10% by weight and a non-crosslinkable polymer which is a polymer which is fully saturated with a double bond content of less than 1% by weight and is not capable of undergoing a crosslinking reaction under the action of a crosslinking agent.
As a preferred embodiment of the damping composite system of the present invention, the crosslinkable polymer is butyl rubber and the non-crosslinkable polymer is polyisobutylene.
As a further preferred embodiment of the damping composite system of the present invention, the content of unsaturated monomer isoprene in the butyl rubber is 3-8 wt%.
As a preferred embodiment of the damping composite system of the present invention, the crosslinkable polymer is a partially hydrogenated nitrile rubber and the non-crosslinkable polymer is a fully hydrogenated nitrile rubber.
As a further preferred embodiment of the damping composite system of the present invention, the degree of hydrogenation of the partially hydrogenated nitrile rubber is from 90 to 96% and the acrylonitrile content in the partially hydrogenated nitrile rubber differs from the acrylonitrile content in the fully hydrogenated nitrile rubber by less than 5% by weight.
As a preferred embodiment of the damping composite system of the present invention, the crosslinkable polymer is ethylene propylene diene monomer and the non-crosslinkable polymer is ethylene propylene diene monomer.
As a further preferred embodiment of the damping composite system of the present invention, the diene monomer content in the ethylene propylene diene monomer is 4-10wt% and the ethylene content in the ethylene propylene diene monomer differs from the ethylene propylene diene monomer by less than 5wt%.
As a preferred embodiment of the damping composite system of the present invention, the ratio of the viscosity of the high viscosity polymer to the viscosity of the low viscosity polymer in both the crosslinkable polymer and the non-crosslinkable polymer of any one of the above described damping composite systems is less than 3.
A damping composite material comprising the damping composite system according to any one of the above, wherein the damping composite material comprises the following components in parts by weight: 50-80 parts of crosslinkable polymer, 20-50 parts of non-crosslinkable polymer, 20-60 parts of reinforcing agent, 5-30 parts of operating oil, 0.2-3 parts of anti-aging agent and 4-10 parts of vulcanization system.
As a preferred embodiment of the damping composite material of the present invention, the reinforcing agent includes one or more of carbon black, white carbon black, talc and mica powder.
As a preferred embodiment of the damping composite of the present invention, the vulcanization system comprises a sulfur vulcanization system comprising a vulcanization accelerator, a vulcanization activator, and sulfur.
The method for preparing the damping composite material according to any one of the above, comprising the following steps:
s1, uniformly mixing the crosslinkable polymer, the non-crosslinkable polymer and the anti-aging agent;
s2, adding the reinforcing agent, and uniformly mixing;
s3, adding the operation oil, and uniformly mixing;
s4, adding the vulcanization system, uniformly mixing, and vulcanizing to obtain the damping composite material.
As a preferred embodiment of the method for producing a damping composite according to the invention, the mixing described in S1, S3 is carried out in an internal mixer at a temperature of 40-70℃for 2-5 minutes at 60-80 rpm.
As a preferred embodiment of the method for producing a damping composite according to the present invention, the mixing described in S2 is mixing at 60-80rpm for 2-5 minutes in an internal mixer at 40-70 ℃.
As a preferred embodiment of the method for preparing a damping composite according to the present invention, the mixing described in S4 is carried out uniformly on an open mill, more preferably at 60-80rpm for 5 minutes at 40-70℃in the open mill.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the damping composite system of the invention adopts polymers with complete compatibility and different crosslinking mechanisms, and according to the selection of different polymer types, the friction movement of non-crosslinked molecules in a crosslinked molecular network can be utilized to form high-performance damping systems with different uses, so that the corresponding damping composite material has the characteristics of high damping, high strength and wide material selection range.
The damping composite material is based on the damping composite system, and the cross-linkable polymer in the damping composite system generates a cross-linking effect to form the interpenetrating double-network polymer with a cross-linked gel network and an unlimited entanglement network, so that the non-cross-linked polymer can realize energy consumption in the cross-linked polymer network in a manner of entanglement-disentanglement, creeping movement and the like, generates a damping effect, has the characteristics of high damping, high strength and wide application temperature range of the material, and can be a high-performance damping material with different uses such as a low-temperature-resistant damping material, an oil-resistant damping material, an ageing-resistant damping material, a foaming damping material and the like according to the selection of different polymer types of the damping composite system, and can be applied to various fields such as automobiles, household appliances, traffic and the like.
According to the preparation method disclosed by the invention, the cross-linking of the cross-linkable polymer in the damping composite system is realized through mixing processing, the cross-linking density of the cross-linkable polymer is regulated, and the damping factor or damping modulus of the damping material is greatly improved through the combination of the polymer, the application of the filler and the cooperation of the cross-linking system, so that the damping effect of the material is improved, and meanwhile, the higher mechanical property is ensured, so that the damping composite material is obtained.
Drawings
FIG. 1 is a schematic illustration of the polymer blend molecular phase of the damping composite system of the present invention in an embodiment.
FIG. 2 is a flow chart of a process for preparing a damping composite according to the present invention in an embodiment.
Detailed Description
The technical scheme of the present invention will be described in further detail with reference to specific examples, but the scope and embodiments of the present invention are not limited thereto. This invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Also, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
As used herein, the singular forms "a", "an", and "the" are understood to include plural referents unless the context clearly dictates otherwise. Furthermore, the terms "comprising," "including," "having," and "containing" are intended to be open-ended, i.e., to include the meaning of the terms noted herein, but not to exclude other elements. In other words, the term also includes "consisting essentially of …," or "consisting of ….
In addition, "and combinations thereof" in the specification refer to any combination of all the items listed. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Unless otherwise specified, all technical and scientific terms used herein have the standard meaning of the art to which the claimed subject matter belongs. In case there are multiple definitions for a term, the definitions herein control.
The present invention employs, unless otherwise indicated, standard nomenclature for analytical chemistry, organic synthetic chemistry and optics, and standard laboratory procedures and techniques.
The above preferred conditions can be arbitrarily combined on the basis of not deviating from the common knowledge in the art, and thus, each preferred embodiment of the present invention can be obtained.
The damping composite system of the present invention comprises a crosslinkable polymer and a non-crosslinkable polymer having completely compatible, but different crosslinking mechanisms, and is composed of a mixture of a crosslinkable polymer and a non-crosslinkable polymer.
Wherein the crosslinkable polymer is a polymer with the content of unsaturated double bonds of 1-10wt%, such as a polymer with the content of unsaturated double bonds of 1-8wt%, 2-6wt%, 3-5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% and 10wt%; while the non-crosslinkable polymer is a polymer which is fully saturated with a double bond content of less than 1% and is not capable of undergoing a crosslinking reaction by the action of a crosslinking agent, for example, a fully saturated polymer having a double bond content of less than 0.8wt%, less than 0.7wt%, less than 0.6wt%, less than 0.5wt%, less than 0.4wt%, less than 0.3wt% or less than 0.2wt% may be used.
As a preferred embodiment of the damping composite system of the present invention, the crosslinkable polymer may be butyl rubber and the non-crosslinkable polymer may be polyisobutylene, i.e. a butyl rubber/polyisobutylene combination.
As a further preferred embodiment of the damping composite system of the present invention, the butyl rubber/polyisobutylene combination has an unsaturated monomer isoprene content of 3-8 wt%, such as butyl rubber having an unsaturated monomer isoprene content of 3wt%, 4wt%, 4.5wt%, 5wt%, 5.5 wt%, 6wt%, 6.5 wt%, 7wt%, 8 wt%.
As a preferred embodiment of the damping composite system of the present invention, the crosslinkable polymer may be a partially hydrogenated nitrile rubber and the non-crosslinkable polymer may be a fully hydrogenated nitrile rubber, i.e., a partially hydrogenated nitrile rubber/fully hydrogenated nitrile rubber combination.
As a further preferred embodiment of the damping composite system according to the invention, the degree of hydrogenation of the partially hydrogenated nitrile rubber is from 85 to 96%, for example hydrogenated nitrile rubber having a degree of lightening of 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96% may be used.
Moreover, the acrylonitrile content in the partially hydrogenated nitrile rubber may differ from the acrylonitrile content in the fully hydrogenated nitrile rubber by less than 5wt%, e.g., the acrylonitrile content in the partially hydrogenated nitrile rubber may differ from the acrylonitrile content in the fully hydrogenated nitrile rubber by less than 4.5wt%, less than 4wt%, less than 3.5wt%, less than 3wt%, less than 2.5wt%, less than 2wt%, less than 1.5wt%, less than 1wt%, less than 0.5wt%, less than 0.2wt%, less than 0.1wt%.
As a preferred embodiment of the damping composite system of the present invention, the crosslinkable polymer may be ethylene propylene diene monomer and the non-crosslinkable polymer may be ethylene propylene diene monomer, i.e. ethylene propylene diene monomer/ethylene propylene diene monomer combination.
As a further preferred embodiment of the damping composite system of the present invention, the diene monomer content in the ethylene propylene diene monomer is 4-10wt%, such as ethylene propylene diene monomer having a diene monomer content of 4-9wt%, 4-8wt%, 4-7wt%, 4-6wt%, 4-5wt%, 5-8wt%, 6-8wt%, 7-8wt%, 4wt%, 4.5wt%, 5wt%, 6wt%, 7wt%, 8 wt%.
Moreover, the ethylene content in the ethylene propylene diene monomer may differ from the ethylene propylene diene monomer by less than 5wt%, i.e., the ethylene percentage difference may be less than 4.5wt%, less than 4wt%, less than 3.5wt%, less than 3wt%, less than 2.5wt%, less than 2wt%, less than 1.5wt%, less than 1wt%, less than 0.5wt%, less than 0.2wt%, less than 0.1wt% of the ethylene content in the ethylene propylene diene monomer.
As a preferred embodiment of the damping composite system of the present invention, the viscosity of the crosslinkable polymer and the viscosity of the non-crosslinkable polymer are different, wherein one of the two is higher than the viscosity of the other, for example, the viscosity of the crosslinkable polymer is higher than the viscosity of the non-crosslinkable polymer, or the viscosity of the non-crosslinkable polymer is higher than the viscosity of the crosslinkable polymer, which is determined according to the different selected combinations of the crosslinkable polymer and the non-crosslinkable polymer. Wherein the ratio of the viscosity of the high viscosity polymer to the viscosity of the low viscosity polymer is less than 3, such as may be less than 2.5, less than 2, less than 1.5, less than 1, less than 0.5.
The damping composite material contains the damping composite system, and comprises the following components in parts by weight: 50-80 parts of crosslinkable polymer, 20-50 parts of non-crosslinkable polymer, 20-60 parts of reinforcing agent, 5-30 parts of operating oil, 0.2-3 parts of anti-aging agent and 4-10 parts of vulcanization system.
In the damping composite material of the present invention, please refer to fig. 1, wherein solid lines represent molecular segments of crosslinkable polymers, circles represent crosslinking nodes of crosslinkable polymers, and broken lines represent molecular segments of non-crosslinkable polymers; the cross-linkable polymer and the uncrosslinkable polymer of the damping composite system are compatible in molecular level, and the cross-linked polymer forms an interpenetrating double-network polymer with a cross-linked network and an entanglement network through the cross-linking action of the cross-linkable polymer, and the uncrosslinked polymer molecules can realize energy consumption in the cross-linked polymer gel network through entanglement-disentanglement, crawling movement and other modes. And according to the selection of different polymer types in the damping composite system, high-performance damping materials with different uses, such as low-temperature-resistant damping materials, oil-resistant damping materials, ageing-resistant damping materials, foaming damping materials and the like, can be obtained, and can be applied to various fields of automobiles, household appliances, traffic and the like.
As a preferred embodiment of the damping composite material of the present invention, the reinforcing agent includes one or more of carbon black, white carbon black, talc and mica powder. In some preferred embodiments, the reinforcing agent is carbon black.
As a preferred embodiment of the damping composite of the present invention, the operating oil includes one or more of paraffin oil and dioctyl phthalate.
As a preferred embodiment of the damping composite material of the present invention, the anti-aging agent comprises one or more compound antioxidants selected from the group consisting of hindered phenol antioxidants, phosphite antioxidants and hindered amine antioxidants.
As a preferred embodiment of the damping composite of the present invention, the vulcanization system comprises a sulfur vulcanization system, and the sulfur vulcanization system comprises a vulcanization accelerator, a vulcanization activator, and sulfur.
In some preferred embodiments, the sulfur vulcanization system consists of a vulcanization accelerator, a vulcanization activator, and sulfur.
As a further preferred embodiment of the damping composite of the present invention, the vulcanization accelerator comprises one or more of N-tert-butyl-2-benzothiazole sulfenamide and 2-mercaptobenzothiazole.
As a further preferred embodiment of the damping composite of the present invention, the vulcanization activator is a mixture of zinc oxide and stearic acid.
Referring to fig. 2, the preparation method of the damping composite material of the present invention includes the following steps:
s1, uniformly mixing the crosslinkable polymer, the non-crosslinkable polymer and the anti-aging agent;
s2, adding the reinforcing agent, and continuously and uniformly mixing;
s3, adding the operation oil, and uniformly mixing;
s4, adding the vulcanization system, uniformly mixing, and vulcanizing to obtain the damping composite material.
As a preferred embodiment of the method for producing a damping composite according to the present invention, the mixing described in S1 is carried out in an internal mixer at 40-70℃for 2-5 minutes at 60-80 rpm.
As a preferred embodiment of the method for producing a damping composite according to the present invention, the mixing described in S2 is mixing at 60-80rpm for 2-5 minutes in an internal mixer at 40-70 ℃.
As a preferred embodiment of the method for producing a damping composite according to the present invention, the mixing described in S3 is mixing at 60-80rpm for 2-5 minutes in an internal mixer at 40-70 ℃. After being uniformly mixed, the rubber is discharged, and the mixed materials are discharged from an internal mixer to enter the next step of vulcanization mixing.
As a preferred embodiment of the method for preparing a damping composite according to the present invention, the mixing described in S4 is carried out uniformly on an open mill, more preferably at 60-80rpm for 5 minutes at 40-70℃in the open mill.
The technical scheme of the present invention is described in detail below with reference to specific embodiments.
In the following specific examples, the sources and characteristics of the partial raw materials used are as follows:
partially hydrogenated nitrile rubber, therban LT 1757, alkanin high Performance elastomer Co., ltd., mooney viscosity 70MU, acrylonitrile content 17wt%, unsaturation 5.5%.
Fully hydrogenated nitrile rubber, therban LT 1707, allangneate high performance elastomer Co., ltd., mooney viscosity 74MU, acrylonitrile content 17wt%, unsaturation less than 1%.
Partially hydrogenated nitrile rubber, zetpol 1420L, rui Weng Zhushi, mooney viscosity 72MU, 10% unsaturation.
Fully hydrogenated nitrile rubber, zetpol 1000L, mooney viscosity 70MU, rui Weng Zhushi Co., ltd, has less than 1% unsaturation.
Polyethylene-propylene-norbornene copolymer (ethylene propylene diene monomer), EPDM keltan 6950, high performance elastomer limited of aroneaceae, ethylene content about 45wt%, norbornene content 9wt%, oil-extended content 100PHR, mooney viscosity 62MU, unsaturation 9%.
Polyethylene-propylene copolymer (ethylene propylene diene monomer), EPR 0050, jilin petrochemical Co., ltd., mooney viscosity 55MU, and unsaturation degree 0%.
Butyl rubber, IIR 2255, exkesen mobil (china), mooney viscosity 46MU, unsaturation 2.2%.
Polyisobutylene-isoprene random copolymer rubber (butyl rubber), HIP-6, allangneate high performance elastomer Co., ltd., mooney viscosity 50MU, isoprene content 5-6wt%, and unsaturation 5-6%.
Polyisobutene, B50, basoff chemical Co., ltd., mooney viscosity 45MU, and 0% unsaturation.
Carbon black N330, cabo chemical limited.
Carbon black N550, cabo chemical limited.
Paraffin oil, chinese petrochemical group company.
Dioctyl phthalate, DOP, china petrochemical company.
Accelerator TBBS, N-tert-butyl-2-benzothiazole sulfonamide, available from Ku Xiang chemical Co., ltd.
MBT, 2-mercaptobenzothiazole, available from Ku Xiang chemical Co., ltd.
BBPIB-40%, qingdao Rhine chemical Co., ltd.
TAIC-70%, qingdao Rhine chemical Co., ltd.
The compositions of the damping composites of examples 1-8 are shown in Table 1 below.
TABLE 1 composition of damping composite materials of examples 1-8 (parts by weight/part)
Damping composites of examples 1-8 were prepared as follows:
under the selected crosslinking system, the crosslinkable polymer, the non-crosslinkable polymer and the anti-aging agent are mixed in an internal mixer for 5 minutes at 60 ℃ and 60-80RPM until the mixture is uniform.
Adding the reinforcing agent, and continuing mixing for 3 minutes until the reinforcing agent filler is uniformly mixed;
adding the operation oil, and continuously mixing until the mixture is completely and uniformly mixed;
discharging the adhesive, and discharging the mixed materials from the internal mixer; and uniformly mixing the mixed material mixed by the internal mixer with a vulcanization system on an open mill, and vulcanizing at a high temperature in a die to obtain the high-damping rubber material.
The compositions of the damping composites of comparative examples 1-8 are shown in Table 2 below.
Table 2 composition (parts by weight/part) of damping composite materials of comparative examples 1 to 8
The damping composites of comparative examples 1-8 were prepared in the same manner as the damping composites of examples 1-8.
Performance testing
The damping composites prepared in examples 1-8 and comparative examples 1-8 were subjected to performance tests including tensile strength (GB/T528), loss modulus, and damping factor (GB/T17809). Among them, the results of the performance test of the damping composites of examples 1 to 8 are shown in the following Table 3, and the results of the performance test of the damping composites of comparative examples 1 to 8 are shown in the following Table 4.
Table 3 Performance test results of damping composites of examples 1-8
Table 4 Performance test results of damping composite materials of comparative examples 1 to 8
From the test results of tables 3 and 4, it is understood that the sulfur crosslinking system can realize an interpenetrating double network structure of gel network-entangled network in the polymer composite system used, and improve the damping performance of the materials, such as the damping composites of comparative examples 1, 2, and 5, but the corresponding loss modulus is severely reduced, compared to the damping composites of examples 1 to 8. When the content of the non-crosslinkable polymer is too high or too low, the damping performance and the strength of the material cannot be kept balanced, the comprehensive performance is poor, and when the content of the non-crosslinkable component is too low, the damping effect of the material is low, such as damping composite materials of comparative examples 3, 5 and 6; when the non-crosslinkable component is too high, the material strength is reduced compared to the damping composites of examples 1-8, such as the damping composites of comparative examples 7, 8. When the crosslinkable double bonds of the crosslinkable polymer are too few and the crosslinking degree is insufficient, the damping effect is not improved, and the damping modulus and the loss factor are also reduced to a certain extent.
The technical features of the foregoing embodiments may be combined in any manner, and in this specification, for brevity, all of the possible combinations of the technical features of the foregoing embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, it should be considered as the scope described in the present specification. Moreover, the foregoing examples represent only a few embodiments of the present invention, which are described in detail and are not thereby to be construed as limiting the scope of the invention.
It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (4)
1. The damping composite material is characterized by comprising the following components in parts by weight: 50-80 parts of crosslinkable polymer, 20-50 parts of non-crosslinkable polymer, 20-60 parts of reinforcing agent, 5-30 parts of operating oil, 0.2-3 parts of anti-aging agent and 4-10 parts of vulcanization system;
the cross-linkable polymer is a partially hydrogenated nitrile rubber with the trade name of Therban LT 1757, and the non-cross-linkable polymer is a fully hydrogenated nitrile rubber with the trade name of Therban LT 1707; the vulcanization system is a sulfur vulcanization system, and the sulfur vulcanization system is a vulcanization accelerator, a vulcanization activator and sulfur.
2. The damping composite according to claim 1, wherein the reinforcing agent comprises one or more of carbon black, white carbon black, talc and mica powder.
3. A method of preparing a damping composite according to claim 1 or 2, comprising the steps of:
s1, uniformly mixing the crosslinkable polymer, the non-crosslinkable polymer and the anti-aging agent;
s2, adding the reinforcing agent, and uniformly mixing;
s3, adding the operation oil, and uniformly mixing;
s4, adding the vulcanization system, uniformly mixing, and vulcanizing to obtain the damping composite material.
4. A method of preparing a damping composite according to claim 3, wherein the mixing in S1, S3 is carried out in an internal mixer at 40-70 ℃ for 5 minutes at 60-80 rpm;
and/or, mixing in the step S2, wherein the mixing is carried out in an internal mixer at the temperature of 40-70 ℃ for 3 minutes at the speed of 60-80 rpm;
and/or, mixing described in S4 at 60℃in an open mill at 60-80rpm for 2-5 minutes.
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| US10875994B2 (en) * | 2016-03-29 | 2020-12-29 | Toyoda Gosei Co., Ltd. | Rubber, seal component, and hose |
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| CN101717531A (en) * | 2009-11-25 | 2010-06-02 | 青岛开世密封工业有限公司 | Sealing sleeve for locomotive damper and preparation method thereof |
| CN114621530A (en) * | 2022-03-30 | 2022-06-14 | 中国第一汽车股份有限公司 | Ethylene propylene rubber rectangular sealing ring for automobile brake calipers and preparation method thereof |
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