High and low temperature resistant softening agent as well as preparation method and application thereof

Abstract

The invention discloses a high and low temperature resistant softening agent and a preparation method and application thereof.The high and low temperature resistant softening agent comprises adipic acid, alcohol ether, butanediol and a catalyst, the molar ratio of the adipic acid to the alcohol ether to the butanediol is (0.5-3): (1-5): (0-3), the dosage of the catalyst is 1-4% of the total content of the components, and the content of the catalyst is 1-3% of the total content of the components. The alcohol ether comprises at least one of diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether and ethylene glycol monomethyl ether. The polyether ester softener simultaneously contains ester groups and ether bonds, is relatively high in molecular weight and good in molecular flexibility, and can be better combined with polar rubber and plastic materials; and the softening agent has the advantages of excellent cold resistance (low temperature resistance), heat resistance (high temperature resistance) and the like, can be used in products with high and low temperature resistance, and can easily widen the use temperature range of rubber products.

Description

Technical Field

[0001] The invention relates to the technical field of softeners, and in particular to a high and low temperature resistant softener and a preparation method and application thereof. Background Art

[0002] Softeners are additives used in rubber mixtures for tires (pneumatic tires, bicycle tires, solid rubber tires) and in industrial rubber products (hoses, transmission belts, other belts, printed blankets, films, gaskets, air springs, airbags, automotive interior trims, synthetic leather). Softeners are added to rubber mixtures in order to reduce the cost of the mixture, improve the flow characteristics of the mixture (saving energy during processing, avoiding energy peaks), improve filler dispersion, improve further processing behavior and adhesion behavior, and change the physical properties of the mixture and the cured rubber produced therefrom.

[0003] Softener is a kind of additive that is widely used in rubber. It can effectively improve the processing performance of rubber and reduce the glass transition temperature of rubber. However, most softeners are now used in combination to provide better overall performance. This is because although the softener has a good plasticizing effect when the molecular weight is low, its heat resistance and durability are poor. Although the high molecular weight softener has low volatility and high temperature resistance, its low temperature performance and softening efficiency are poor.

[0004] Based on the above background, the softeners currently used in rubber products on the market are still lacking in high and low temperature resistance and cannot meet production needs. Summary of the invention

[0005] The purpose of the present invention is to provide a high and low temperature resistant softener and a preparation method and application thereof. The polyether ester softener of the present invention contains both an ester group and an ether bond, has a high molecular weight and good molecular flexibility, and can be better combined with polar rubber and plastic materials; and the softener of the present invention has the advantages of excellent cold resistance (low temperature resistance) and heat resistance (high temperature resistance), etc., and can be used in products with high and low temperature resistance, and can easily broaden the use temperature range of rubber products.

[0006] To this end, the present invention provides a high and low temperature resistant softener, comprising the following components: adipic acid, alcohol ether, butanediol and a catalyst, wherein the molar ratio of adipic acid, alcohol ether and butanediol is (0.5-3):(1-5):(0-3), the amount of the catalyst is 1-4% of the total component content, and the alcohol ether comprises at least one of diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether and ethylene glycol monomethyl ether.

[0007] Preferably, the molar ratio of adipic acid, alcohol ether and butanediol is (1-2.5):(1-3):(0-2).

[0008] Preferably, the catalyst comprises at least one of concentrated sulfuric acid, concentrated hydrochloric acid, p-toluenesulfonic acid, thionyl chloride and trifluoromethanesulfonic acid.

[0009] Preferably, the high and low temperature resistant softener has a number average molecular weight of 500-1500, a weight average molecular weight of 600-1800, and a molecular weight distribution greater than 1.

[0010] Preferably, the ether-ester bond content of the high and low temperature resistant softener is 10-25%, and the acid value of the high and low temperature resistant softener is 3-18%.

[0011] The present invention also provides a method for preparing the high and low temperature resistant softener, comprising:

[0012] (1) adding adipic acid, butanediol, alcohol ether and a catalyst into a reactor, evacuating the reactor and heating the reactor to react;

[0013] (2) After the reaction is completed, the reaction liquid is collected to obtain the softener.

[0014] Preferably, in step (1), the vacuum degree is -0.02-0.08 MPa, the reaction temperature is 80-150° C., and the reaction time is 1-6 h.

[0015] The present invention also provides the use of the high and low temperature resistant softener in the preparation of a rubber composition, wherein the rubber composition comprises the following components in parts by weight: 100 parts by weight of raw rubber, 40-90 parts by weight of a reinforcing agent, 15-30 parts by weight of a softener, 1-3 parts by weight of an antioxidant, 2-5 parts by weight of a vulcanizing agent, and 7-10 parts by weight of a cross-linking agent.

[0016] Preferably, the method for preparing the rubber composition comprises:

[0017] (1) the raw rubber is subjected to a first banburying alone, and then half of the reinforcing agent is added to perform a second banburying, and then half of the softening agent is added to perform a third banburying, and then the remaining half of the reinforcing agent is added to perform a fourth banburying, and then the remaining half of the softening agent is added to perform a fifth banburying to obtain a banburying rubber;

[0018] (2) mixing the internal rubber, the vulcanizing agent and the cross-linking agent, and after the mixing is completed, thinning and discharging the rubber to obtain a mixed rubber;

[0019] (3) The rubber mixture is vulcanized to obtain a rubber composition.

[0020] Preferably, in the step (1), the first banburying time is 1-5 min and the temperature of the first banburying is 60-80°C; the second banburying time is 1-5 min and the temperature of the second banburying is 80-90°C; the third banburying time is 1-5 min and the temperature of the third banburying is 90-100°C; the fourth banburying time is 1-5 min and the temperature of the fourth banburying is 100-110°C; the fifth banburying time is 1-5 min and the temperature of the fifth banburying is 110-130°C; in the step (2), the number of thin passes is 3-10 times, and the mixed rubber is left to cool for 8-20 hours after the rubber is discharged; in the step (3), the vulcanization time is 0.5-5 min and the vulcanization temperature is 150-200°C.

[0021] Compared with the prior art, the advantages and positive effects of the present invention include:

[0022] (1) The polyetherester softener of the present invention contains both ester groups and ether bonds, has a high molecular weight and good molecular flexibility, and can be better combined with polar rubber and plastic materials; and the softener of the present invention has the advantages of excellent cold resistance (low temperature resistance) and heat resistance (high temperature resistance), and can be used in products with high and low temperature resistance, which can easily broaden the use temperature range of rubber products. The preparation method of the softener of the present invention is green and environmentally friendly. The softener prepared by this method does not contain toxic substances such as polycyclic aromatic hydrocarbons and has good environmental protection.

[0023] (2) The softener of the present application can greatly reduce the Mooney viscosity and torque of the rubber compound, improve the fluidity of the rubber compound, improve its processing performance, and shorten the vulcanization time, but has little effect on the operational safety of the rubber compound. The softener of the present application reduces the rigidity of the rubber compound and reduces the tensile strength and tear strength. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a Fourier infrared spectrum detection data diagram of the softening agent of Example 1 to Example 5;

[0025] Figure 2 The nuclear magnetic resonance detection data diagram of the softening agent of Example 1 to Example 5;

[0026] Figure 3 It is the GPC test data diagram of the softener of Example 1-Example 5;

[0027] Figure 4 TG and DTG test data diagram of the softeners of Examples 1 to 5;

[0028] Figure 5 The Mooney viscosity test data of the hydrogenated nitrile rubber compositions of Examples 6 to 11, Comparative Example 1 and Comparative Example 2 are shown;

[0029] Figure 6It is a graph showing the mechanical properties test data of the hydrogenated nitrile rubber compositions of Examples 6 to 11, Comparative Example 1, and Comparative Example 2;

[0030] Figure 7 It is a graph showing the aging performance test data of the hydrogenated nitrile rubber compositions of Examples 6 to 11, Comparative Example 1, and Comparative Example 2;

[0031] Figure 8 The data graph of mass loss rate after aging of the hydrogenated nitrile rubber compositions of Examples 6 to 11, Comparative Example 1 and Comparative Example 2;

[0032] Fig. 9 The oil resistance and water resistance test data of the hydrogenated nitrile rubber compositions of Examples 6 to 11, Comparative Example 1 and Comparative Example 2 after aging are shown;

[0033] Fig.10 This is a graph of cold resistance test data of the hydrogenated nitrile rubber compositions of Example 6 to Example 11, Comparative Example 1, and Comparative Example 2 after aging. DETAILED DESCRIPTION

[0034] In order to make the purpose, technical scheme and advantages of the present invention more clearly understood, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood by those skilled in the art that the content described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0035] The invention provides a high and low temperature resistant softener, comprising the following components: adipic acid, alcohol ether, butanediol and a catalyst, wherein the molar ratio of adipic acid, alcohol ether and butanediol is (0.5-3):(1-5):(0-3), the amount of the catalyst is 1-4% of the total component content, and the alcohol ether comprises at least one of diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether and ethylene glycol monomethyl ether.

[0036] The present invention uses adipic acid and alcohol ether for polycondensation reaction, and synthesizes a polyether ester softener with a high esterification rate by changing the reaction temperature, time, reactant molar ratio, catalyst dosage, etc.; the molecular structure and molecular weight of the softener are changed by adding butanediol and changing the type of end-capping agent alcohol ether, and synthesizes polyether ester softeners with different structures. The polyether ester softener of the present invention contains both ester groups and ether bonds, has a high molecular weight and good molecular flexibility, and can be better combined with polar rubber and plastic materials; and the softener of the present invention has the advantages of excellent cold resistance (low temperature resistance) and heat resistance (high temperature resistance), etc., and can be used in products with high and low temperature resistance, and can easily broaden the use temperature range of rubber products. The preparation method of the softener of the present invention is green and environmentally friendly. The softener prepared by the method does not contain toxic substances such as polycyclic aromatic hydrocarbons, and has good environmental protection.

[0037] The molar ratio of adipic acid, alcohol ether and butanediol is (1-2.5):(1-3):(0-2), which can make adipic acid and alcohol ether undergo sufficient polycondensation reaction to obtain a polyether ester softener with a high esterification rate, and can also improve the molecular weight and molecular flexibility of the softener, improve the low temperature resistance and high temperature resistance of the softener, and make the softener better combined with rubber and plastic materials.

[0038] The catalyst includes at least one of concentrated sulfuric acid, concentrated hydrochloric acid, p-toluenesulfonic acid, thionyl chloride and trifluoromethanesulfonic acid, and can catalyze adipic acid and alcohol ether to fully perform polycondensation reaction to obtain a polyether ester softener with a high esterification rate.

[0039] The dosage of the catalyst is 1-4% of the total component content, which can catalyze the sufficient polycondensation reaction of adipic acid and alcohol ether to obtain a polyether ester softener with a high esterification rate, and can improve the molecular weight and molecular flexibility of the softener, so that the softener can be better combined with rubber and plastic materials.

[0040] The number average molecular weight of the softener is 500-1500, the weight average molecular weight is 600-1800, and the molecular weight distribution is greater than 1. The softener of the present invention has a high molecular weight and good molecular flexibility, has good high temperature resistance, and can be better combined with polar rubber and plastic materials.

[0041] The ether-ester bond content of the softener is 10-25%, which can make the softener have good low-temperature resistance.

[0042] The acid value of the softener is 3-18%, which can make the softener better combined with polar rubber and plastic materials.

[0043] The preparation method of the high and low temperature resistant softener of the present invention comprises the following steps:

[0044] (1) Add adipic acid, butanediol, alcohol ether and catalyst into a 250mL three-necked flask, and then place a magnet in the flask; seal the left and right openings of the flask with glass stoppers, connect the middle opening with a distillation elbow, a straight condenser and a vacuum tail pipe in sequence, and connect the vacuum tail pipe to a single-necked flask and a vacuum pump. Turn on the cooling water, heat, and evacuate to carry out the reaction;

[0045] The vacuum degree is -0.02 -0.08Mpa, the reaction temperature is 80-150°C, and the reaction time is 1-6h.

[0046] (2) After the reaction time is up, stop heating, turn off the vacuum, heating, and cooling water in sequence, dismantle the device, collect the reaction liquid, and obtain the softener.

[0047] The preparation method of the softener of the present invention is green and environmentally friendly. The softener prepared by the method does not contain toxic substances such as polycyclic aromatic hydrocarbons and has good environmental protection.

[0048] The high and low temperature resistant softener of the present invention has excellent high and low temperature resistance and can be used for the preparation of a rubber composition. The softener can reduce the tensile strength, tear strength and elongation at break of the rubber composition and can improve the flexibility and high temperature resistance and low temperature resistance of the rubber composition.

[0049] The present invention also provides a rubber composition, comprising the following components in parts by weight:

[0050] 100 parts by weight of raw rubber, 40-90 parts by weight of reinforcing agent, 15-30 parts by weight of softener, 1-3 parts by weight of antioxidant, 2-5 parts by weight of vulcanizing agent and 7-10 parts by weight of crosslinking agent.

[0051] In the present invention, the raw rubber may be hydrogenated nitrile rubber HNBR, or other rubber commonly used in the technical field, which is not specifically limited herein.

[0052] The reinforcing agent may include 10-50 parts of N330 carbon black, 10-50 parts of N550 carbon black, 10-40 parts of kaolin and 10-50 parts of white carbon black; the above-mentioned multiple reinforcing agents cooperate with each other and are used in coordination to achieve the best reinforcing effect on rubber.

[0053] The softener includes at least one of polydibutyl adipate, polydibutyl adipate, polybutylene glycol butyl adipate, polydimethyl adipate, and polymethyl adipate.

[0054] Alternatively, the softener includes any two of dibutyl adipate, polybutylene glycol dibutyl adipate, polybutylene glycol butyl adipate, polybutylene glycol dimethyl adipate and polybutylene glycol methyl adipate, and the mass ratio thereof is 1:1.

[0055] The antioxidant includes at least one of an amine antioxidant, a phenol antioxidant, a quinoline antioxidant and a benzimidazole antioxidant.

[0056] The vulcanizing agent includes at least one of dicumyl peroxide, di-tert-butyl dicumyl peroxide, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.

[0057] The crosslinking agent includes at least one of triallyl isocyanurate, triallyl cyanurate, N,N'-m-phenylene bismaleimide, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate.

[0058] The present invention also provides a rubber composition and a preparation method thereof, comprising:

[0059] (1) the raw rubber is subjected to a first banburying alone, and then half of the reinforcing agent is added to perform a second banburying, and then half of the softening agent is added to perform a third banburying, and then the remaining half of the reinforcing agent is added to perform a fourth banburying, and then the remaining half of the softening agent is added to perform a fifth banburying to obtain a banburying rubber;

[0060] (2) mixing the internal rubber, the vulcanizing agent and the cross-linking agent, and after the mixing is completed, thinning and discharging the rubber to obtain a mixed rubber;

[0061] (3) vulcanizing the rubber mix to obtain the hydrogenated nitrile rubber composition.

[0062] Step (1), the first banburying time is 1-5min, and the first banburying temperature is 60-80°C; the second banburying time is 1-5min, and the second banburying temperature is 80-90°C; the third banburying time is 1-5min, and the third banburying temperature is 90-100°C; the fourth banburying time is 1-5min, and the fourth banburying temperature is 100-110°C; the fifth banburying time is 1-5min, and the fifth banburying temperature is 11-130°C;

[0063] Step (2), the number of thin passes is 3-10 times, and after the rubber is discharged, the mixed rubber is left to cool for 10-20 hours;

[0064] Step (3), the vulcanization time is 0.5-5min, and the vulcanization temperature is 150-200°C.

[0065] Example 1

[0066] The preparation method of the softener of this embodiment comprises:

[0067] (1) Add adipic acid, diethylene glycol monobutyl ether and catalyst into a 250mL three-necked flask, and then place a magnet in the flask; seal the left and right openings of the flask with glass stoppers, connect the middle opening with a distillation elbow, a straight condenser and a vacuum tail pipe in sequence, and connect the vacuum tail pipe to a single-necked flask and a vacuum pump. Turn on the cooling water, heat, and evacuate to carry out the reaction;

[0068] (2) After the reaction time is up, the heating is stopped, and the vacuum, heating, and cooling water are turned off in sequence. The device is disassembled, and the reaction liquid is collected to obtain softener A: poly(dibutyl adipate).

[0069] Example 2

[0070] The preparation method of the softener of this embodiment comprises:

[0071] (1) Add adipic acid, butanediol, diethylene glycol monobutyl ether and catalyst into a 250mL three-necked flask, and then place a magnet in the flask; seal the left and right openings of the flask with glass stoppers, connect the middle opening with a distillation elbow, a straight condenser and a vacuum tail pipe in sequence, and connect the vacuum tail pipe to a single-necked flask and a vacuum pump. Turn on the cooling water, heat, and evacuate to carry out the reaction;

[0072] (2) After the reaction time is up, the heating is stopped, and the vacuum, heating, and cooling water are turned off in sequence. The device is disassembled, and the reaction liquid is collected to obtain softener B: polybutylene adipate dibutyl ether ester.

[0073] Example 3

[0074] The preparation method of the softener of this embodiment comprises:

[0075] (1) Add adipic acid, butanediol, ethylene glycol monobutyl ether and catalyst into a 250mL three-necked flask, and then place a magnet in the flask; seal the left and right openings of the flask with glass stoppers, connect the middle opening with a distillation elbow, a straight condenser and a vacuum tail pipe in sequence, and connect the vacuum tail pipe to a single-necked flask and a vacuum pump. Turn on the cooling water, heat, and evacuate to carry out the reaction;

[0076] (2) After the reaction time is up, the heating is stopped, and the vacuum, heating, and cooling water are turned off in sequence. The device is disassembled, and the reaction liquid is collected to obtain softener C: polybutylene adipate.

[0077] Example 4

[0078] The preparation method of the softener of this embodiment comprises:

[0079] (1) Add adipic acid, butanediol, diethylene glycol monomethyl ether and catalyst into a 250mL three-necked flask, and then place a magnet in the flask; seal the left and right openings of the flask with glass stoppers, connect the middle opening with a distillation elbow, a straight condenser and a vacuum tail pipe in sequence, and connect the vacuum tail pipe to a single-necked flask and a vacuum pump. Turn on the cooling water, heat, and evacuate to carry out the reaction;

[0080] (2) After the reaction time is up, the heating is stopped, and the vacuum, heating, and cooling water are turned off in sequence. The device is disassembled, and the reaction liquid is collected to obtain softener D: polybutylene adipate dimethyl ether ester.

[0081] Example 5

[0082] The preparation method of the softener of this embodiment comprises:

[0083] (1) Add adipic acid, butanediol, ethylene glycol monomethyl ether and catalyst into a 250mL three-necked flask, and then place a magnet in the flask; seal the left and right openings of the flask with glass stoppers, connect the middle opening with a distillation elbow, a straight condenser and a vacuum tail pipe in sequence, and connect the vacuum tail pipe to a single-necked flask and a vacuum pump. Turn on the cooling water, heat, and evacuate to carry out the reaction;

[0084] (2) After the reaction time is up, the heating is stopped, and the vacuum, heating, and cooling water are turned off in sequence. The device is disassembled, and the reaction liquid is collected to obtain softener E: polybutylene adipate methyl ether ester.

[0085] The process parameters of Examples 1 to 5 can be referred to as shown in Table 1.

[0086] Table 1

[0087] Molar ratio of adipic acid, alcohol ether and butanediol Catalyst dosage% Reaction time Reaction temperature℃ Example 1 1:2.3:0 1.5 2 120 Example 2 2:2.6:1 1.5 4 140 Example 3 2:2.6:1 1.5 4 140 Example 4 2:2.6:1 1.5 4 140 Example 5 2:2.6:1 1.5 4 140

[0088] The softeners of Examples 1 to 5 were tested as follows:

[0089] The acid values ​​and esterification rates of the softeners of Examples 1 to 5 are shown in Table 2. From the data in Table 2, it can be concluded that the synthetic reactions of the softeners of the Examples are substantially complete, and the esterification rates are all higher than 99%.

[0090] Table 2

[0091] Example 1 Example 2 Example 3 Example 4 Example 5 <![CDATA[Acid value mgKOH·g -1 > 6.9 5.4 9.6 8.2 15.6 Esterification rate% 99.6 99.7 99.1 99.4 99.0

[0092] The softeners of Examples 1 to 5 were subjected to Fourier transform infrared spectroscopy detection, and the results were as follows: Figure 1 As shown. Figure 1 It can be seen that the main characteristic absorption peak of the softener corresponds to the wave number: 2920cm -1 The left and right sides are the strong stretching vibration absorption peaks of -CH-, 1600cm -1 The position on the left and right is the strong stretching vibration absorption peak of C=O in the ester group, 1430cm -1 The left and right sides are the symmetrical stretching vibration absorption peaks of -CH3, 1090cm -1 The left and right are asymmetric stretching vibration absorption peaks of ether group COC. In general, the infrared spectra of the softeners of Examples 1 to 5 are basically the same, and the composition structures are similar.

[0093] The softeners of Examples 1 to 5 were subjected to nuclear magnetic resonance detection, and the results were as follows: Figure 2 As shown. Figure 2It can be seen that the nuclear magnetic hydrogen spectra of the five softeners correspond to the theoretical chemical structural formula. Since the softeners of Example 1 and Example 2 use the same alcohol ether, butanediol is not added to the softener of Example 1, and the softener of Example 2 contains butanediol, the chemical shift in the 1H-NMR of the softener of Example 2 has two more peaks at 4.0 and 1.56, namely, two groups of H on CH2-OH and CH2-CH2 in butanediol. The softeners of Example 2 to Example 5 have changes in the chemical shift of active hydrogen due to the different types of alcohol ethers used. The softener of Example 2 has 3.5 more peaks in ethylene glycol-CH2-OH than the softener of Example 3. The softeners of Example 4 and Example 5 increase the chemical shift of H on -CH3 at the end of the molecular chain due to the presence of methyl ether groups.

[0094] The softeners of Examples 1 to 5 were subjected to GPC testing, and the results were as follows: Figure 3 As shown. Figure 3 It can be seen that 10-11 minutes is the test sample peak, and about 11.7 minutes is the solvent peak. The softeners of Examples 1 to 5 have molecular weight distribution due to different polymerization degrees.

[0095] The molecular weight and molecular weight distribution of the softeners of Examples 1 to 5 are shown in Table 3. It can be seen from Table 3 that the molecular weights of softener B of Example 2, softener D of Example 4, softener C of Example 3, softener E of Example 5, and softener A of Example 1 decrease in sequence. The molecular weight distributions of softener B of Example 2, softener D of Example 4, softener C of Example 3, softener E of Example 5, and softener A of Example 1 become narrower in sequence.

[0096] Table 3

[0097] Molecular weight range / mol Mn M Mw / Mn Example 1 391-1396 636 653 1.027 Example 2 356-4438 1105 1226 1.109 Example 3 372-4438 967 1058 1.094 Example 4 372-4438 987 1083 1.097 Example 5 384-4187 740 774 1.046

[0098] The softeners of Examples 1 to 5, dioctyl sebacate DOS, softener B and softener D in a mass ratio of 1:1 were subjected to TG and DTG tests. The results are as follows: Figure 4 As shown. Figure 4It can be seen that the initial weight loss temperature of softener A in Example 1 is 106°C, the complete weight loss temperature is about 297°C, and the weight loss rate is fastest at 293°C. The initial weight loss temperatures of softener B in Example 2, softener C in Example 3, softener D in Example 4, and softener E in Example 5 are about 126°C, the complete weight loss temperature of softener B in Example 2 is 382°C, and the weight loss rate is fastest at about 360°C, the complete weight loss temperature of softener C in Example 3 is 347°C, and the weight loss rate is fastest at about 340°C, the complete weight loss temperature of softener E in Example 5 is 330°C, and the weight loss rate is fastest at about 324°C, and the complete weight loss temperature of softener D in Example 4 is 350°C, and the weight loss rate is fastest at about 346°C. The volatility resistance of softener B in Example 2, softener D in Example 4, softener C in Example 3, softener E in Example 5, and softener A in Example 1 decreases in sequence. The volatility is proportional to the molecular weight of the softener. The larger the molecular weight, the higher the decomposition temperature of the softener and the lower the volatility.

[0099] Example 6

[0100] The hydrogenated nitrile rubber composition HA of the present embodiment includes 100 parts by mass of hydrogenated nitrile rubber, 70 parts by mass of a reinforcing agent, 20 parts by mass of a softener A polydibutyl adipate, 1.5 parts by mass of an antioxidant, 3.5 parts by mass of a vulcanizing agent, and 8.25 parts by mass of a crosslinking agent.

[0101] The preparation method of the hydrogenated nitrile rubber composition HA of the present embodiment comprises:

[0102] Add hydrogenated nitrile rubber to the mixer, start at 70℃, mix for 1.5min, rotate at 60r / min, then add half of the carbon black, mix for 1.5min, add half of the softener, add the remaining carbon black after 1.5min, add the remaining softener after 1.5min, mix for 1.5min; lift the bolt and pressurize to continue mixing for 2min, discharge the rubber, immediately release the mixer to mix, add DCP and TAIC, mix evenly, pass through 5 times, discharge the rubber, and leave it for 16h. Cut the mixed rubber and vulcanize it on a flat vulcanizer, the vulcanization time is t90 plus 1min, the temperature is 170℃, and the vulcanized rubber is left at room temperature for 16h before use.

[0103] Example 7

[0104] The hydrogenated nitrile rubber composition HB of this embodiment is substantially the same as that of embodiment 6, except that the softener B polybutylene adipate dibutyl ether ester is used in this embodiment.

[0105] Example 8

[0106] The hydrogenated nitrile rubber composition HC of this embodiment is substantially the same as that of embodiment 6, except that the softener C polybutylene adipate is used in this embodiment.

[0107] Example 9

[0108] The hydrogenated nitrile rubber composition HD of this embodiment is substantially the same as that of embodiment 6, except that the softener D polybutylene adipate dimethyl ether is used in this embodiment.

[0109] Example 10

[0110] The hydrogenated nitrile rubber composition HE of this embodiment is substantially the same as that of embodiment 6, except that the softener E polybutylene adipate methyl ether is used in this embodiment.

[0111] Embodiment 11

[0112] The hydrogenated nitrile rubber composition H-BD of this embodiment is substantially the same as that of embodiment 6, except that the softener B polybutylene adipate dibutyl ether ester and the softener D polybutylene adipate dimethyl ether ester are used in a mass ratio of 1:1 in this embodiment.

[0113] Comparative Example 1

[0114] The hydrogenated nitrile rubber composition Blank Sample of this comparative example is substantially the same as that of Example 6, except that no softener is used in this comparative example.

[0115] Comparative Example 2

[0116] The hydrogenated nitrile rubber composition H-DOS of this comparative example is substantially the same as that of Example 6, except that the softener used in this comparative example is diisooctyl sebacate DOS.

[0117] The hydrogenated nitrile rubber compositions of Example 6-Example 11, Comparative Example 1 and Comparative Example 2 were tested as follows:

[0118] The Mooney viscosity of the hydrogenated nitrile rubber compositions of Example 6-Example 11, Comparative Example 1 and Comparative Example 2 was tested. The test results are as follows: Figure 5 As shown. Figure 5 It can be seen that compared with Comparative Example 1 and Comparative Example 2, the addition of the softener in the embodiment greatly reduces the Mooney viscosity of the polar rubber hydrogenated nitrile rubber composition, significantly improves the fluidity of the rubber material, and improves its processing performance. The Mooney viscosity of the hydrogenated nitrile rubber composition HA and the hydrogenated nitrile rubber composition H-BD are both small, and their fluidity is good and their processing performance is excellent.

[0119] The vulcanization performance of the hydrogenated nitrile rubber compositions of Examples 6 to 11, Comparative Example 1, and Comparative Example 2 was tested, and the test results are shown in Table 4. As can be seen from Table 4, compared with Comparative Example 1 and Comparative Example 2, the addition of the softener in the examples greatly reduces the torque of the polar rubber hydrogenated nitrile rubber composition and improves its processing performance. The scorch time (t 10 ) are roughly the same, indicating that the softener has little effect on the operational safety of the HNBR rubber compound. The process positive vulcanization time (t 90 ) is compared with the process positive vulcanization time (t 90 ) is short, which shows that adding the softener of the present invention can accelerate the vulcanization speed of the rubber compound and improve the processing performance of the rubber compound. The process positive vulcanization time (t 90 ) are relatively small and have excellent processing performance.

[0120] Table 4

[0121]

[0122] The mechanical properties of the hydrogenated nitrile rubber compositions of Example 6-Example 11, Comparative Example 1 and Comparative Example 2 were tested. The test results are as follows: Figure 6 As shown. Figure 6 It can be seen that, compared with Comparative Example 1 and Comparative Example 2, the addition of the softener in the embodiment can reduce the tensile strength and tear strength of the HNBR rubber, and can increase the elongation at break and the compression permanent deformation, thereby improving the flexibility of the HNBR rubber, reducing the rigidity, and improving the processing performance of the rubber.

[0123] The aging properties of the hydrogenated nitrile rubber compositions of Example 6-Example 11, Comparative Example 1 and Comparative Example 2 were tested. The test results are as follows: Figure 7 As shown. Figure 7It can be seen that compared with Comparative Examples 1 and 2, the addition of a softener in the embodiment can reduce the hardness of the HNBR rubber. Compared with before aging, the tensile strength of the HNBR with a softener after aging is increased, and the elongation at break is decreased, while the tensile strength and elongation at break of the HNBR without a softener after aging are both decreased. This is because aging causes the acrylonitrile double bonds contained in the HNBR to break, resulting in a decrease in the tensile strength and elongation at break of the rubber, while the HNBR rubber with a softener has a partial softener volatilization loss, resulting in a recovery of the tensile strength of the rubber; compared with Comparative Examples 1 and 2, the addition of a softener in the embodiment of the present invention reduces the tensile strength of the HNBR rubber after aging and increases the elongation at break. On the whole, the performance changes of hydrogenated nitrile rubber composition HB, hydrogenated nitrile rubber composition HD, and hydrogenated nitrile rubber composition H-BD before and after aging are small; this is because softener B and softener D have high molecular weight and good aging resistance; the combination of softener B and softener D can effectively improve the aging resistance of HNBR rubber.

[0124] The mass loss rate of the hydrogenated nitrile rubber compositions of Examples 6 to 11, Comparative Example 1 and Comparative Example 2 after aging was tested. The test results are as follows: Figure 8 As shown. Figure 8 It can be seen that, compared with Comparative Examples 1 and 2, the addition of the softener in the embodiment can cause the HNBR rubber compound to have a higher mass loss. This is because during the aging process, the volatilization of the softener will cause the rubber compound to which the softener is added to have a higher mass loss.

[0125] The oil resistance and water resistance of the hydrogenated nitrile rubber compositions of Example 6 to Example 11, Comparative Example 1 and Comparative Example 2 were tested. The test results are as follows: Fig. 9 As shown, Fig. 9 (a) is the rate of mass change; Fig. 9 (b) is the volume change rate. Fig. 9 It can be seen that in 901# oil, HNBR vulcanizate mainly shows extraction effect, and the volume change rate and mass change rate of HE are the smallest, followed by HD, HC, HA, and HB; in 901# oil, as the proportion of softener ester group increases, the rubber has higher oil resistance. In 903# oil, HNBR vulcanizate shows the result of the combined effect of swelling and extraction. The volume change rate and mass change rate of the blank rubber of comparative example 1 in 903# oil are the largest, and the hydrogenated nitrile rubber composition HB is the smallest, indicating that the addition of the softener in this embodiment improves the oil resistance of HNBR vulcanizate in 903# oil; on the whole, the oil resistance of softener D is better. In water, there is no obvious regularity in the volume change rate and mass change rate of HNBR vulcanizate with the addition of softener and blank sample.

[0126] The hydrogenated nitrile rubber compositions of Example 6-Example 11, Comparative Example 1 and Comparative Example 2 were subjected to DSC test. The test results are as follows: Fig.10 As shown. Fig.10 It can be seen that the glass transition temperature of the hydrogenated nitrile rubber composition HD is the lowest, followed by the glass transition temperature of the hydrogenated nitrile rubber composition H-BD. This shows that softener D and softener B+D can effectively improve the low-temperature performance of HNBR rubber and effectively enhance the low-temperature resistance of HNBR rubber.

[0127] The cold resistance of the hydrogenated nitrile rubber compositions of Examples 6 to 11, Comparative Example 1 and Comparative Example 2 after aging was tested, and the test results are shown in Table 5. As can be seen from Table 5, compared with Comparative Example 1 and Comparative Example 2, the addition of the softener in the example can reduce the TR of the HNBR rubber compound. 10 ,TR 30 ,TR 50 , brittle temperature, that is, the softener in this embodiment can greatly improve the cold resistance of HNBR rubber. Among them, the hydrogenated nitrile rubber composition HB has the lowest brittle temperature, indicating that it has the best low-temperature impact resistance; the TR of the hydrogenated nitrile rubber composition HD 10 The temperature is the lowest, indicating that its low-temperature deformation recovery ability is the best; in general, the brittle temperature and TR of the hydrogenated nitrile rubber composition H-BD 10 The temperature is very low, the brittle temperature of the hydrogenated nitrile rubber composition H-BD is basically close to the brittle temperature of the hydrogenated nitrile rubber composition HB, and the TR of the hydrogenated nitrile rubber composition H-BD is 10 The temperature is basically close to the TR of the hydrogenated nitrile rubber composition HD 10 temperature; therefore, the low-temperature impact resistance and low-temperature deformation recovery ability of the hydrogenated nitrile rubber composition H-BD are relatively excellent, and the softener B + D can effectively improve the low-temperature resistance of the HNBR rubber compound.

[0128] Table 5

[0129]

[0130] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for a person skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to replace some of the technical features therein by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions claimed to be protected by the present invention.

Claims

1. A high and low temperature resistant softener, characterized in that: The invention comprises the following components: adipic acid, alcohol ether, butanediol and a catalyst. The molar ratio of adipic acid, alcohol ether and butanediol is (0.5-3): (1-5): (0-3), The amount of catalyst used is 1-4% of the total component content. The alcohol ether includes at least one of diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether and ethylene glycol monomethyl ether.

2. The high and low temperature resistant softener according to claim 1, characterized in that: The molar ratio of adipic acid, alcohol ether and butanediol is (1-2.5):(1-3):(0-2).

3. The high and low temperature resistant softener according to claim 1, characterized in that: The catalyst comprises at least one of concentrated sulfuric acid, concentrated hydrochloric acid, p-toluenesulfonic acid, thionyl chloride and trifluoromethanesulfonic acid.

4. The high and low temperature resistant softener according to claim 1, characterized in that: The high and low temperature resistant softener has a number average molecular weight of 500-1500, a weight average molecular weight of 600-1800, and a molecular weight distribution greater than 1.

5. The high and low temperature resistant softener according to claim 1, characterized in that: The ether-ester bond content of the high and low temperature resistant softener is 10-25%, and the acid value of the high and low temperature resistant softener is 3-18%.

6. The method for preparing a high and low temperature resistant softener according to any one of claims 1 to 5, characterized in that: include (1) Add adipic acid, butanediol, alcohol ether and catalyst into the reactor, evacuate the reactor and heat the reactor to react; (2) After the reaction is completed, the reaction liquid is collected to obtain the softener.

7. The method for preparing the high and low temperature resistant softener according to claim 6, characterized in that: In the step (1), the vacuum degree is -0.02-0.08 MPa, the reaction temperature is 80-150° C., and the reaction time is 1-6 h.

8. Use of the high and low temperature resistant softener according to any one of claims 1 to 5 in preparing a rubber composition, characterized in that: The rubber composition comprises the following components in parts by weight: 100 parts by weight of raw rubber, 40-90 parts by weight of reinforcing agent, 15-30 parts by weight of softener, 1-3 parts by weight of antioxidant, 2-5 parts by weight of vulcanizing agent and 7-10 parts by weight of crosslinking agent.

9. Use of the high and low temperature resistant softener according to claim 8 in preparing a rubber composition, characterized in that: The preparation method of the rubber composition comprises: (1) The raw rubber is subjected to a first internal kneading, and then half of the reinforcing agent is added to perform a second internal kneading, and then half of the softening agent is added to perform a third internal kneading, and then the remaining half of the reinforcing agent is added to perform a fourth internal kneading, and then the remaining half of the softening agent is added to perform a fifth internal kneading to obtain internal kneaded rubber; (2) mixing the internal rubber, the vulcanizing agent and the cross-linking agent, and after mixing, performing thinning and discharging to obtain a mixed rubber; (3) The rubber mixture is vulcanized to obtain a rubber composition.

10. Use of the high and low temperature resistant softener according to claim 9 in preparing a rubber composition, characterized in that: In the step (1), the first banburying time is 1-5 minutes and the first banburying temperature is 60-80°C; the second banburying time is 1-5 minutes and the second banburying temperature is 80-90°C; the third banburying time is 1-5 minutes and the third banburying temperature is 90-100°C; the fourth banburying time is 1-5 minutes and the fourth banburying temperature is 100-110°C; the fifth banburying time is 1-5 minutes and the fifth banburying temperature is 110-130°C; In the step (2), the number of thin passes is 3-10 times, and after the rubber is discharged, the mixed rubber is left to cool for 8-20 hours; In the step (3), the vulcanization time is 0.5-5 min and the vulcanization temperature is 150-200°C.

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