CN117659599A

CN117659599A - Fumarate damping elastomer material and preparation method thereof

Info

Publication number: CN117659599A
Application number: CN202211098642.0A
Authority: CN
Inventors: 王润国; 杨慧; 吉海军; 张立群; 周鑫鑫; 李利伟; 孙超英
Original assignee: Beijing University of Chemical Technology
Current assignee: Beijing University of Chemical Technology
Priority date: 2022-09-08
Filing date: 2022-09-08
Publication date: 2024-03-08

Abstract

The invention discloses a fumarate damping elastomer material and a preparation method thereof. The maleate damping elastomer material is prepared from the following raw materials: 100 parts of fumaric acid ester elastomer, 5-100 parts of phenolic organic small molecules and 0.1-10 parts of vulcanizing agent. The matrix used in the invention is a bio-based material, can keep excellent damping performance at normal temperature and high temperature, and has important significance in reducing dependence of petroleum and other fossil resources in rubber industry.

Description

Fumarate damping elastomer material and preparation method thereof

Technical Field

The invention relates to the technical field of rubber, in particular to a fumarate damping elastomer material and a preparation method thereof, and in particular relates to a damping material prepared by doping small organic molecules containing phenols.

Background

Vibration and noise generated by mechanical operation not only pollute the environment, but also influence the machining precision and the product quality of the machine, accelerate the fatigue damage of a mechanical structure, shorten the service life of the machine, and utilize the energy loss of a mechanical system to lighten the mechanical vibration and reduce the damping research of the noise, which is always a focus of attention at home and abroad. Now, many new materials and new technologies are continuously applied to damping vibration attenuation, wherein polymer materials, especially rubber damping vibration attenuation materials, are getting more and more attention due to their excellent properties. By adopting the rubber damping material, the mechanical noise can be reduced to the maximum extent, the mechanical vibration can be lightened, the working efficiency can be improved, and the product quality can be improved.

The rubber material has unique viscoelasticity and excellent damping performance in a glass transition region, so that the rubber material is an ideal damping material. In general rubber, butyl rubber has a high loss factor because methyl groups on the upper side of a molecular chain are very dense to form a worm-shaped structure. And because of the secondary transition around the glass transition temperature, the damping performance of the elastomer is different from that of a common elastomer, so that the internal consumption peak is high and wide. For further nitrile rubber, the strong polarity of the nitrile groups contributes significantly to damping and therefore also has a large loss factor. However, the synthetic raw materials of the rubber polymer matrix are all dependent on fossil resources, and are very unfavorable for long-term sustainable development today because of serious challenges in energy, resources and environment.

The fumarate has a double bond and two symmetrical ester groups in the molecule, and the fumarate replaces acrylic ester as a main monomer for polymerization, so that the consumption of fossil resources can be effectively reduced, the damage to the environment is reduced, the more enhanced polarity of the fumarate and the more dense ester groups bring more loss to the material, the composite material with damping performance can be prepared based on the fumarate, and the method has important significance in reducing the dependence of the rubber industry on fossil resources such as petroleum and the like.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a fumarate bio-based damping elastomer material and a preparation method thereof. The synthetic fumarate elastomer is added with the organic micromolecular damping additive containing phenolic hydroxyl, so that the damping performance of the material can be further improved.

The invention aims to provide a fumarate damping elastomer material which is prepared from the following raw materials in parts by weight:

100 parts of a fumarate elastomer;

5-100 parts of phenolic organic small molecules; preferably 10 to 90 parts;

0.1-10 parts of vulcanizing agent; preferably 0.3 to 6 parts.

The fumarate elastomer comprises a fumarate structural unit, a saturated monomer structural unit and a crosslinking monomer structural unit, wherein the content of the fumarate structural unit is 1-90 wt%, preferably 5-85 wt%, such as 5wt%, 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, 85wt%, and the like; the content of the saturated monomer structural unit is 5 to 95wt%, preferably 10 to 90wt%, such as 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, 90wt%, etc.; the content of the crosslinking monomer structural unit is 1 to 10wt%, preferably 1 to 7wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, etc.

The fumarate structural units are derived from a fumarate monomer, the saturated monomer structural units are derived from a saturated monomer, and the crosslinking monomer structural units are derived from a crosslinking monomer.

The fumarate elastomer is prepared by the following steps: emulsion polymerization of components including fumarate monomer, saturated monomer and crosslinking monomer is performed.

The fumarate elastomer needs to be prepared from the following monomers: a fumarate monomer; b a saturated monomer for copolymerization; and C a crosslinking monomer for improving crosslinking points.

A: the fumarate monomer has a structure shown in formula (I):

wherein R is ₁ 、R ₂ Is a hydrogen atom or C _1-10 Alkyl of R ₁ 、R ₂ Identical, or different, and R ₁ 、R ₂ Not both hydrogen atoms. Preferably, R ₁ 、R ₂ Is a hydrogen atom or C _1-4 Is a hydrocarbon group.

The fumarate monomer is particularly preferably a short-side-chain fumarate monomer, and comprises at least one of dimethyl fumarate, monomethyl fumarate, diethyl fumarate, monoethyl fumarate, dipropyl fumarate, monopropyl fumarate, dibutyl fumarate and monobutyl fumarate.

The amount of the fumarate monomer is 1 to 90wt% based on the total amount of the monomers, preferably 5 to 85wt%, such as 5wt%, 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, 85wt%, etc., and the above proportions are mass ratios.

B: copolymerized saturated monomer:

the copolymerized saturated monomer includes: one or more of methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate and alkoxyl ether acrylate.

The amount of the saturated monomer is 5 to 95wt%, preferably 10 to 90wt%, such as 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, 90wt% and the like, based on the total amount of the monomers, and the specific amount is appropriately adjusted according to the amount of the fumarate monomer, and the above proportions are mass ratios.

C: crosslinking monomer:

the crosslinking points preferably, but not exclusively, include the following monomers: one or more of vinyl chloride, vinyl chloride ether, glycidyl methacrylate, propenyl glycidyl ether, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, acrylamide, isoprene, cyclopentadiene, ethylidene norbornene and N-methylolacrylamide.

The amount of the crosslinking monomer is 1 to 10wt%, preferably 1 to 7wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, etc., based on the total amount of the monomers, and the above proportions are mass ratios.

Preferably, the step of polymerizing comprises the steps of:

mixing an emulsifying agent, an activating agent, water, fumaric acid ester, a saturated monomer and a crosslinking monomer in a reaction device, purging with nitrogen for 1-2 min, pre-emulsifying for 0.5-2 h at 10-30 ℃, adding an initiator, performing polymerization for 2-18 h at 0-60 ℃ and adding a terminator to obtain the fumaric acid ester elastomer.

Wherein, the dosage of the emulsifier is 0.1-7% of the total monomer input amount, preferably 2-5%; the dosage of the activator is 0.01 to 3 percent, preferably 0.02 to 1.5 percent of the total monomer; the initiator is used in an amount of 0.01 to 3% by weight, preferably 0.03 to 0.2% by weight, based on the total amount of the monomers charged. The percentages are mass percentages.

The polymerization temperature is preferably 20-50 ℃, the reaction time is preferably 4-10 h, and the rotating speed is preferably 210-240 r/min.

The emulsifier is selected from one of alkylphenol ethoxylates (OP-10), sodium Dodecyl Benzene Sulfonate (SDBS) and potassium disproportionated abietic acid, and preferably Sodium Dodecyl Benzene Sulfonate (SDBS) is used as the emulsifier.

The activator is at least one selected from sodium formaldehyde sulfoxylate, ferric ethylenediamine tetraacetic acid sodium salt, ferric EDTA sodium salt, sodium bisulphite, sodium bicarbonate and ammonium bicarbonate.

The initiator is selected from one of tert-butyl hydroperoxide (TBH), azobisisobutyronitrile (AIBN) and p-menthane hydroperoxide (PMH), preferably tert-butyl hydroperoxide (TBH) as the initiator.

The terminator is one of hydroxylamine (H-hydroxylamine), dimethyl dithiocarbamic acid sodium, sodium polysulfide and sodium nitrite, hydroquinone, p-tert-butyl catechol, wood tar and the like, which are common in the field, and the dosage of the terminator is adjusted according to the actual situation.

The phenolic organic small molecule is selected from one or more than two of the following substances, such as p-hydroxybenzoic acid, vanillic acid, anthocyanin, flavonol, 3, 9-bis [2- [3- (3-tertiary butyl-4-hydroxy-5-methylphenyl) -propionyloxy ] -1, 1-dimethylethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane (AO-80), tetra (bis-T-butylhydroxyhydrocinnamate) (AO-1010) and the like.

The vulcanizing agent is at least one selected from amine compounds (such as polyamine, hexamethylenediamine vulcanizing agent, etc.), triazine compounds, soaps (such as disproportionated potassium rosin acid soap or sodium soap)/sulfur, ammonium carboxylate salts, dithiocarbamate and quaternary ammonium salt/urea vulcanizing agent.

The vulcanizing agent can be different according to the different crosslinking point monomers. If the chlorine-containing unsaturated monomer is used as a crosslinking point monomer for copolymerization, the vulcanizing agent can be one or more of amine compounds, triazine compounds, soap/sulfur and the like, and when the soap/sulfur is adopted, the sulfur dosage is not higher than 0.8 part by mass; when the unsaturated monomer containing epoxy is used as a crosslinking point monomer for copolymerization, the vulcanizing agent can be polyamine, carboxylic acid ammonium salt such as organic carboxylic acid ammonium salt, quaternary ammonium salt/urea vulcanizing agent and the like; when the carboxyl group-containing unsaturated monomer is copolymerized as the crosslinking point monomer, the vulcanizing agent may be a hexamethylenediamine-based vulcanizing agent.

The fumarate damping elastomeric material may also include at least one of stearic acid, an accelerator.

The accelerator can be at least one of diphenyl guanidine (D promoter), 2-mercaptobenzothiazole (M promoter), zinc dibutyl dithiocarbamate (BZ promoter) and N-cyclohexyl 2-benzothiazole sulfenamide (CZ promoter), but is not limited to the above species.

The stearic acid and the accelerator may be used in amounts usual in the art. Preferably, the accelerator is used in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the fumarate elastomer; the amount of stearic acid is 0.2 to 10 parts by weight, more preferably 0.5 to 2 parts by weight.

The invention takes the raw rubber of the fumarate elastomer as a matrix, and is compounded with phenolic organic micromolecules, and a hydrogen bond network structure penetrating through the matrix is formed by utilizing the polar ester groups and the phenolic micromolecules, and the structure generates high mechanical loss in the process of destruction and reformation, thereby playing a damping effect.

The second purpose of the invention is to provide a preparation method of the fumarate damping elastomer, which comprises the steps of mixing raw materials comprising the fumarate elastomer and phenolic small organic molecules at 120-150 ℃, and then adding a vulcanizing agent for mixing and vulcanizing.

Preferably, the preparation method may be as follows:

(1) Placing the prepared raw rubber of the fumarate rubber into a Hark for plasticating for 1min, adding phenolic organic micromolecules, and mixing for 4-6 min at 60+/-10 ℃;

(2) In order to fully and uniformly mix, the prepared rubber compound is heated to 120-150 ℃ for mixing for 5-8 min, and cooled to obtain a sheet;

(3) Then adding other auxiliary agents such as stearic acid, an accelerator, a cross-linking agent and the like, mixing for 5-10 min, and carrying out thin-pass on the mixture for 3-5 times on an open mill. And (5) hot pressing and vulcanizing at 160-200 ℃ on a plate vulcanizing machine to prepare a test sample.

The vulcanization system and the rubber processing technology involved in the preparation method are all conventional means for rubber processing in the field and are known in the prior art.

The invention has the following effects: the matrix used is a bio-based material, so that a new field can be developed for the application of bio-based rubber, and a feasible way is provided for energy crisis; secondly, the biobased rubber matrix itself has extremely high polarity and dense side groups, which is very beneficial to damping; finally, the damping performance is further improved by using phenolic micromolecules, and the preparation process is simple and suitable for large-scale application.

Detailed Description

The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.

The raw materials used in the examples and comparative examples are all commercially available.

Example 1

Into a 1000ml flask, 500g of deionized water, 5g of sodium dodecylbenzenesulfonate, 20g of an aqueous solution of ferric sodium EDTA salt (concentration: 3%), 8g of an aqueous solution of sodium formaldehyde sulfoxylate (concentration: 6%) were each charged, followed by N-charging ₂ A mixture of 100g of diethyl fumarate, 100g of butyl acrylate and 10g of vinyl chloride acetate was poured into the flask after 3 times of air atmosphere exchange with nitrogen atmosphere. Stirring was carried out at 400 r/min. After pre-emulsification for 1h at 30 ℃, 0.06wt% of initiator t-butyl hydroperoxide of the total monomer is injected into the flask and reacted for 8h at 50 ℃. After completion of the polymerization, 0.5g of a terminator, namely, hydroxylamine was injected into the flask to obtain a latex. The latex is flocculated by ethanol to obtain flocculated gel, the flocculated gel is washed by water and ethanol in sequence to remove impurities and purify, and then the flocculated gel is put into a vacuum oven at 60 ℃ to be dried for 24 hours, thus obtaining the raw rubber.

Placing 100g of the prepared raw rubber of the fumarate rubber into a Hark for plasticating for 1min, adding 40g of phenolic organic micromolecule AO-80, and mixing for 5min at 60+/-10 ℃; in order to fully and uniformly mix, the prepared rubber compound is heated to 150 ℃ for mixing for 6min, and then cooled to obtain a sheet; then adding 1g of stearic acid, 2g of accelerator BZ and 1g of triazine cross-linking agent cyanuric acid (TCY), mixing for 8min, and carrying out thin pass through for 5 times on an open mill. Hot press vulcanization was performed at 180 ℃ on a plate vulcanizing machine to prepare a test sample.

Example 2

Into a 1000ml flask, 500g of deionized water, 5g of sodium dodecylbenzenesulfonate, 20g of an aqueous solution of ferric sodium EDTA salt (concentration: 3%), 8g of an aqueous solution of sodium formaldehyde sulfoxylate (concentration: 6%) were each charged, followed by N-charging ₂ A mixture of 100g of diethyl fumarate, 100g of methoxyethyl acrylate and 10g of vinyl chloride acetate was poured into the flask after 3 times of air atmosphere exchange with nitrogen atmosphere. Stirring was carried out at 400 r/min. After pre-emulsification for 1h at 30 ℃, 0.06wt% of initiator t-butyl hydroperoxide of the total monomer is injected into the flask and reacted for 8h at 50 ℃. After completion of the polymerization, 0.5g of a terminator, namely, hydroxylamine was injected into the flask to obtain a latex. The latex is flocculated by ethanol to obtain flocculated gel, the flocculated gel is washed by water and ethanol in sequence to remove impurities and purify, and then the flocculated gel is put into a vacuum oven at 60 ℃ to be dried for 24 hours, thus obtaining the raw rubber.

Placing 100g of the prepared raw rubber of the fumarate rubber into a Hark for plasticating for 1min, adding 40g of phenolic organic micromolecule AO-80, and mixing for 5min at 60+/-10 ℃; in order to fully and uniformly mix, the prepared rubber compound is heated to 150 ℃ for mixing for 6min, and then cooled to obtain a sheet; then adding 1g of stearic acid, 2g of accelerator BZ and 1g of cross-linking agent TCY, mixing for 8min, and carrying out thin pass on an open mill for 5 times. Hot press vulcanization was performed at 180 ℃ on a plate vulcanizing machine to prepare a test sample.

Example 3

Into a 1000ml flask, 500g of deionized water, 5g of sodium dodecylbenzenesulfonate, 20g of an aqueous solution of ferric sodium EDTA salt (concentration: 3%), 8g of an aqueous solution of sodium formaldehyde sulfoxylate (concentration: 6%) were each charged, followed by N-charging ₂ A mixture of 100g of diethyl fumarate, 100g of ethyl acrylate and 10g of vinyl chloride acetate was poured into the flask after 3 times of air atmosphere exchange with nitrogen atmosphere. Stirring was carried out at 400 r/min. After pre-emulsification for 1h at 30 ℃, 0.06wt% of initiator t-butyl hydroperoxide of the total monomer is injected into the flask and reacted for 8h at 50 ℃. After completion of the polymerization, 0.5g of a terminator, namely, hydroxylamine was injected into the flask to obtain a latex. The latex is flocculated by ethanol to obtain flocculated gel, the flocculated gel is washed by water and ethanol in sequence to remove impurities and purify, and then the flocculated gel is put into a vacuum oven at 60 ℃ to be dried for 24 hours, thus obtaining the raw rubber.

Example 4

Into a 1000ml flask, 500g of deionized water, 5g of sodium dodecylbenzenesulfonate, 20g of an aqueous solution of ferric sodium EDTA salt (concentration: 3%), 8g of an aqueous solution of sodium formaldehyde sulfoxylate (concentration: 6%) were each charged, followed by N-charging ₂ A mixture of 100g of dimethyl fumarate, 100g of methoxyethyl acrylate and 10g of vinyl chloride acetate was poured into the flask after 3 times of air atmosphere exchange with nitrogen atmosphere. Stirring was carried out at 400 r/min. After pre-emulsification for 1h at 30 ℃, 0.06wt% of initiator t-butyl hydroperoxide of the total monomer is injected into the flask and reacted for 8h at 50 ℃. After completion of the polymerization, 0.5g of a terminator, namely, hydroxylamine was injected into the flask to obtain a latex. The latex is flocculated by ethanol to obtain flocculated gel, the flocculated gel is washed by water and ethanol in sequence to remove impurities and purify, and then the flocculated gel is put into a vacuum oven at 60 ℃ to be dried for 24 hours, thus obtaining the raw rubber.

Example 5

Into a 1000ml flask, 500g of deionized water, 5g of sodium dodecylbenzenesulfonate, 20g of an aqueous solution of ferric sodium EDTA salt (concentration: 3%), 8g of an aqueous solution of sodium formaldehyde sulfoxylate (concentration: 6%) were each charged, followed by N-charging ₂ A mixture of 100g of dibutyl fumarate, 100g of methoxyethyl acrylate and 10g of vinyl chloride acetate was poured into the flask after 3 times of air atmosphere exchange with nitrogen atmosphere. Stirring was carried out at 400 r/min. After pre-emulsification for 1h at 30 ℃, the flask was filled withThe total monomer content is 0.06wt% of initiator tert-butyl hydroperoxide and the reaction is carried out for 8 hours at 50 ℃. After completion of the polymerization, 0.5g of a terminator, namely, hydroxylamine was injected into the flask to obtain a latex. The latex is flocculated by ethanol to obtain flocculated gel, the flocculated gel is washed by water and ethanol in sequence to remove impurities and purify, and then the flocculated gel is put into a vacuum oven at 60 ℃ to be dried for 24 hours, thus obtaining the raw rubber.

Example 6

Into a 1000ml flask, 500g of deionized water, 5g of sodium dodecylbenzenesulfonate, 20g of an aqueous solution of ferric sodium EDTA salt (concentration: 3%), 8g of an aqueous solution of sodium formaldehyde sulfoxylate (concentration: 6%) were each charged, followed by N-charging ₂ A mixture of 100g of diethyl fumarate, 100g of methoxyethyl acrylate and 10g of glycidyl methacrylate was poured into the flask after 3 times of air atmosphere exchange with nitrogen atmosphere. Stirring was carried out at 400 r/min. After pre-emulsification for 1h at 30 ℃, 0.06wt% of initiator t-butyl hydroperoxide of the total monomer is injected into the flask and reacted for 8h at 50 ℃. After completion of the polymerization, 0.5g of a terminator, namely, hydroxylamine was injected into the flask to obtain a latex. The latex is flocculated by ethanol to obtain flocculated gel, the flocculated gel is washed by water and ethanol in sequence to remove impurities and purify, and then the flocculated gel is put into a vacuum oven at 60 ℃ to be dried for 24 hours, thus obtaining the raw rubber.

Placing 100g of the prepared raw rubber of the fumarate rubber into a Hark for plasticating for 1min, adding 40g of phenolic organic micromolecule AO-80, and mixing for 5min at 60+/-10 ℃; in order to fully and uniformly mix, the prepared rubber compound is heated to 150 ℃ for mixing for 6min, and then cooled to obtain a sheet; then adding 1g of stearic acid, 2g of accelerator BZ and 1g of cross-linking agent ammonium benzoate, mixing for 8min, and carrying out thin pass through for 5 times on an open mill. Hot press vulcanization was performed at 180 ℃ on a plate vulcanizing machine to prepare a test sample.

Example 7

Into a 1000ml flask, 500g of deionized water, 5g of sodium dodecylbenzenesulfonate, 20g of an aqueous solution of ferric sodium EDTA salt (concentration: 3%), 8g of an aqueous solution of sodium formaldehyde sulfoxylate (concentration: 6%) were each charged, followed by N-charging ₂ A mixture of 100g of diethyl fumarate, 100g of methoxyethyl acrylate and 10g of methacrylic acid was poured into the flask after 3 times of air atmosphere exchange with nitrogen atmosphere. After pre-emulsification at 30℃for 1 hour with stirring at 400r/min, t-butyl hydroperoxide as an initiator was injected into the flask in an amount of 0.06wt% based on the total amount of the monomers, and reacted at 50℃for 8 hours. After completion of the polymerization, 0.5g of a terminator, namely, hydroxylamine was injected into the flask to obtain a latex. The latex is flocculated by ethanol to obtain flocculated gel, the flocculated gel is washed by water and ethanol in sequence to remove impurities and purify, and then the flocculated gel is put into a vacuum oven at 60 ℃ to be dried for 24 hours, thus obtaining the raw rubber.

Placing 100g of the prepared raw rubber of the fumarate rubber into a Hark for plasticating for 1min, adding 40g of phenolic organic micromolecule AO-80, and mixing for 5min at 60+/-10 ℃; in order to fully and uniformly mix, the prepared rubber compound is heated to 150 ℃ for mixing for 6min, and then cooled to obtain a sheet; then adding 1g of stearic acid, 2g of accelerator di-o-toluene guanidine and 1g of cross-linking agent hexamethylenediamine, mixing for 8min, and carrying out thin pass through on an open mill for 5 times. Hot press vulcanization was performed at 180 ℃ on a plate vulcanizing machine to prepare a test sample.

Example 8

Into a 1000ml flask, 500g of deionized water, 5g of sodium dodecylbenzenesulfonate, 220g of an aqueous solution of ferric sodium EDTA salt (concentration: 3%), 8g of an aqueous solution of sodium formaldehyde sulfoxylate (concentration: 6%) were each charged, followed by N-charging ₂ A mixture of 100g of diethyl fumarate, 100g of methoxyethyl acrylate and 10g of vinyl chloride acetate was poured into the flask after 3 times of air atmosphere exchange with nitrogen atmosphere. Stirring was carried out at 400 r/min. After pre-emulsification for 1h at 30 ℃, 0.06wt% of initiator t-butyl hydroperoxide of the total monomer is injected into the flask and reacted for 8h at 50 ℃. After completion of the polymerization, 0.5g of a terminator, namely, hydroxylamine was injected into the flask to obtain a latex. The latex is flocculated by ethanol to obtain flocculated gel, the flocculated gel is washed by water and ethanol in sequence to remove impurities and purify, and then the flocculated gel is put into a vacuum oven at 60 ℃ to be dried for 24 hours, thus obtaining the raw rubber.

Placing 100g of the prepared raw rubber of the fumarate rubber into a Hark for plasticating for 1min, adding 20g of phenolic organic micromolecule AO-80, and mixing for 5min at 60+/-10 ℃; in order to fully and uniformly mix, the prepared rubber compound is heated to 150 ℃ for mixing for 6min, and then cooled to obtain a sheet; then adding 1g of stearic acid, 2g of accelerator BZ and 1g of cross-linking agent TCY, mixing for 8min, and carrying out thin pass on an open mill for 5 times. Hot press vulcanization was performed at 180 ℃ on a plate vulcanizing machine to prepare a test sample.

Example 9

Placing 100g of the prepared raw rubber of the fumarate rubber into a Hark for plasticating for 1min, adding 100g of phenolic organic micromolecule AO-80, and mixing for 5min at 60+/-10 ℃; in order to fully and uniformly mix, the prepared rubber compound is heated to 150 ℃ for mixing for 6min, and then cooled to obtain a sheet; then adding 1g of stearic acid, 2g of accelerator BZ and 1g of cross-linking agent TCY, mixing for 8min, and carrying out thin pass on an open mill for 5 times. Hot press vulcanization was performed at 180 ℃ on a plate vulcanizing machine to prepare a test sample.

Example 10

Into a 1000ml flask, 500g of deionized water, 5g of sodium dodecylbenzenesulfonate, 20g of an aqueous solution of ferric sodium EDTA salt (concentration: 3%), 8g of an aqueous solution of sodium formaldehyde sulfoxylate (concentration: 6%) were each charged, followed by N-charging ₂ A mixture of 100g of diethyl fumarate, 100g of methoxyethyl acrylate and 10g of vinyl chloride acetate was poured into the flask after 3 times of air atmosphere exchange with nitrogen atmosphere. To be used forStirring was carried out at 400 r/min. After pre-emulsification for 1h at 30 ℃, 0.06wt% of initiator t-butyl hydroperoxide of the total monomer is injected into the flask and reacted for 8h at 50 ℃. After completion of the polymerization, 0.5g of a terminator, namely, hydroxylamine was injected into the flask to obtain a latex. The latex is flocculated by ethanol to obtain flocculated gel, the flocculated gel is washed by water and ethanol in sequence to remove impurities and purify, and then the flocculated gel is put into a vacuum oven at 60 ℃ to be dried for 24 hours, thus obtaining the raw rubber.

Placing 100g of the prepared raw rubber of the fumarate rubber into a Hark for plasticating for 1min, adding 100g of phenolic organic micromolecule AO-1010, and mixing for 5min at 60+/-10 ℃; in order to fully and uniformly mix, the prepared rubber compound is heated to 150 ℃ for mixing for 6min, and then cooled to obtain a sheet; then adding 1g of stearic acid, 2g of accelerator BZ and 1g of cross-linking agent TCY, mixing for 8min, and carrying out thin pass on an open mill for 5 times. Hot press vulcanization was performed at 180 ℃ on a plate vulcanizing machine to prepare a test sample.

Example 11

Placing 100g of the prepared raw rubber of the fumarate rubber into a Hark for plasticating for 1min, adding 40g of phenolic organic micromolecular vanillic acid, and mixing at 60+/-10 ℃ for 5min; in order to fully and uniformly mix, the prepared rubber compound is heated to 150 ℃ for mixing for 6min, and then cooled to obtain a sheet; then adding 1g of stearic acid, 2g of accelerator BZ and 1g of cross-linking agent TCY, mixing for 8min, and carrying out thin pass on an open mill for 5 times. Hot press vulcanization was performed at 180 ℃ on a plate vulcanizing machine to prepare a test sample.

Example 12

Into a 1000ml flask, 500g of deionized water, 5g of sodium dodecylbenzenesulfonate, 20g of an aqueous solution of ferric sodium EDTA salt (concentration: 3%), 8g of an aqueous solution of sodium formaldehyde sulfoxylate (concentration: 6%) were each charged, followed by N-charging ₂ A mixture of 20g of diethyl fumarate, 180g of butyl acrylate and 10g of vinyl chloride acetate was poured into the flask after 3 times of air atmosphere exchange with nitrogen atmosphere. Stirring was carried out at 400 r/min. After pre-emulsification for 1h at 30 ℃, 0.06wt% of initiator t-butyl hydroperoxide of the total monomer is injected into the flask and reacted for 8h at 50 ℃. After completion of the polymerization, 0.5g of a terminator, namely, hydroxylamine was injected into the flask to obtain a latex. The latex is flocculated by ethanol to obtain flocculated gel, the flocculated gel is washed by water and ethanol in sequence to remove impurities and purify, and then the flocculated gel is put into a vacuum oven at 60 ℃ to be dried for 24 hours, thus obtaining the raw rubber.

Placing 100g of the prepared raw rubber of the fumarate rubber into a Hark for plasticating for 1min, adding 80g of phenolic organic micromolecule AO for 5min at 60+/-10 ℃; in order to fully and uniformly mix, the prepared rubber compound is heated to 150 ℃ for mixing for 6min, and then cooled to obtain a sheet; then adding 1g of stearic acid, 2g of accelerator BZ and 1g of cross-linking agent TCY, mixing for 8min, and carrying out thin pass on an open mill for 5 times. Hot press vulcanization was performed at 180 ℃ on a plate vulcanizing machine to prepare a test sample.

Example 13

Into a 1000ml flask, 500g of deionized water, 5g of sodium dodecylbenzenesulfonate, 20g of an aqueous solution of ferric sodium EDTA salt (concentration: 3%), 8g of an aqueous solution of sodium formaldehyde sulfoxylate (concentration: 6%) were each charged, followed by N-charging ₂ A mixture of 140g of diethyl fumarate, 60g of butyl acrylate and 10g of vinyl chloride acetate was poured into the flask after 3 times of air atmosphere exchange with nitrogen atmosphere. Stirring was carried out at 400 r/min. After pre-emulsification for 1h at 30 ℃, 0.06wt% of initiator t-butyl hydroperoxide of the total monomer is injected into the flask and reacted for 8h at 50 ℃. After completion of the polymerization, 0.5g of a terminator, namely, hydroxylamine was injected into the flask to obtain a latex. The latex is flocculated by ethanol to obtain flocculated gel, the flocculated gel is washed by water and ethanol in sequence to remove impurities and purify, and then the flocculated gel is put into a vacuum oven at 60 ℃ to be dried for 24 hours, thus obtaining the raw rubber.

Example 14

Into a 1000ml flask, 500g of deionized water, 5g of sodium dodecylbenzenesulfonate, 20g of an aqueous solution of ferric sodium EDTA salt (concentration: 3%), 8g of an aqueous solution of sodium formaldehyde sulfoxylate (concentration: 6%) were each charged, followed by N-charging ₂ A mixture of 100g of diethyl fumarate, 100g of methoxyethyl acrylate and 14g of vinyl chloride acetate was poured into the flask after 3 times of air atmosphere exchange with nitrogen atmosphere. Stirring was carried out at 400 r/min. After pre-emulsification for 1h at 30 ℃, 0.06wt% of initiator t-butyl hydroperoxide of the total monomer is injected into the flask and reacted for 8h at 50 ℃. After completion of the polymerization, 0.5g of a terminator, namely, hydroxylamine was injected into the flask to obtain a latex. The latex is flocculated by ethanol to obtain flocculated gel, the flocculated gel is washed by water and ethanol in sequence to remove impurities and purify, and then the flocculated gel is put into a vacuum oven at 60 ℃ to be dried for 24 hours, thus obtaining the raw rubber.

Comparative example 1

Into a 1000ml flask, 500g of deionized water, 5g of sodium dodecylbenzenesulfonate, 20g of an aqueous solution of ferric sodium EDTA salt (concentration: 3%), 8g of an aqueous solution of sodium formaldehyde sulfoxylate (concentration: 6%) were each charged, followed by N-charging ₂ A mixture of 100g of diethyl fumarate, 100g of butyl acrylate and 10g of vinyl chloride acetate was poured into the flask after 3 times of air atmosphere exchange with nitrogen atmosphere. At 400r/mAnd (5) stirring. After pre-emulsification for 1h at 30 ℃, 0.06wt% of initiator t-butyl hydroperoxide of the total monomer is injected into the flask and reacted for 8h at 50 ℃. After completion of the polymerization, 0.5g of a terminator, namely, hydroxylamine was injected into the flask to obtain a latex. The latex is flocculated by ethanol to obtain flocculated gel, the flocculated gel is washed by water and ethanol in sequence to remove impurities and purify, and then the flocculated gel is put into a vacuum oven at 60 ℃ to be dried for 24 hours, thus obtaining the raw rubber.

100g of the prepared raw rubber of fumarate rubber is put into a Hark for plasticating for 1min, then 1g of stearic acid, 2g of accelerator BZ and 1g of cross-linking agent TCY are added for 8min, and the raw rubber is thinned and passed through an open mill for 5 times. Hot press vulcanization was performed at 180 ℃ on a plate vulcanizing machine to prepare a test sample.

Comparative example 2

Into a 1000ml flask, 500g of deionized water, 5g of sodium dodecylbenzenesulfonate, 20g of an aqueous solution of ferric sodium EDTA salt (concentration: 3%), 8g of an aqueous solution of sodium formaldehyde sulfoxylate (concentration: 6%) were each charged, followed by N-charging ₂ The air atmosphere was replaced with nitrogen atmosphere 3 times, and a mixture of 200g of methoxyethyl acrylate and 10g of vinyl chloroacetate was poured into the flask. Stirring was carried out at 400 r/min. After pre-emulsification for 1h at 30 ℃, 0.06wt% of initiator t-butyl hydroperoxide of the total monomer is injected into the flask and reacted for 8h at 50 ℃. After completion of the polymerization, 0.5g of a terminator, namely, hydroxylamine was injected into the flask to obtain a latex. The latex is flocculated by ethanol to obtain flocculated gel, the flocculated gel is washed by water and ethanol in sequence to remove impurities and purify, and then the flocculated gel is put into a vacuum oven at 60 ℃ to be dried for 24 hours, thus obtaining the acrylic rubber raw rubber.

Placing 100g of the prepared acrylic rubber raw rubber into a Hark for plasticating for 1min, adding 40g of phenolic organic micromolecule AO-80, and mixing for 5min at 60+/-10 ℃; in order to fully and uniformly mix, the prepared rubber compound is heated to 150 ℃ for mixing for 6min, and then cooled to obtain a sheet; then adding 1g of stearic acid, 2g of accelerator BZ and 1g of cross-linking agent TCY, mixing for 8min, and carrying out thin pass on an open mill for 5 times. Hot press vulcanization was performed at 180 ℃ on a plate vulcanizing machine to prepare a test sample.

Comparative example 3

Placing the commercial acrylic crude rubber AR72LS in a Hark for plasticating for 1min, adding phenolic organic micromolecule AO-80 40g, and mixing at 60+/-10 ℃ for 5min; in order to fully and uniformly mix, the prepared rubber compound is heated to 150 ℃ for mixing for 6min, and then cooled to obtain a sheet; then adding 1g of stearic acid, 2g of accelerator BZ and 1g of cross-linking agent TCY, mixing for 8min, and carrying out thin pass 5 times on an open mill. Hot press vulcanization was performed at 180 ℃ on a plate vulcanizing machine to prepare a test sample.

Comparative example 4

Into a 1000ml flask, 500g of deionized water, 5g of sodium dodecylbenzenesulfonate, 20g of an aqueous solution of ferric sodium EDTA salt (concentration: 3%), 8g of an aqueous solution of sodium formaldehyde sulfoxylate (concentration: 6%) were each charged, followed by N-charging ₂ 3 times, the atmosphere of air was replaced with nitrogen, and 100g of diethyl fumarate and 100g of butadiene were added to the reaction vessel. Stirring was carried out at 400 r/min. After pre-emulsification for 1h at 30 ℃, 0.06wt% of initiator t-butyl hydroperoxide of the total monomer is injected into the flask and reacted for 8h at 50 ℃. After completion of the polymerization, 0.5g of a terminator, namely, hydroxylamine was injected into the flask to obtain a latex. The latex is flocculated by ethanol to obtain flocculated gel, the flocculated gel is washed by water and ethanol in sequence to remove impurities and purify, and then the flocculated gel is put into a vacuum oven at 60 ℃ to be dried for 24 hours, thus obtaining the raw rubber.

100g of the prepared raw rubber of the fumarate rubber is put into a Hark for plasticating for 1min, then 1g of stearic acid, 2g of accelerator BZ and 1g of cross-linking agent sulfur (S) are added for 8min, and the raw rubber is thinned and passed through an open mill for 5 times. Hot press vulcanization was performed at 180 ℃ on a plate vulcanizing machine to prepare a test sample.

TABLE 1

As can be seen from table 1: the fumarate damping elastomer has a damping temperature range which is obviously higher than that of AR72LS under the condition of 80 parts of the same AO, so that the bio-based damping material prepared by the invention can keep excellent damping performance at normal temperature and high temperature and has great damping application potential.

Claims

1. The fumarate damping elastomer material is prepared from the following raw materials in parts by weight:

100 parts of a fumarate elastomer;

5-100 parts of phenolic organic small molecules; preferably 10 to 90 parts;

0.1-10 parts of vulcanizing agent; preferably 0.3 to 6 parts.

2. The fumarate damping elastomeric material of claim 1, wherein:

the phenolic organic small molecule is selected from at least one of p-hydroxybenzoic acid, vanillic acid, anthocyanin, flavonol, 3, 9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy ] -1, 1-dimethylethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane and tetra (bis-T-butyl hydroxy hydrocinnamate); and/or the number of the groups of groups,

the vulcanizing agent is at least one selected from amine compounds, triazine compounds, soap/sulfur, ammonium carboxylate salts, dithiocarbamate and quaternary ammonium salt/urea vulcanizing agents.

3. The fumarate damping elastomeric material of claim 1, wherein:

the fumarate elastomer comprises a fumarate structural unit, a saturated monomer structural unit and a crosslinking monomer structural unit, wherein the content of the fumarate structural unit is 1-90 wt%, preferably 5-85 wt%; the content of the saturated monomer structural unit is 5-95 wt%, preferably 10-90 wt%; the content of the crosslinking monomer structural units is 1 to 10wt%, preferably 1 to 7wt%.

4. The fumarate damping elastomeric material of claim 1, wherein said fumarate elastomer is prepared by the steps of: emulsion polymerization of components including fumarate monomer, saturated monomer and crosslinking monomer is performed.

5. The fumarate damping elastomeric material of claim 4, wherein said fumarate monomer has the structure of formula (I):

wherein R is ₁ 、R ₂ Each independently is a hydrogen atom or C _1-10 And R is an alkyl group of ₁ 、R ₂ Not both hydrogen atoms; the fumarate monomer is preferably at least one of dimethyl fumarate, monomethyl fumarate, diethyl fumarate, monoethyl fumarate, dipropyl fumarate, monopropyl fumarate, dibutyl fumarate and monobutyl fumarate; and/or the number of the groups of groups,

the saturated monomer is at least one selected from methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate and alkoxyl ether acrylate; and/or the number of the groups of groups,

the crosslinking monomer is at least one selected from vinyl chloride acetate, vinyl chloride ether, glycidyl methacrylate, propenyl glycidyl ether, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, acrylamide, isoprene, cyclopentadiene, ethylidene norbornene and N-methylol acrylamide.

6. The fumarate damping elastomeric material of claim 4, wherein said fumarate elastomer is prepared by the steps of: the method comprises the following steps:

mixing an emulsifying agent, an activating agent, water, a fumarate monomer, a saturated monomer and a crosslinking monomer, pre-emulsifying for 0.5-2 h at 10-30 ℃, adding an initiator, performing polymerization for 2-18 h at 0-60 ℃, and adding a terminator to obtain the fumarate elastomer.

7. The fumarate damping elastomeric material of claim 4, wherein:

the amount of the emulsifier is 0.1 to 7 weight percent, preferably 2 to 5 weight percent of the total monomer; the amount of the activator is 0.01 to 3wt% of the total amount of the monomers, preferably 0.02 to 1.5wt%; the initiator is used in an amount of 0.01 to 3wt%, preferably 0.03 to 0.2wt% based on the total amount of the monomers.

8. The fumarate damping elastomeric material of claim 4, wherein:

the emulsifier is at least one selected from alkylphenol ethoxylates, sodium dodecyl benzene sulfonate and disproportionated potassium abietate; and/or the number of the groups of groups,

the initiator is at least one selected from tert-butyl hydroperoxide, azodiisobutyronitrile and p-menthane hydroperoxide.

9. The fumarate damping elastomeric material of claim 1, further comprising at least one of stearic acid, a promoter.

10. A process for producing the fumarate damping elastomer material according to any one of claims 1 to 9, which comprises kneading raw materials comprising a fumarate elastomer and a phenolic small organic molecule at 120 to 150 ℃, and then adding a vulcanizing agent to carry out kneading and vulcanization.