Acrylonitrile copolymer and preparation method thereof, rubber composition, rubber product and application thereof

Abstract

The invention relates to the field of rubber preparation, and discloses an acrylonitrile copolymer, based on the total weight of the acrylonitrile copolymer, in the acrylonitrile copolymer, the content of a structural unit from butadiene is 0-87wt%, the content of a structural unit from acrylonitrile is 8-42wt%, and the content of a structural unit from acyclic terpene is 5-65wt%. The rubber product prepared from the acrylonitrile copolymer provided by the invention has the advantages of wide damping temperature range, polar medium resistance, high loss factor and excellent physical and mechanical properties.

Description

Technical Field

[0001] The invention relates to the field of rubber preparation, and in particular to an acrylonitrile copolymer and a preparation method thereof, a rubber composition, a rubber product and applications thereof. Background Art

[0002] Damping material is a functional material that can convert mechanical vibration or sound energy into heat energy and dissipate it. It is widely used in the fields of sound absorption and noise reduction of national defense equipment, vibration reduction and seismic isolation of bridge buildings, vibration suppression and noise reduction of mechanical industry, etc. Rubber material is the key matrix material for the preparation of damping products due to its unique viscoelasticity. Its damping mechanism is that when subjected to external alternating stress, due to the viscosity inside the rubber molecules, that is, the interaction force between molecules, the strain will lag behind the stress. In the process of responding to the change of stress, the strain needs to overcome the internal friction to do work, and then convert part of the energy into heat energy and consume it to achieve the damping effect. According to the damping mechanism of rubber materials, it can be seen that the damping performance depends on the internal friction of the polymer, and the internal friction of the polymer is directly related to its own structure.

[0003] Rubber materials have significant damping effects in the glass transition temperature region, but the glass transition temperature of general rubber is below zero, and the actual application environment of damping materials is usually used at room temperature. Obviously, the use temperature and the damping temperature range do not match, and with the development of aerospace, mechanical equipment and other fields, more stringent requirements are put forward for the damping temperature range, damping performance, weather resistance, and medium resistance of damping materials. CN102936377A discloses a preparation method of EPDM rubber with wide temperature range and high damping, and adopts an under-vulcanization method to improve the damping temperature range of EPDM rubber, but the degree of under-vulcanization is greatly affected by temperature, time, and pressure, and is difficult to control. The degree of under-vulcanization is greatly affected by temperature, pressure, and vulcanization time, which affects the product's medium resistance, wear resistance and other properties. CN108659282A discloses a method for preparing a wide temperature range oil-resistant shock-absorbing rubber composite material, which adopts nitrile / polyimide blended elastomer and butyl rubber for mixing. However, due to the difference in polarity of each component, the compatibility is poor, the mechanical properties of the composite material are poor, and it is difficult to maximize the advantages of each component material in terms of oil resistance and damping performance.

[0004] In summary, there is an urgent need for a rubber with a wide damping temperature range, medium resistance, high loss factor and excellent physical and mechanical properties. Summary of the invention

[0005] The purpose of the present invention is to overcome the problem that the rubber in the prior art is difficult to have a wide damping temperature range, resistance to polar media, a high loss factor and excellent physical and mechanical properties, and to provide an acrylonitrile copolymer and a preparation method thereof, a rubber composition, a rubber product and applications thereof.

[0006] In order to achieve the above object, the first aspect of the present invention provides an acrylonitrile copolymer, wherein, based on the total weight of the acrylonitrile copolymer, the content of the structural unit derived from butadiene is 0-87wt%, the content of the structural unit derived from acrylonitrile is 8-42wt%, and the content of the structural unit derived from acyclic terpene is 5-65wt%.

[0007] The second aspect of the present invention provides a method for preparing an acrylonitrile copolymer, wherein a reaction system containing a butadiene monomer, an acrylonitrile monomer, an acyclic terpene monomer, water, an emulsifier, an oxidant and a reducing agent is reacted;

[0008] Wherein, based on 100 parts by weight of the total weight of the butadiene monomer, the acrylonitrile monomer and the acyclic terpene monomer, the butadiene monomer accounts for 0-87 parts by weight, the acrylonitrile monomer accounts for 8-42 parts by weight, and the acyclic terpene monomer accounts for 5-65 parts by weight.

[0009] The third aspect of the present invention provides an acrylonitrile copolymer prepared by the above preparation method.

[0010] A fourth aspect of the present invention provides a rubber composition, wherein the rubber comprises the above-mentioned acrylonitrile copolymer and nitrile rubber;

[0011] Wherein, based on 100 parts by weight of the acrylonitrile copolymer and the nitrile rubber, the acrylonitrile copolymer accounts for 70-100 parts by weight; and the nitrile rubber accounts for 0-30 parts by weight.

[0012] A fifth aspect of the present invention provides a rubber product, wherein the rubber product is obtained by mixing and vulcanizing the rubber composition described above.

[0013] A sixth aspect of the present invention provides use of the acrylonitrile copolymer, the rubber composition, and the rubber product as a damping material.

[0014] Through the above technical scheme, the acrylonitrile copolymer of the present invention contains specific contents of structural units derived from butadiene, structural units derived from acrylonitrile and structural units derived from acyclic terpene, and the rubber prepared therefrom has a wide damping temperature range, resistance to polar media, high loss factor and excellent physical and mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is the H-NMR spectrum of acrylonitrile copolymer A1. DETAILED DESCRIPTION

[0016] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0017] The first aspect of the present invention provides an acrylonitrile copolymer, wherein, based on the total weight of the acrylonitrile copolymer, the content of structural units derived from butadiene is 0-87wt%, the content of structural units derived from acrylonitrile is 8-42wt%, and the content of structural units derived from acyclic terpene is 5-65wt%.

[0018] In the present invention, an acyclic terpene monomer is introduced for copolymerization to obtain an acrylonitrile copolymer with high alkyl side branches, thereby increasing the viscosity within the molecule and improving the damping performance of the acrylonitrile copolymer.

[0019] According to the present invention, the weight average molecular weight of the acrylonitrile copolymer is 150,000 g / mol-350,000 g / mol.

[0020] Preferably, the weight average molecular weight of the acrylonitrile copolymer is 200,000 g / mol-320,000 g / mol.

[0021] According to the present invention, the molecular weight distribution of the acrylonitrile copolymer is 2.1-3.5.

[0022] According to the present invention, the acyclic terpene has the general formula shown in Formula I;

[0023] (C5H8) n Formula I, wherein n is an integer from 2 to 8.

[0024] Preferably, the acyclic terpene is selected from at least one of myrcene, farnesene and ocimene.

[0025] In the present invention, the above-mentioned specific type of acyclic terpene is selected to increase the side branches of the copolymer, reduce the flexibility of the molecular chain, increase the internal friction, and enhance the damping performance of the acrylonitrile copolymer.

[0026] According to the present invention, the glass transition temperature of the acrylonitrile copolymer is -56°C to -1°C.

[0027] In the present invention, the inventors found that the glass transition temperature of the acrylonitrile copolymer changes by controlling the content of the structural unit derived from acyclic terpene. When the content of acrylonitrile is the same, the glass transition temperature of the acrylonitrile copolymer increases with the increase of the acyclic terpene content.

[0028] In the present invention, the gel content of the acrylonitrile copolymer is less than or equal to 0.4 wt %, preferably less than or equal to 0.2 wt %.

[0029] In the present invention, the Mooney viscosity of the acrylonitrile copolymer is 40-70.

[0030] Specific implementation method I

[0031] Based on the total weight of the acrylonitrile copolymer, the content of the structural unit derived from butadiene in the acrylonitrile copolymer is 74-87wt%, the content of the structural unit derived from acrylonitrile is 8-16wt%, and the content of the structural unit derived from acyclic terpene is 5-10wt%.

[0032] According to the present invention, the weight average molecular weight of the acrylonitrile copolymer is 280,000 g / mol-350,000 g / mol.

[0033] According to the present invention, the molecular weight distribution of the acrylonitrile copolymer is 2.8-3.2.

[0034] According to the present invention, the glass transition temperature of the acrylonitrile copolymer is -56°C to -40°C.

[0035] Specific implementation II

[0036] Based on the total weight of the acrylonitrile copolymer, the content of the structural unit derived from butadiene in the acrylonitrile copolymer is 44-72wt%, the content of the structural unit derived from acrylonitrile is 17-26wt%, and the content of the structural unit derived from acyclic terpene is 11-30wt%.

[0037] According to the present invention, the weight average molecular weight of the acrylonitrile copolymer is 250,000 g / mol-290,000 g / mol.

[0038] According to the present invention, the molecular weight distribution of the acrylonitrile copolymer is 2.5-2.9.

[0039] According to the present invention, the glass transition temperature of the acrylonitrile copolymer is -42°C to -30°C.

[0040] Specific implementation III

[0041] Based on the total weight of the acrylonitrile copolymer, the content of the structural unit derived from butadiene in the acrylonitrile copolymer is 7-42wt%, the content of the structural unit derived from acrylonitrile is 27-34wt%, and the content of the structural unit derived from acyclic terpene is 31-59wt%.

[0042] According to the present invention, the weight average molecular weight of the acrylonitrile copolymer is 240,000 g / mol-310,000 g / mol.

[0043] According to the present invention, the molecular weight distribution of the acrylonitrile copolymer is 2.1-2.8.

[0044] According to the present invention, the glass transition temperature of the acrylonitrile copolymer is -35°C to -21°C.

[0045] Specific implementation IV

[0046] Based on the total weight of the acrylonitrile copolymer, the content of the structural unit derived from butadiene in the acrylonitrile copolymer is 0wt%, the content of the structural unit derived from acrylonitrile is 35-42wt%, and the content of the structural unit derived from acyclic terpene is 58-65wt%.

[0047] According to the present invention, the weight average molecular weight of the acrylonitrile copolymer is 180,000 g / mol-230,000 g / mol.

[0048] According to the present invention, the molecular weight distribution of the acrylonitrile copolymer is 2.1-3.

[0049] According to the present invention, the glass transition temperature of the acrylonitrile copolymer is -12°C to -1°C.

[0050] The second aspect of the present invention provides a method for preparing an acrylonitrile copolymer, wherein a reaction system containing a butadiene monomer, an acrylonitrile monomer, an acyclic terpene monomer, water, an emulsifier, an oxidant and a reducing agent is reacted;

[0051] Wherein, based on 100 parts by weight of the total weight of the butadiene monomer, the acrylonitrile monomer and the acyclic terpene monomer, the butadiene monomer accounts for 0-87 parts by weight, the acrylonitrile monomer accounts for 8-42 parts by weight, and the acyclic terpene monomer accounts for 5-65 parts by weight.

[0052] In the present invention, an emulsion polymerization method is adopted to prepare an acrylonitrile copolymer. The reaction conditions of the method are mild, stable and controllable, and a polar group nitrile group can be introduced into the molecular chain of the acrylonitrile copolymer. Under the synergistic effect of the high alkyl side branch chain, the interaction force and viscosity between molecules of the acrylonitrile copolymer are increased, and the damping performance of the polymer is improved.

[0053] According to the present invention, the reaction system further contains a terminator.

[0054] According to the present invention, when the reaction conversion rate reaches 72-85%, the terminator is added.

[0055] In the present invention, the reaction is terminated at the above-mentioned specific reaction conversion rate, which can effectively prevent the increase of the gel content of the acrylonitrile copolymer and improve the processing performance and mechanical properties of the acrylonitrile copolymer.

[0056] In the present invention, the reaction conversion rate is determined by the following method:

[0057] The conversion rate is determined by the gravimetric method. 1-2 g of the reaction system (i.e., emulsion) is weighed and dried in an oven at 100°C to constant weight. The conversion rate is calculated according to formula (1) and formula (2):

[0058] C = [S × TO - NV] Formula (1);

[0059] S = m0 / m1 Formula (2);

[0060] In the formula: C is the conversion rate; S is the actual total solid mass fraction; TO is the total mass of the initial feed materials, that is, the initial feed weight of butadiene monomer, acrylonitrile monomer, acyclic terpene monomer, water, emulsifier, oxidant, reductant, initiator, pH buffer, chelating agent, scavenger, and molecular weight regulator; NV is the mass of non-rubber components, that is, the mass of TO minus the total mass of butadiene monomer, acrylonitrile monomer, acyclic terpene monomer and water.

[0061] In some embodiments of the present invention, preferably, the terminator is selected from at least one of hydroxylamine sulfate, diethylhydroxylamine and hydroquinone. Based on the total weight of the butadiene monomer, the acrylonitrile monomer and the acyclic terpene monomer as 100 parts by weight, the terminator is 0.1-1 parts by weight.

[0062] According to a preferred embodiment of the present invention, the terminator is diethylhydroxylamine and hydroxylamine sulfate in a weight ratio of 1:0.4-0.75.

[0063] In the present invention, the inventors found that the terminator selected from diethylhydroxylamine and hydroxylamine sulfate in a specific weight ratio has a better effect on terminating the polymerization reaction, and the gel content in the polymer after termination is lower.

[0064] According to the present invention, the reaction conditions include: the reaction temperature is 3-25°C, preferably 4-12°C.

[0065] In the present invention, the acrylonitrile copolymer is prepared at low temperature, so that the polymerization system is relatively stable, and the explosion and demulsification phenomena are avoided. Furthermore, at the preferred temperature, the branching and cross-linking of the polymer can be effectively reduced, the gel content in the acrylonitrile copolymer is low, and the processing performance and mechanical properties of the acrylonitrile copolymer are improved.

[0066] According to the present invention, in the reaction system, based on 100 parts by weight of the total weight of butadiene monomer, acrylonitrile monomer and acyclic terpene monomer, the emulsifier is 1.5-12 parts by weight, the oxidant is 0.005-0.5 parts by weight, and the reducing agent is 0.0009-0.4 parts by weight.

[0067] More preferably, in the reaction system, based on 100 parts by weight of the total weight of butadiene monomer, acrylonitrile monomer and acyclic terpene monomer, the emulsifier is 2-7 parts by weight, the oxidant is 0.008-0.36 parts by weight, and the reducing agent is 0.001-0.1 parts by weight.

[0068] According to the present invention, the acyclic terpene has the general formula shown in Formula I;

[0069] (C5H8) n Formula I, wherein n is an integer from 2 to 8.

[0070] In some embodiments of the present invention, preferably, the acyclic terpene monomer is selected from at least one of myrcene, farnesene and ocimene.

[0071] According to the present invention, the emulsifier is selected from anionic emulsifiers.

[0072] In some embodiments of the present invention, preferably, the emulsifier is selected from at least one of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, diffusant N, fatty acid potassium, potassium oleate and disproportionated rosin acid potassium.

[0073] According to a preferred embodiment of the present invention, the emulsifier is sodium dodecylbenzene sulfonate and diffusing agent N in a weight ratio of 1:0.01-0.25.

[0074] In the present invention, the inventors found that the selection of the emulsifier combination in the above specific weight ratio has a low critical micelle concentration, a good emulsification effect, and a relatively stable latex, which is beneficial to the synthesis of acrylonitrile copolymers.

[0075] According to the present invention, the oxidant is a peroxide oxidant.

[0076] In some embodiments of the present invention, preferably, the oxidant is selected from at least one of cumene hydroperoxide, diisopropyl hydroperoxide, p-menthane hydroperoxide, isopropyl tert-butyl peroxide and isopropyl n-butyl peroxide.

[0077] In some embodiments of the present invention, preferably, the reducing agent is selected from at least one of ferrous sulfate, cuprous sulfate, sodium ferrous EDTA, sodium copper EDTA, sodium formaldehyde sulfoxylate and glucose.

[0078] According to a preferred embodiment of the present invention, the reducing agent is sodium formaldehyde sulfoxylate and EDTA sodium iron salt in a weight ratio of 1:0.1-0.3.

[0079] In the present invention, the inventors found that the polymerization reaction rate is stable and controllable when sodium formaldehyde sulfoxylate and sodium EDTA iron salt in a specific weight ratio are selected as reducing agents, the molecular weight distribution of the obtained acrylonitrile copolymer is narrow, and the branching and crosslinking degree of the acrylonitrile copolymer are low.

[0080] According to the present invention, the reaction system further comprises at least one of a pH buffer, a chelating agent, an oxygen scavenger and a molecular weight regulator.

[0081] In some embodiments of the present invention, preferably, the chelating agent is selected from at least one of EDTA tetrasodium salt, EDTA disodium salt and sodium aminotriacetate.

[0082] In some embodiments of the present invention, preferably, the molecular weight regulator is selected from alkyl mercaptan compounds and / or thiocarboxylate compounds, preferably at least one of tert-dodecyl mercaptan, n-dodecyl mercaptan, diisopropyl dithioxanthate and 2,2',4,4',6,8,8',10,10'-nonamethylundecane-6-thiol, more preferably tert-dodecyl mercaptan.

[0083] According to the invention, the molecular weight regulator is added in stages.

[0084] Preferably, when the reaction conversion rate reaches 50-70%, the molecular weight regulator is added for the second time.

[0085] In the present invention, the first molecular weight regulator is added to the reaction system together with butadiene monomer, acrylonitrile monomer, acyclic terpene monomer, water, emulsifier, oxidant and reducing agent to react. When the molecular weight regulator is added at the above-mentioned specific reaction conversion rate, the polymerization reaction rate can be adjusted, the molecular weight and its distribution can be controlled, and the gel content can be reduced, so that the Mooney viscosity is effectively controlled, thereby obtaining an acrylonitrile copolymer with high mechanical properties.

[0086] In some embodiments of the present invention, preferably, the oxygen scavenger is selected from at least one of sodium dithionite, dimethyl ketoxime, isoascorbic acid, carbohydrazide and N-isopropylhydroxylamine.

[0087] According to the present invention, the pH buffer is an alkaline substance.

[0088] In some embodiments of the present invention, preferably, the pH buffer is selected from one of sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium carbonate and sodium acetate.

[0089] According to the present invention, the method of low-temperature emulsion polymerization is adopted, and the selected initiator can be an initiator that can decompose under low temperature conditions to generate free radicals and initiate monomer polymerization. The initiator is an oxidation-reduction initiator.

[0090] According to the present invention, the pH buffer is 0.001-0.5 parts by weight, the deoxidizer is 0.01-0.1 parts by weight, the chelating agent is 0.0003-0.4 parts by weight, and the molecular weight regulator is 0.11-2 parts by weight.

[0091] Preferably, the pH buffer is 0.001-0.38 parts by weight, the deoxidizer is 0.08-0.1 parts by weight, the chelating agent is 0.001-0.35 parts by weight, and the molecular weight regulator is 0.2-1.5 parts by weight.

[0092] According to the present invention, the additional molecular weight regulator is 0.01-0.5 parts by weight.

[0093] Preferably, the additional molecular weight regulator is 0.05-0.45 parts by weight.

[0094] In the present invention, in order to ensure that the reaction proceeds smoothly, it is preferred that the reaction is carried out under a protective atmosphere, and the protective gas may be at least one of nitrogen and an inert gas.

[0095] In the present invention, the latex is then degassed, flocculated, washed and dried to obtain an acrylonitrile copolymer. The degassing, flocculating and drying processes are conventional in the art and are not limited thereto. For example, the coagulant is selected from at least one of calcium chloride, sodium chloride and methanol. The coagulant is 3-8 parts by weight based on 100 parts by weight of the total weight of the solids in the latex.

[0096] Specific implementation method I

[0097] In a specific embodiment of the present invention, based on the total weight of the acrylonitrile copolymer, the content of the structural unit derived from butadiene in the acrylonitrile copolymer is 74-87wt%, the content of the structural unit derived from acrylonitrile is 8-16wt%, and the content of the structural unit derived from acyclic terpene is 5-10wt%. The preparation method of the acrylonitrile copolymer comprises:

[0098] reacting a reaction system containing butadiene monomer, acrylonitrile monomer, acyclic terpene monomer, water, an emulsifier, an oxidant and a reducing agent;

[0099] Wherein, based on 100 parts by weight of the total weight of butadiene monomer, acrylonitrile monomer and acyclic terpene monomer, the butadiene monomer accounts for 74-87 parts by weight, the acrylonitrile monomer accounts for 8-16 parts by weight, and the acyclic terpene monomer accounts for 5-10 parts by weight.

[0100] According to the present invention, the reaction system further contains a terminator.

[0101] Preferably, the terminator is added when the reaction conversion rate reaches 72-85%.

[0102] In some embodiments of the present invention, preferably, the terminator is selected from at least one of hydroxylamine sulfate, diethylhydroxylamine and hydroquinone. Based on the total weight of the butadiene monomer, the acrylonitrile monomer and the acyclic terpene monomer as 100 parts by weight, the terminator is 0.1-1 parts by weight.

[0103] More preferably, the terminator is diethylhydroxylamine and hydroxylamine sulfate in a weight ratio of 1:0.4-0.75.

[0104] Preferably, the reaction conditions include: the reaction temperature is 3-25°C, preferably 4-12°C.

[0105] According to the present invention, in the reaction system, based on 100 parts by weight of the total weight of butadiene monomer, acrylonitrile monomer and acyclic terpene monomer, the emulsifier is 1.5-12 parts by weight, the oxidant is 0.005-0.5 parts by weight, and the reducing agent is 0.0009-0.4 parts by weight.

[0106] More preferably, in the reaction system, based on 100 parts by weight of the total weight of butadiene monomer, acrylonitrile monomer and acyclic terpene monomer, the emulsifier is 2-7 parts by weight, the oxidant is 0.008-0.36 parts by weight, and the reducing agent is 0.001-0.1 parts by weight.

[0107] According to the present invention, the acyclic terpene has the general formula shown in Formula I;

[0108] (C5H8) n Formula I, wherein n is an integer from 2 to 8.

[0109] In some embodiments of the present invention, preferably, the acyclic terpene monomer is selected from at least one of myrcene, farnesene and ocimene.

[0110] According to the present invention, the emulsifier is selected from anionic emulsifiers.

[0111] In some embodiments of the present invention, preferably, the emulsifier is selected from at least one of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, diffusant N, fatty acid potassium, potassium oleate and disproportionated rosin acid potassium.

[0112] More preferably, the emulsifier is sodium dodecylbenzene sulfonate and diffusant N in a weight ratio of 1:0.01-0.25.

[0113] According to the present invention, the oxidant is a peroxide oxidant.

[0114] In some embodiments of the present invention, preferably, the oxidant is selected from at least one of cumene hydroperoxide, diisopropyl hydroperoxide, p-menthane hydroperoxide, isopropyl tert-butyl peroxide and isopropyl n-butyl peroxide.

[0115] In some embodiments of the present invention, preferably, the reducing agent is selected from at least one of ferrous sulfate, cuprous sulfate, sodium ferrous EDTA, sodium copper EDTA, sodium formaldehyde sulfoxylate and glucose.

[0116] More preferably, the reducing agent is sodium formaldehyde sulfoxylate and EDTA sodium iron salt in a weight ratio of 1:0.1-0.3.

[0117] Preferably, the reaction system further comprises at least one of a pH buffer, a chelating agent, an oxygen scavenger and a molecular weight regulator.

[0118] In some embodiments of the present invention, preferably, the chelating agent is selected from at least one of EDTA tetrasodium salt, EDTA disodium salt and sodium aminotriacetate.

[0119] In some embodiments of the present invention, preferably, the molecular weight regulator is selected from alkyl mercaptan compounds and / or thiocarboxylate compounds, preferably at least one of tert-dodecyl mercaptan, n-dodecyl mercaptan, diisopropyl dithioxanthate and 2,2',4,4',6,8,8',10,10'-nonamethylundecane-6-thiol, more preferably tert-dodecyl mercaptan.

[0120] According to the present invention, the molecular weight regulator is added in steps, and more preferably, the molecular weight regulator is added for the second time when the reaction conversion rate reaches 50-70%.

[0121] In some embodiments of the present invention, preferably, the oxygen scavenger is selected from at least one of sodium dithionite, dimethyl ketoxime, isoascorbic acid, carbohydrazide and N-isopropylhydroxylamine.

[0122] According to the present invention, the pH buffer is an alkaline substance.

[0123] In some embodiments of the present invention, preferably, the pH buffer is selected from one of sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium carbonate and sodium acetate.

[0124] Preferably, the pH buffer is 0.001-0.5 parts by weight, the deoxidizer is 0.01-0.1 parts by weight, the chelating agent is 0.0003-0.4 parts by weight, and the molecular weight regulator is 0.11-2 parts by weight.

[0125] More preferably, the pH buffer is 0.001-0.38 parts by weight, the deoxidizer is 0.08-0.1 parts by weight, the chelating agent is 0.001-0.35 parts by weight, and the molecular weight regulator is 0.2-1.5 parts by weight.

[0126] Preferably, the molecular weight regulator added for the second time is 0.01-0.5 parts by weight, preferably 0.05-0.45 parts by weight.

[0127] In the present invention, in order to ensure that the reaction proceeds smoothly, it is preferred that the reaction is carried out under a protective atmosphere, and the protective gas may be at least one of nitrogen and an inert gas.

[0128] In the present invention, the latex is then degassed, flocculated, washed and dried to obtain an acrylonitrile copolymer. The degassing, flocculating and drying processes are conventional in the art and are not limited thereto. For example, the coagulant is selected from at least one of calcium chloride, sodium chloride and methanol. The coagulant is 3-8 parts by weight based on 100 parts by weight of the total weight of the solids in the latex.

[0129] Specific implementation II

[0130] In a specific embodiment of the present invention, based on the total weight of the acrylonitrile copolymer, the content of the structural unit derived from butadiene in the acrylonitrile copolymer is 44-72wt%, the content of the structural unit derived from acrylonitrile is 17-26wt%, and the content of the structural unit derived from acyclic terpene is 11-30wt%. The preparation method of the acrylonitrile copolymer comprises:

[0131] reacting a reaction system containing butadiene monomer, acrylonitrile monomer, acyclic terpene monomer, water, an emulsifier, an oxidant and a reducing agent;

[0132] Wherein, based on 100 parts by weight of the total weight of the butadiene monomer, the acrylonitrile monomer and the acyclic terpene monomer, the butadiene monomer accounts for 44-72 parts by weight, the acrylonitrile monomer accounts for 17-26 parts by weight, and the acyclic terpene monomer accounts for 11-30 parts by weight.

[0133] According to the present invention, the reaction system further contains a terminator.

[0134] Preferably, the terminator is added when the reaction conversion rate reaches 72-85%.

[0135] In some embodiments of the present invention, preferably, the terminator is selected from at least one of hydroxylamine sulfate, diethylhydroxylamine and hydroquinone. Based on the total weight of the butadiene monomer, the acrylonitrile monomer and the acyclic terpene monomer as 100 parts by weight, the terminator is 0.1-1 parts by weight.

[0136] More preferably, the terminator is diethylhydroxylamine and hydroxylamine sulfate in a weight ratio of 1:0.4-0.75.

[0137] Preferably, the reaction conditions include: the reaction temperature is 3-25°C, preferably 4-12°C.

[0138] According to the present invention, in the reaction system, based on 100 parts by weight of the total weight of butadiene monomer, acrylonitrile monomer and acyclic terpene monomer, the emulsifier is 1.5-12 parts by weight, the oxidant is 0.005-0.5 parts by weight, and the reducing agent is 0.0009-0.4 parts by weight.

[0139] More preferably, in the reaction system, based on 100 parts by weight of the total weight of butadiene monomer, acrylonitrile monomer and acyclic terpene monomer, the emulsifier is 2-7 parts by weight, the oxidant is 0.008-0.36 parts by weight, and the reducing agent is 0.001-0.1 parts by weight.

[0140] According to the present invention, the acyclic terpene has the general formula shown in Formula I;

[0141] (C5H8) n Formula I, wherein n is an integer from 2 to 8.

[0142] In some embodiments of the present invention, preferably, the acyclic terpene monomer is selected from at least one of myrcene, farnesene and ocimene.

[0143] According to the present invention, the emulsifier is selected from anionic emulsifiers.

[0144] In some embodiments of the present invention, preferably, the emulsifier is selected from at least one of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, diffusant N, fatty acid potassium, potassium oleate and disproportionated rosin acid potassium.

[0145] More preferably, the emulsifier is sodium dodecylbenzene sulfonate and diffusant N in a weight ratio of 1:0.01-0.25.

[0146] According to the present invention, the oxidant is a peroxide oxidant.

[0147] In some embodiments of the present invention, preferably, the oxidant is selected from at least one of cumene hydroperoxide, diisopropyl hydroperoxide, p-menthane hydroperoxide, isopropyl tert-butyl peroxide and isopropyl n-butyl peroxide.

[0148] In some embodiments of the present invention, preferably, the reducing agent is selected from at least one of ferrous sulfate, cuprous sulfate, sodium ferrous EDTA, sodium copper EDTA, sodium formaldehyde sulfoxylate and glucose.

[0149] More preferably, the reducing agent is sodium formaldehyde sulfoxylate and EDTA sodium iron salt in a weight ratio of 1:0.1-0.3.

[0150] Preferably, the reaction system further comprises at least one of a pH buffer, a chelating agent, an oxygen scavenger and a molecular weight regulator.

[0151] In some embodiments of the present invention, preferably, the chelating agent is selected from at least one of EDTA tetrasodium salt, EDTA disodium salt and sodium aminotriacetate.

[0152] In some embodiments of the present invention, preferably, the molecular weight regulator is selected from alkyl mercaptan compounds and / or thiocarboxylate compounds, preferably at least one of tert-dodecyl mercaptan, n-dodecyl mercaptan, diisopropyl dithioxanthate and 2,2',4,4',6,8,8',10,10'-nonamethylundecane-6-thiol, more preferably tert-dodecyl mercaptan.

[0153] More preferably, the molecular weight regulator is added in steps, and more preferably, when the reaction conversion rate reaches 50-70%, the molecular weight regulator is added for the second time.

[0154] According to the present invention, the pH buffer is an alkaline substance.

[0155] In some embodiments of the present invention, preferably, the pH buffer is selected from one of sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium carbonate and sodium acetate.

[0156] In some embodiments of the present invention, preferably, the oxygen scavenger is selected from at least one of sodium dithionite, dimethyl ketoxime, isoascorbic acid, carbohydrazide and N-isopropylhydroxylamine.

[0157] Preferably, the pH buffer is 0.001-0.5 parts by weight, the deoxidizer is 0.01-0.1 parts by weight, the chelating agent is 0.0003-0.4 parts by weight, and the molecular weight regulator is 0.11-2 parts by weight.

[0158] More preferably, the pH buffer is 0.001-0.38 parts by weight, the deoxidizer is 0.08-0.1 parts by weight, the chelating agent is 0.001-0.35 parts by weight, and the molecular weight regulator is 0.2-1.5 parts by weight.

[0159] Preferably, the molecular weight regulator added for the second time is 0.01-0.5 parts by weight, preferably 0.05-0.45 parts by weight.

[0160] In the present invention, in order to ensure that the reaction proceeds smoothly, it is preferred that the reaction is carried out under a protective atmosphere, and the protective gas may be at least one of nitrogen and an inert gas.

[0161] In the present invention, the latex is then degassed, flocculated, washed and dried to obtain an acrylonitrile copolymer. The degassing, flocculating and drying processes are conventional in the art and are not limited thereto. For example, the coagulant is selected from at least one of calcium chloride, sodium chloride and methanol. The coagulant is 3-8 parts by weight based on 100 parts by weight of the total weight of the solids in the latex.

[0162] Specific implementation III

[0163] In a specific embodiment of the present invention, based on the total weight of the acrylonitrile copolymer, the content of the structural unit derived from butadiene in the acrylonitrile copolymer is 7-42wt%, the content of the structural unit derived from acrylonitrile is 27-34wt%, and the content of the structural unit derived from acyclic terpene is 31-59wt%. The preparation method of the acrylonitrile copolymer comprises:

[0164] reacting a reaction system containing butadiene monomer, acrylonitrile monomer, acyclic terpene monomer, water, an emulsifier, an oxidant and a reducing agent;

[0165] Wherein, based on 100 parts by weight of the total weight of butadiene monomer, acrylonitrile monomer and acyclic terpene monomer, the butadiene monomer accounts for 7-42 parts by weight, the acrylonitrile monomer accounts for 27-34 parts by weight, and the acyclic terpene monomer accounts for 31-59 parts by weight.

[0166] According to the present invention, the reaction system further contains a terminator.

[0167] Preferably, the terminator is added when the reaction conversion rate reaches 72-85%.

[0168] In some embodiments of the present invention, preferably, the terminator is selected from at least one of hydroxylamine sulfate, diethylhydroxylamine and hydroquinone. Based on the total weight of the butadiene monomer, the acrylonitrile monomer and the acyclic terpene monomer as 100 parts by weight, the terminator is 0.1-1 parts by weight.

[0169] More preferably, the terminator is diethylhydroxylamine and hydroxylamine sulfate in a weight ratio of 1:0.4-0.75.

[0170] Preferably, the reaction conditions include: the reaction temperature is 3-25°C, preferably 4-12°C.

[0171] According to the present invention, in the reaction system, based on 100 parts by weight of the total weight of butadiene monomer, acrylonitrile monomer and acyclic terpene monomer, the emulsifier is 1.5-12 parts by weight, the oxidant is 0.005-0.5 parts by weight, and the reducing agent is 0.0009-0.4 parts by weight.

[0172] More preferably, in the reaction system, based on 100 parts by weight of the total weight of butadiene monomer, acrylonitrile monomer and acyclic terpene monomer, the emulsifier is 2-7 parts by weight, the oxidant is 0.008-0.36 parts by weight, and the reducing agent is 0.001-0.1 parts by weight.

[0173] According to the present invention, the acyclic terpene has the general formula shown in Formula I;

[0174] (C5H8) n Formula I, wherein n is an integer from 2 to 8.

[0175] In some embodiments of the present invention, preferably, the acyclic terpene monomer is selected from at least one of myrcene, farnesene and ocimene.

[0176] According to the present invention, the emulsifier is selected from anionic emulsifiers.

[0177] In some embodiments of the present invention, preferably, the emulsifier is selected from at least one of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, diffusant N, fatty acid potassium, potassium oleate and disproportionated rosin acid potassium.

[0178] More preferably, the emulsifier is sodium dodecylbenzene sulfonate and diffusant N in a weight ratio of 1:0.01-0.25.

[0179] According to the present invention, the oxidant is a peroxide oxidant.

[0180] In some embodiments of the present invention, preferably, the oxidant is selected from at least one of cumene hydroperoxide, diisopropyl hydroperoxide, p-menthane hydroperoxide, isopropyl tert-butyl peroxide and isopropyl n-butyl peroxide.

[0181] In some embodiments of the present invention, preferably, the reducing agent is selected from at least one of ferrous sulfate, cuprous sulfate, sodium ferrous EDTA, sodium copper EDTA, sodium formaldehyde sulfoxylate and glucose.

[0182] More preferably, the reducing agent is sodium formaldehyde sulfoxylate and EDTA sodium iron salt in a weight ratio of 1:0.1-0.3.

[0183] Preferably, the reaction system further comprises at least one of a pH buffer, a chelating agent, an oxygen scavenger and a molecular weight regulator.

[0184] In some embodiments of the present invention, preferably, the chelating agent is selected from at least one of EDTA tetrasodium salt, EDTA disodium salt and sodium aminotriacetate.

[0185] In some embodiments of the present invention, preferably, the molecular weight regulator is selected from alkyl mercaptan compounds and / or thiocarboxylate compounds, preferably at least one of tert-dodecyl mercaptan, n-dodecyl mercaptan, diisopropyl dithioxanthate and 2,2',4,4',6,8,8',10,10'-nonamethylundecane-6-thiol, more preferably tert-dodecyl mercaptan.

[0186] More preferably, the molecular weight regulator is added in steps, and more preferably, when the reaction conversion rate reaches 50-70%, the molecular weight regulator is added for the second time.

[0187] According to the present invention, the pH buffer is an alkaline substance.

[0188] In some embodiments of the present invention, preferably, the pH buffer is selected from one of sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium carbonate and sodium acetate.

[0189] In some embodiments of the present invention, preferably, the oxygen scavenger is selected from at least one of sodium dithionite, dimethyl ketoxime, isoascorbic acid, carbohydrazide and N-isopropylhydroxylamine.

[0190] Preferably, the pH buffer is 0.001-0.5 parts by weight, the deoxidizer is 0.01-0.1 parts by weight, the chelating agent is 0.0003-0.4 parts by weight, and the molecular weight regulator is 0.11-2 parts by weight.

[0191] More preferably, the pH buffer is 0.001-0.38 parts by weight, the deoxidizer is 0.08-0.01 parts by weight, the chelating agent is 0.001-0.35 parts by weight, and the molecular weight regulator is 0.2-1.5 parts by weight.

[0192] Preferably, the molecular weight regulator added for the second time is 0.01-0.5 parts by weight, preferably 0.05-0.45 parts by weight.

[0193] In the present invention, in order to ensure that the reaction proceeds smoothly, it is preferred that the reaction is carried out under a protective atmosphere, and the protective gas may be at least one of nitrogen and an inert gas.

[0194] In the present invention, the latex is then degassed, flocculated, washed and dried to obtain an acrylonitrile copolymer. The degassing, flocculating and drying processes are conventional in the art and are not limited thereto. For example, the coagulant is selected from at least one of calcium chloride, sodium chloride and methanol. The coagulant is 3-8 parts by weight based on 100 parts by weight of the total weight of the solids in the latex.

[0195] Specific implementation IV

[0196] In a specific embodiment of the present invention, based on the total weight of the acrylonitrile copolymer, the content of the structural unit derived from butadiene in the acrylonitrile copolymer is 0wt%, the content of the structural unit derived from acrylonitrile is 35-42wt%, and the content of the structural unit derived from acyclic terpene is 58-65wt%. The preparation method of the acrylonitrile copolymer comprises:

[0197] reacting a reaction system containing butadiene monomer, acrylonitrile monomer, acyclic terpene monomer, water, an emulsifier, an oxidant and a reducing agent;

[0198] Wherein, based on the total weight of the butadiene monomer, the acrylonitrile monomer and the acyclic terpene monomer being 100 parts by weight, the butadiene monomer is 0 parts by weight, the acrylonitrile monomer is 35-42 parts by weight, and the acyclic terpene monomer is 58-65 parts by weight.

[0199] According to the present invention, the reaction system further contains a terminator.

[0200] Preferably, the terminator is added when the reaction conversion rate reaches 72-85%.

[0201] In some embodiments of the present invention, preferably, the terminator is selected from at least one of hydroxylamine sulfate, diethylhydroxylamine and hydroquinone. Based on the total weight of the butadiene monomer, the acrylonitrile monomer and the acyclic terpene monomer as 100 parts by weight, the terminator is 0.1-1 parts by weight.

[0202] More preferably, the terminator is diethylhydroxylamine and hydroxylamine sulfate in a weight ratio of 1:0.4-0.75.

[0203] Preferably, the reaction conditions include: the reaction temperature is 3-25°C, preferably 4-12°C.

[0204] According to the present invention, in the reaction system, based on 100 parts by weight of the total weight of butadiene monomer, acrylonitrile monomer and acyclic terpene monomer, the emulsifier is 1.5-12 parts by weight, the oxidant is 0.005-0.5 parts by weight, and the reducing agent is 0.0009-0.4 parts by weight.

[0205] More preferably, in the reaction system, based on 100 parts by weight of the total weight of butadiene monomer, acrylonitrile monomer and acyclic terpene monomer, the emulsifier is 2-7 parts by weight, the oxidant is 0.008-0.36 parts by weight, and the reducing agent is 0.001-0.1 parts by weight.

[0206] According to the present invention, the acyclic terpene has the general formula shown in Formula I;

[0207] (C5H8) n Formula I, wherein n is an integer from 2 to 8.

[0208] In some embodiments of the present invention, preferably, the acyclic terpene monomer is selected from at least one of myrcene, farnesene and ocimene.

[0209] According to the present invention, the emulsifier is selected from anionic emulsifiers.

[0210] In some embodiments of the present invention, preferably, the emulsifier is selected from at least one of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, diffusant N, fatty acid potassium, potassium oleate and disproportionated rosin acid potassium.

[0211] More preferably, the emulsifier is sodium dodecylbenzene sulfonate and a dispersant in a weight ratio of 1:0.01-0.25.

[0212] According to the present invention, the oxidant is a peroxide oxidant.

[0213] In some embodiments of the present invention, preferably, the oxidant is selected from at least one of cumene hydroperoxide, diisopropyl hydroperoxide, p-menthane hydroperoxide, isopropyl tert-butyl peroxide and isopropyl n-butyl peroxide.

[0214] In some embodiments of the present invention, preferably, the reducing agent is selected from at least one of ferrous sulfate, cuprous sulfate, sodium ferrous EDTA, sodium copper EDTA, sodium formaldehyde sulfoxylate and glucose.

[0215] More preferably, the reducing agent is sodium formaldehyde sulfoxylate and EDTA sodium iron salt in a weight ratio of 1:0.1-0.3.

[0216] Preferably, the reaction system further comprises at least one of a pH buffer, a chelating agent, an oxygen scavenger and a molecular weight regulator.

[0217] In some embodiments of the present invention, preferably, the chelating agent is selected from at least one of EDTA tetrasodium salt, EDTA disodium salt and sodium aminotriacetate.

[0218] In some embodiments of the present invention, preferably, the molecular weight regulator is selected from alkyl mercaptan compounds and / or thiocarboxylate compounds, preferably at least one of tert-dodecyl mercaptan, n-dodecyl mercaptan, diisopropyl dithioxanthate and 2,2',4,4',6,8,8',10,10'-nonamethylundecane-6-thiol, more preferably tert-dodecyl mercaptan.

[0219] More preferably, the molecular weight regulator is added in steps, and more preferably, when the reaction conversion rate reaches 50-70%, the molecular weight regulator is added for the second time.

[0220] According to the present invention, the pH buffer is an alkaline substance.

[0221] In some embodiments of the present invention, preferably, the pH buffer is selected from one of sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium carbonate and sodium acetate.

[0222] In some embodiments of the present invention, preferably, the oxygen scavenger is selected from at least one of sodium dithionite, dimethyl ketoxime, isoascorbic acid, carbohydrazide and N-isopropylhydroxylamine.

[0223] Preferably, the pH buffer is 0.001-0.5 parts by weight, the deoxidizer is 0.01-0.1 parts by weight, the chelating agent is 0.0003-0.4 parts by weight, and the molecular weight regulator is 0.11-2 parts by weight.

[0224] More preferably, the pH buffer is 0.001-0.38 parts by weight, the deoxidizer is 0.08-0.1 parts by weight, the chelating agent is 0.001-0.35 parts by weight, and the molecular weight regulator is 0.2-1.5 parts by weight.

[0225] Preferably, the molecular weight regulator added for the second time is 0.01-0.5 parts by weight, preferably 0.05-0.45 parts by weight.

[0226] In the present invention, in order to ensure that the reaction proceeds smoothly, it is preferred that the reaction is carried out under a protective atmosphere, and the protective gas may be at least one of nitrogen and an inert gas.

[0227] In the present invention, the latex is then degassed, flocculated, washed and dried to obtain an acrylonitrile copolymer. The degassing, flocculating and drying processes are conventional in the art and are not limited thereto. For example, the coagulant is selected from at least one of calcium chloride, sodium chloride and methanol. The coagulant is 3-8 parts by weight based on 100 parts by weight of the total weight of the solids in the latex.

[0228] The third aspect of the present invention provides an acrylonitrile copolymer prepared by the above preparation method.

[0229] A fourth aspect of the present invention provides a rubber composition, wherein the rubber comprises the above-mentioned acrylonitrile copolymer and nitrile rubber;

[0230] Wherein, based on 100 parts by weight of the acrylonitrile copolymer and the nitrile rubber, the acrylonitrile copolymer accounts for 70-100 parts by weight; and the nitrile rubber accounts for 0-30 parts by weight.

[0231] According to the present invention, the acrylonitrile copolymer is selected from at least one of a first acrylonitrile copolymer, a second acrylonitrile copolymer, a third acrylonitrile copolymer and a fourth acrylonitrile copolymer.

[0232] In the present invention, acrylonitrile copolymers with different glass transition temperatures and different damping temperature ranges are prepared by regulating the content of acyclic terpene monomers and combined acrylonitrile.

[0233] Preferably, in the first acrylonitrile copolymer, based on the total weight of the first acrylonitrile copolymer, the content of the structural unit derived from butadiene is 74-87wt%, the content of the structural unit derived from acrylonitrile is 8-16wt%, and the content of the structural unit derived from acyclic terpene is 5-10wt%.

[0234] Preferably, in the second acrylonitrile copolymer, based on the total weight of the second acrylonitrile copolymer, the content of the structural unit derived from butadiene is 44-72wt%, the content of the structural unit derived from acrylonitrile is 17-26wt%, and the content of the structural unit derived from acyclic terpene is 11-30wt%.

[0235] Preferably, in the third acrylonitrile copolymer, based on the total weight of the third acrylonitrile copolymer, the content of the structural unit derived from butadiene is 7-42wt%, the content of the structural unit derived from acrylonitrile is 27-34wt%, and the content of the structural unit derived from acyclic terpene is 31-59wt%.

[0236] Preferably, in the fourth acrylonitrile copolymer, based on the total weight of the fourth acrylonitrile copolymer, the content of the structural unit derived from butadiene is 0wt%, the content of the structural unit derived from acrylonitrile is 35-42wt%, and the content of the structural unit derived from acyclic terpene is 58-65wt%.

[0237] According to the present invention, the weight ratio of the first acrylonitrile copolymer, the second acrylonitrile copolymer, the third acrylonitrile copolymer and the fourth acrylonitrile copolymer is 1:0-1:0-1:0-1.

[0238] According to the present invention, based on 100 parts by weight of the acrylonitrile copolymer and the nitrile rubber, the rubber composition further comprises 1-2 parts by weight of a vulcanizing agent, 0.5-1 parts by weight of an accelerator, and 40-42 parts by weight of carbon black.

[0239] In the present invention, the vulcanizing agent, accelerator and carbon black are not particularly limited as long as they can perform vulcanization. For example, the vulcanizing agent is sulfur and the accelerator is N-tert-butyl-2-benzothiazolesulfenamide.

[0240] A fifth aspect of the present invention provides a rubber product, wherein the rubber product is obtained by mixing and vulcanizing the rubber composition described above.

[0241] In the present invention, the damping performance of the rubber product made of the acrylonitrile copolymer containing the structural unit derived from the acyclic terpene is superior to the damping performance, mechanical properties and polar medium resistance characteristics of the traditional nitrile rubber.

[0242] Furthermore, acrylonitrile copolymers with different contents of structural units from acyclic terpenes have different glass transition temperatures, and rubber products made therefrom have more excellent damping properties, mechanical properties and polar medium resistance.

[0243] According to the present invention, the effective damping temperature range of the rubber product is -50°C to 36°C.

[0244] According to the present invention, the loss factor of the rubber product is 1-1.55.

[0245] According to the present invention, the tensile strength of the rubber product is 18-27 MPa.

[0246] In the present invention, there is no particular limitation on the mixing and vulcanization of the rubber composition, as long as the rubber product can be obtained. For example, the mixing conditions include: mixing in an open mixer or internal mixer for 8-20 minutes; the vulcanization conditions include: vulcanization time of 30-50 minutes; vulcanization temperature of 145-150°C.

[0247] A sixth aspect of the present invention provides use of the acrylonitrile copolymer, the rubber composition, and the rubber product as a damping material.

[0248] The present invention will be described in detail below through examples.

[0249] All the raw materials used are commercially available.

[0250] Acyclic terpenes are myrcene ( C 10 H 16 , n=2, a1), farnesene ( C 15 H 24 , n=3, a2) and ocimene ( C 10 H 16 , n=2, a3).

[0251] The structural compositions of the acrylonitrile copolymers prepared in the following preparation examples and comparative preparation examples were determined by nuclear magnetic resonance spectroscopy.

[0252] The weight average molecular weight of the prepared acrylonitrile copolymer was measured by gel permeation chromatography.

[0253] The bound acrylonitrile content of the rubber was determined according to SH / T1157.2-2015. Specifically, the test method is method A.

[0254] The mechanical properties of rubber were determined according to GB / T 528-2009.

[0255] The swelling degree of rubber is determined according to SH / T 1159-2010. Specifically, the test method is method I.

[0256] The gel content was measured by SH / T 1050-2014 method.

[0257] The Mooney viscosity was tested according to GB / T 1232.1-2000 on a Mooney viscometer (GT-7080-S2, China Taiwan High Speed ​​Rail Testing Instrument Co., Ltd.) at a test temperature of 100°C for 1+4 min.

[0258] Damping performance [effective damping temperature range and loss factor (tanδ max )] Dynamic mechanical analyzer was used to test in accordance with GB / T33061.0-2016 “Determination of dynamic mechanical properties of plastics Part 1: General principles”. The test conditions were: frequency 10 Hz, temperature range -80°C to 100°C, and heating rate 2°C / min.

[0259] The glass transition temperature was tested by differential calorimetry with a heating rate of 10°C / min and a test temperature range of -100°C to 80°C.

[0260] Preparation Example - Preparation of Acrylonitrile Copolymer

[0261] Preparation Example 1

[0262] In a reactor, 220 parts by weight of desalted water, 3.8 parts by weight of sodium dodecylbenzene sulfonate, 0.5 parts by weight of diffusant N, 0.058 parts by weight of sodium formaldehyde sulfoxylate, 0.01 parts by weight of EDTA-sodium iron salt, 0.025 parts by weight of EDTA-tetrasodium salt, 0.2 parts by weight of sodium carbonate, 0.37 parts by weight of tert-dodecyl mercaptan, 80 parts by weight of butadiene, 13 parts by weight of acrylonitrile, and 7 parts by weight of myrcene were added. After evacuation, the gas was replaced with nitrogen three times, and then 0.08 parts by weight of deoxidizer sodium dithionite was added. When the temperature of the reactor dropped to 8°C, 0.062 parts by weight of diisopropylbenzene hydroperoxide were added to start polymerization. When the reaction conversion rate reaches 60%, 0.12 weight parts of tert-dodecyl mercaptan (second addition) are added. When the reaction conversion rate reaches 78%, 0.1 weight parts of diethylhydroxylamine and 0.05 weight parts of hydroxylamine sulfate are added to terminate the polymerization. The solid content is 25.8wt%. 5 weight parts of calcium chloride are added for condensation. After washing and drying, acrylonitrile copolymer A1 is obtained.

[0263] Preparation Example 2

[0264] An acrylonitrile copolymer was prepared according to the preparation method of Preparation Example 1, except that 50 parts by weight of butadiene, 20 parts by weight of acrylonitrile and 30 parts by weight of myrcene were used to obtain an acrylonitrile copolymer A2.

[0265] Preparation Example 3

[0266] An acrylonitrile copolymer was prepared according to the preparation method of Preparation Example 1, except that 20 parts by weight of butadiene, 29 parts by weight of acrylonitrile and 51 parts by weight of myrcene were used to obtain acrylonitrile copolymer A3.

[0267] Preparation Example 4

[0268] An acrylonitrile copolymer was prepared according to the preparation method of Preparation Example 1, except that 38 parts by weight of acrylonitrile and 62 parts by weight of myrcene were used to obtain acrylonitrile copolymer A4.

[0269] Preparation Example 5

[0270] An acrylonitrile copolymer was prepared according to the preparation method of Preparation Example 1, except that 20 parts by weight of butadiene, 29 parts by weight of acrylonitrile and 51 parts by weight of farnesene were used to obtain acrylonitrile copolymer A5.

[0271] Preparation Example 6

[0272] An acrylonitrile copolymer was prepared according to the preparation method of Preparation Example 1, except that 20 parts by weight of butadiene, 29 parts by weight of acrylonitrile and 51 parts by weight of ocimene were used to obtain acrylonitrile copolymer A6.

[0273] Preparation Example 7

[0274] An acrylonitrile copolymer was prepared according to the preparation method of Preparation Example 3, except that 1.5 parts by weight of sodium dodecylbenzene sulfonate, 0.0004 parts by weight of sodium formaldehyde sulfoxylate, 0.0005 parts by weight of EDTA-sodium iron salt, 0.025 parts by weight of EDTA-tetrasodium salt, 0.001 parts by weight of sodium carbonate, 0.1 parts by weight of tert-dodecyl mercaptan, 0.01 parts by weight of deoxidizer sodium dithionite, 0.005 parts by weight of diisopropylbenzene hydroperoxide, 0.01 parts by weight of tert-dodecyl mercaptan (added for the second time), 0.05 parts by weight of diethylhydroxylamine and 0.05 parts by weight of hydroxylamine sulfate, and 5 parts by weight of calcium chloride were used to prepare acrylonitrile copolymer A7.

[0275] Preparation Example 8

[0276] An acrylonitrile copolymer was prepared according to the preparation method of Preparation Example 3, except that 12 parts by weight of sodium dodecylbenzene sulfonate, 0.2 parts by weight of sodium formaldehyde sulfoxylate, 0.2 parts by weight of EDTA-sodium iron salt, 0.4 parts by weight of EDTA-tetrasodium salt, 0.5 parts by weight of sodium carbonate, 1.5 parts by weight of tert-dodecyl mercaptan, 0.01 parts by weight of deoxidizer sodium dithionite, 0.5 parts by weight of diisopropylbenzene hydroperoxide, 0.5 parts by weight of tert-dodecyl mercaptan (second addition), 0.5 parts by weight of diethylhydroxylamine and 0.5 parts by weight of hydroxylamine sulfate, and 5 parts by weight of calcium chloride were added to obtain acrylonitrile copolymer A8.

[0277] Preparation Example 9

[0278] An acrylonitrile copolymer was prepared according to the preparation method of Preparation Example 3, except that 4.2 parts by weight of sodium dodecylbenzene sulfonate, 0.84 parts by weight of diffusant N, 0.058 parts by weight of sodium formaldehyde sulfoxylate, 0.0174 parts by weight of EDTA-sodium iron salt, 0.025 parts by weight of EDTA-tetrasodium salt, 0.1 parts by weight of sodium carbonate, 0.38 parts by weight of tert-dodecyl mercaptan, 0.1 parts by weight of deoxidizer sodium dithionite, 0.072 parts by weight of diisopropylbenzene hydroperoxide, 0.12 parts by weight of tert-dodecyl mercaptan (added for the second time), 0.1 parts by weight of diethylhydroxylamine and 0.06 parts by weight of hydroxylamine sulfate, and 5 parts by weight of calcium chloride were used for condensation to obtain acrylonitrile copolymer A9.

[0279] Preparation Example 10

[0280] An acrylonitrile copolymer was prepared according to the preparation method of Preparation Example 3, except that when the reaction conversion rate reached 78%, 0.15 parts by weight of diethylhydroxylamine was added to terminate the polymerization, and hydroxylamine sulfate was not added to obtain an acrylonitrile copolymer A10.

[0281] Preparation Example 11

[0282] An acrylonitrile copolymer was prepared according to the preparation method of Preparation Example 3, except that 5 parts by weight of sodium dodecylbenzene sulfonate and 0 parts by weight of diffusing agent N were used as the emulsifier to obtain an acrylonitrile copolymer A11.

[0283] Preparation Comparative Example 1

[0284] Acrylonitrile copolymer DA1 was prepared according to the preparation method of Preparation Example 1, except that 62 parts by weight of butadiene, 38 parts by weight of acrylonitrile, and no acyclic terpene monomer were added to obtain acrylonitrile copolymer DA1.

[0285] Preparation Comparative Example 2

[0286] Acrylonitrile copolymer DA2 was prepared according to the preparation method of Preparation Example 2, except that 8 parts by weight of butadiene, 2 parts by weight of acrylonitrile and 90 parts by weight of myrcene were used to obtain acrylonitrile copolymer DA2.

[0287] The amount of butadiene monomer used in A1-A11 and DA1-DA2, the amount of acrylonitrile monomer used, the amount and type of acyclic terpene monomer used, the combined butadiene content, the combined acrylonitrile content, the combined acyclic terpene content and the glass transition temperature of the acrylonitrile copolymer are shown in Table 1.

[0288] Table 1

[0289]

[0290]

[0291] Table 1

[0292]

[0293] Example - Rubber Composition Preparation

[0294] The formulations of rubber compositions B1-B14 and DB1-DB2 are shown in Table 2.

[0295] Table 2

[0296]

[0297]

[0298] Example - Rubber Product Preparation

[0299] The rubber compositions B1-B10 and DB1-DB2 were mixed evenly and vulcanized at 145°C for 45 min to obtain rubber products R1-R10 and DR1-DR2. The properties of the rubber products are shown in Table 3.

[0300] Table 3

[0301]

[0302]

[0303] It can be seen from the results in Table 3 that the rubber products R1-R14 provided by the present invention have a wide damping temperature range, resistance to polar media, high loss factor and excellent tensile strength.

[0304] Compared with Example 1, the rubber product prepared in Comparative Example 1 does not contain acrylonitrile copolymer containing structural units derived from acyclic terpenes, but is only vulcanized with conventional vulcanized nitrile rubber, and has poor damping performance.

[0305] Figure 1 This is the H NMR spectrum of acrylonitrile copolymer A1. As can be seen from the figure, the chemical shift δ is 5.75-5.25 (2H, -CH=CH-; 1H, -CH=CH2); 5.25-4.85 (2H, -CH=CH2); 2.45-2.75 (1H, -CH-CN). It can be seen that acyclic terpene is successfully copolymerized into the polymer molecular chain.

[0306] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. An acrylonitrile copolymer, characterized in that Based on the total weight of the acrylonitrile copolymer, the content of the structural unit derived from butadiene in the acrylonitrile copolymer is 0-87wt%, the content of the structural unit derived from acrylonitrile is 8-42wt%, and the content of the structural unit derived from acyclic terpene is 5-65wt%.

2. The acrylonitrile copolymer according to claim 1, wherein The weight average molecular weight of the acrylonitrile copolymer is 150,000 g / mol-360,000 g / mol, preferably 200,000 g / mol-320,000 g / mol; Preferably, the molecular weight distribution of the acrylonitrile copolymer is 2.1-3.

5.

3. The acrylonitrile copolymer according to claim 1 or 2, wherein The acyclic terpene has the general formula shown in Formula I; (C5H8) n Formula I, wherein n is an integer from 2 to 8; Preferably, the acyclic terpene is selected from at least one of myrcene, farnesene and ocimene.

4. The acrylonitrile copolymer according to any one of claims 1 to 3, wherein The acrylonitrile copolymer has a glass transition temperature of -56°C to -1°C.

5. The acrylonitrile copolymer according to any one of claims 1 to 4, wherein Based on the total weight of the acrylonitrile copolymer, the content of the structural unit derived from butadiene in the acrylonitrile copolymer is 74-87wt%, the content of the structural unit derived from acrylonitrile is 8-16wt%, the content of the structural unit derived from acyclic terpene is 5-10wt%, and the glass transition temperature of the acrylonitrile copolymer is -56°C to -40°C; and / or, based on the total weight of the acrylonitrile copolymer, the content of the structural unit derived from butadiene in the acrylonitrile copolymer is 44-72wt%, the content of the structural unit derived from acrylonitrile is 17-26wt%, the content of the structural unit derived from acyclic terpene is 11-30wt%, and the glass transition temperature of the acrylonitrile copolymer is -42°C to -30°C; and / or, based on the total weight of the acrylonitrile copolymer, the content of the structural unit derived from butadiene in the acrylonitrile copolymer is 7-42wt%, the content of the structural unit derived from acrylonitrile is 27-34wt%, the content of the structural unit derived from acyclic terpene is 31-59wt%, and the glass transition temperature of the acrylonitrile copolymer is -35°C to -21°C; And / or, based on the total weight of the acrylonitrile copolymer, in the acrylonitrile copolymer, the content of the structural unit derived from butadiene is 0wt%, the content of the structural unit derived from acrylonitrile is 35-42wt%, the content of the structural unit derived from acyclic terpene is 58-65wt%, and the glass transition temperature of the acrylonitrile copolymer is -12°C to -1°C.

6. A method for preparing an acrylonitrile copolymer, characterized in that: reacting a reaction system containing butadiene monomer, acrylonitrile monomer, acyclic terpene monomer, water, an emulsifier, an oxidant and a reducing agent; Wherein, based on 100 parts by weight of the total weight of the butadiene monomer, the acrylonitrile monomer and the acyclic terpene monomer, the butadiene monomer is 0-87 parts by weight, the acrylonitrile monomer is 8-42 parts by weight, and the acyclic terpene monomer is 5-65 parts by weight.

7. The preparation method according to claim 6, wherein: The reaction system further contains a terminator, preferably, the terminator is added when the reaction conversion rate reaches 72-85%; Preferably, the reaction conditions include: the reaction temperature is 3-25°C, preferably 4-12°C; Preferably, the reaction system further comprises at least one of a pH buffer, a chelating agent, an oxygen scavenger and a molecular weight regulator; Preferably, the molecular weight regulator is added in steps, and more preferably, the molecular weight regulator is added for the second time when the reaction conversion rate reaches 50-70%.

8. The preparation method according to claim 6 or 7, wherein: In the reaction system, based on 100 parts by weight of the total weight of the butadiene monomer, the acrylonitrile monomer, and the acyclic terpene monomer, the emulsifier is 1.5-12 parts by weight, the oxidant is 0.005-0.5 parts by weight, and the reducing agent is 0.0009-0.4 parts by weight; Preferably, in the reaction system, based on 100 parts by weight of the total weight of the butadiene monomer, the acrylonitrile monomer, and the acyclic terpene monomer, the emulsifier is 2-7 parts by weight, the oxidant is 0.008-0.36 parts by weight, and the reducing agent is 0.001-0.1 parts by weight; Preferably, the pH buffer is 0.001-0.5 parts by weight, preferably 0.001-0.38 parts by weight, the deoxidizer is 0.01-0.1 parts by weight, preferably 0.08-0.1 parts by weight, the chelating agent is 0.0003-0.4 parts by weight, preferably 0.001-0.35 parts by weight, and the total weight of the molecular weight regulator is 0.11-2 parts by weight, preferably 0.2-1.5 parts by weight; Preferably, the molecular weight regulator added for the second time is 0.01-0.5 parts by weight, preferably 0.05-0.45 parts by weight.

9. The preparation method according to any one of claims 6 to 8, wherein: The acyclic terpene has the general formula shown in Formula I; (C5H8) n Formula I, wherein n is an integer from 2 to 8; Preferably, the acyclic terpene monomer is selected from at least one of myrcene, farnesene and ocimene.

10. An acrylonitrile copolymer obtained by the preparation method according to any one of claims 6 to 9.

11. A rubber composition, characterized in that: The rubber comprises the acrylonitrile copolymer and nitrile rubber as described in any one of claims 1 to 5 and 10; Wherein, based on 100 parts by weight of the acrylonitrile copolymer and the nitrile rubber, the acrylonitrile copolymer accounts for 70-100 parts by weight; and the nitrile rubber accounts for 0-30 parts by weight.

12. The rubber composition according to claim 11, wherein The acrylonitrile copolymer is selected from at least one of a first acrylonitrile copolymer, a second acrylonitrile copolymer, a third acrylonitrile copolymer and a fourth acrylonitrile copolymer; Preferably, in the first acrylonitrile copolymer, based on the total weight of the first acrylonitrile copolymer, the content of the structural unit derived from butadiene is 74-87wt%, the content of the structural unit derived from acrylonitrile is 8-16wt%, and the content of the structural unit derived from acyclic terpene is 5-10wt%; Preferably, in the second acrylonitrile copolymer, based on the total weight of the second acrylonitrile copolymer, the content of the structural unit derived from butadiene is 44-72wt%, the content of the structural unit derived from acrylonitrile is 17-26wt%, and the content of the structural unit derived from acyclic terpene is 11-30wt%; Preferably, in the third acrylonitrile copolymer, based on the total weight of the third acrylonitrile copolymer, the content of the structural unit derived from butadiene is 7-42wt%, the content of the structural unit derived from acrylonitrile is 27-34wt%, and the content of the structural unit derived from acyclic terpene is 31-59wt%; Preferably, in the fourth acrylonitrile copolymer, based on the total weight of the fourth acrylonitrile copolymer, the content of the structural unit derived from butadiene is 0wt%, the content of the structural unit derived from acrylonitrile is 35-42wt%, and the content of the structural unit derived from acyclic terpene is 58-65wt%; Preferably, the weight ratio of the first acrylonitrile copolymer, the second acrylonitrile copolymer, the third acrylonitrile copolymer and the fourth acrylonitrile copolymer is 1:0-1:0-1:0-1.

13. A rubber product, characterized in that: The rubber product is obtained by mixing and vulcanizing the rubber composition according to claim 11 or 12.

14. The rubber product according to claim 13, wherein: The effective damping temperature range of the rubber product is -50°C to 36°C; Preferably, the loss factor of the rubber product is 1-1.55; Preferably, the rubber product has a tensile strength of 18-27 MPa.

15. Use of the acrylonitrile copolymer according to any one of claims 1 to 5 and 10, the rubber composition according to claim 11 or 12, or the rubber product according to claim 13 or 14 as a damping material.

Images