Functional liquid rubber as well as preparation method and application thereof

Abstract

The invention discloses functional liquid rubber as well as a preparation method and application thereof. Compared with the prior art, the preparation method disclosed by the invention has the advantages that the yield is remarkably improved, the preparation cost is reduced, and the requirements of industrial production can be met; according to the preparation method, a polymerization process is regulated and controlled by using a polymerization regulator, so that a cross-linking reaction is avoided, the molecular weight of the obtained polymer is kept in a thousand-level range, and thiazole groups are reasonably integrated in polymer molecules, so that a co-vulcanization network can be formed with a rubber matrix in a subsequent process, and coordinate bonds are formed on the surface of an inorganic filler; therefore, the dispersity of the inorganic filler and the interface interaction with the rubber matrix are improved. The prepared functional liquid rubber is used for treating an inorganic filler, the inorganic filler is used as a rubber material filler, and the prepared rubber material has remarkable advantages in the aspects of tensile strength, tear strength, elongation at break, reduction of permanent compression deformation and the like.

Description

Technical Field

[0001] The invention relates to the field of polymer materials, and in particular to a functional liquid rubber and a preparation method and application thereof. Background Art

[0002] In recent years, modern industry has increasingly higher requirements for the performance of rubber and plastic materials. In order to enhance their mechanical properties and wear resistance, inorganic fillers are usually added to rubber and plastic materials. Commonly used inorganic fillers include kaolin, talc, clay, brucite, white carbon black and mica. However, most inorganic fillers have polar surfaces, while rubber and plastic materials are usually non-polar and hydrophobic materials, and the compatibility between the two is poor. In order to enhance the interface between inorganic fillers and rubber and plastic matrices, it is necessary to use appropriate methods to modify the filler surface. Surface modification of inorganic fillers is crucial in improving the performance of polymer composites.

[0003] The activity and properties of the surface of inorganic fillers are the basis of modification. The Chinese patent 202420576519.3 previously applied by the inventor provides a preparation device for modified inorganic fillers, which obtains a thiazole-containing functional modifier by RAFT or traditional free radical polymerization of a thiazole-containing functional monomer and isoprene. In further research, the inventor found that the traditional free radical polymerization method has a low preparation cost and a high product yield, and is expected to be industrialized on a large scale. Summary of the invention

[0004] The object of the present invention is to provide a functional liquid rubber.

[0005] Another object of the present invention is to provide a method for preparing functional liquid rubber.

[0006] Another object of the present invention is to provide an application of the functional liquid rubber.

[0007] In order to solve the above technical problems, the present invention intends to adopt the following technical solutions:

[0008] The present invention provides a method for preparing a functional liquid rubber, which is characterized by comprising the following steps:

[0009] (1) dissolving the polymerization regulator and the monomer composition free radicals using an organic medium;

[0010] (2) After dissolution, an initiator is added to initiate a polymerization reaction;

[0011] (3) After the reaction is completed, unreacted reactants and organic medium are removed, and then a precipitant is used to obtain a precipitate, and the precipitate is washed and dried to obtain a functional liquid rubber.

[0012] Furthermore, the polymerization reaction conditions are 125° C. for 10-24 hours.

[0013] Furthermore, the monomer composition is 4-methyl-5-vinylthiazole and isoprene; the polymerization regulator is at least one of diisopropyl xanthate disulfide, 2-(dodecyl trithiocarbonate)-2-methylpropionic acid and α-methylstyrene dimer; the initiator is di-tert-butyl peroxide; the organic medium is at least one of dichloromethane and 1,4-dioxane; and the precipitant is methanol.

[0014] Furthermore, the molar ratio of the 4-methyl-5-vinylthiazole to isoprene is 5%-20%; and the mass ratio of the initiator to 4-methyl-5-vinylthiazole is 2:1-1:85.

[0015] Further, unreacted reactants and organic medium were removed using a rotary evaporator.

[0016] Furthermore, the drying is vacuum drying, and the conditions are vacuum drying at 40° C. for 12 hours.

[0017] The invention also provides functional liquid rubber prepared by the preparation method, the molecular weight of which is 500-20000 g / mol.

[0018] Furthermore, the molecular weight of the functional liquid rubber is lower than 10,000, specifically 500-10,000 g / mol.

[0019] Furthermore, the mass percentage of the thiazole structure in the functional liquid rubber is 5-30wt%.

[0020] The invention also provides application of the functional liquid rubber in preparing a rubber material filler.

[0021] Furthermore, the rubber material filler is a modified inorganic filler, and the preparation steps are: dissolving the functional liquid rubber in an organic solvent, spraying the solvent on the inorganic filler, and drying the solvent to obtain the modified inorganic filler.

[0022] Furthermore, the inorganic filler is at least one of mica powder, slag, kaolin, clay, white carbon black, talcum powder, hydrated magnesium carbonate, calcium magnesium carbonate, albite, calcium carbonate and montmorillonite.

[0023] Furthermore, the concentration of the functional liquid rubber is 0.5wt%-10wt% by mass; and the mass ratio of the functional liquid rubber to the inorganic filler is 3:1-1:3.

[0024] Furthermore, the drying treatment is a vacuum drying treatment, which is carried out in a vacuum oven at a temperature of 40-80° C. for a treatment time of 12-36 hours.

[0025] The present invention also provides a reinforced rubber material, whose raw materials include, by weight: 1-50 parts of rubber material filler, 80-150 parts of rubber material, 1-5 parts of zinc oxide, 0.1-5 parts of stearic acid, 0.1-5 parts of accelerator, and 1-5 parts of vulcanizer.

[0026] The rubber material is at least one of natural rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, nitrile rubber, EPDM rubber and styrene-butadiene-styrene.

[0027] Compared with the prior art, the present invention has the following advantages:

[0028] (1) The present invention provides a novel method for preparing poly(isoprene-4-methyl-5-vinylthiazole) functional liquid rubber, which greatly improves the yield and significantly reduces the preparation cost compared with the methods in the prior art, and can meet the needs of industrial production;

[0029] (2) The present invention provides a method for preparing a functional liquid rubber, which avoids cross-linking reaction by regulating the polymerization process using a polymerization regulator, so that the molecular weight of the obtained polymer is maintained in the thousand-level range, and the thiazole group is reasonably integrated into the polymer molecule. In this way, a co-vulcanization network can be formed with the rubber matrix in the subsequent process, and a coordination bond can be formed on the surface of the inorganic filler, thereby improving the dispersibility of the inorganic filler and the interface interaction with the rubber matrix.

[0030] (3) The present invention optimizes the time, monomer / solvent and polymerization regulator types to improve the polymerization stability and yield of the functional liquid rubber;

[0031] (4) The inorganic filler treated with the functional liquid rubber provided by the present invention is used as a filler for rubber materials. The surface modifier molecules can produce a co-vulcanization effect with the rubber matrix, shorten the rubber vulcanization time, improve the dispersion performance of the inorganic filler in the mixture and improve its interface compatibility with the rubber matrix. In addition, the inorganic filler treated with the functional liquid rubber of the present invention can form a metal ligand that is beneficial to rubber vulcanization with raw materials such as zinc oxide, further promoting the vulcanization reaction;

[0032] (5) The inorganic filler treated with the functional liquid rubber provided by the present invention is used as a filler for rubber materials. The rubber materials prepared have significant advantages in terms of tensile strength, tear strength, elongation at break and reduced permanent compression deformation. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] One or more embodiments are exemplarily described by the pictures in the corresponding drawings, and these exemplary descriptions do not constitute limitations on the embodiments.

[0034] Figure 1is the GPC curve of poly(isoprene-4-methyl-5-vinylthiazole) samples 1 and 2 prepared in Example 1;

[0035] Figure 2 is the GPC curve of poly(isoprene-4-methyl-5-vinylthiazole) sample 3-5 prepared in Example 2;

[0036] Figure 3 is the GPC curve of poly(isoprene-4-methyl-5-vinylthiazole) samples 6 and 7 prepared in Example 2;

[0037] Figure 4 is the GPC curve of poly(isoprene-4-methyl-5-vinylthiazole) samples 8-10 prepared in Example 2;

[0038] Figure 5 is the GPC curve of poly(isoprene-4-methyl-5-vinylthiazole) samples 11-13 prepared in Example 2;

[0039] Figure 6 is the GPC curve of poly(isoprene-4-methyl-5-vinylthiazole) samples 14-16 prepared in Example 2;

[0040] Figure 7 is the GPC curve of poly(isoprene-4-methyl-5-vinylthiazole) samples 17-19 prepared in Example 3;

[0041] Figure 8 are GPC curves of poly(isoprene-4-methyl-5-vinylthiazole) samples 20 and 22 prepared in Example 4;

[0042] Fig. 9 is the GPC curve of poly(isoprene-4-methyl-5-vinylthiazole) samples 23-25 ​​prepared in Example 5;

[0043] Fig.10 1 is the hydrogen nuclear magnetic resonance spectrum of poly(isoprene-4-methyl-5-vinylthiazole) samples 1 and 2 prepared in Example 1.

[0044] Fig.11 1 is the hydrogen nuclear magnetic resonance spectrum of poly(isoprene-4-methyl-5-vinylthiazole) samples 15 and 16 prepared in Example 2. DETAILED DESCRIPTION

[0045] To make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the present invention is further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples that do not specify specific conditions are usually based on conventional conditions or the conditions recommended by the manufacturer. Unless otherwise specified, percentages and parts are weight percentages and weight parts. The experimental materials and reagents used in the following examples can be obtained from commercial channels unless otherwise specified.

[0046] Unless otherwise specified, the technical and scientific terms used herein have the same meaning as commonly understood by ordinary technicians in the technical field to which the application belongs. It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments of the present application.

[0047] Unless otherwise indicated, the term "or" means and is used interchangeably with the term "and / or".

[0048] As used herein, including the appended claims, singular forms of words such as "a," "an," and "the" include their corresponding plural referents unless the context clearly dictates otherwise.

[0049] Example 1

[0050] In this embodiment, a poly(isoprene-4-methyl-5-vinylthiazole) functional liquid rubber was prepared by active free radicals, and 2-(dodecyl trithiocarbonate)-2-methylpropionic acid (DDMAT) was used to regulate the polymerization. The specific method is as follows:

[0051] 1) According to Table 1, add the weighed DDMAT in proportion, then add 4-methyl-5-vinylthiazole (MVT) and isoprene (IP), and take 15 g of 1,4-dioxane and dissolve it in a pressure bottle.

[0052] 2) After adding the weighed initiator di-tert-butyl peroxide, the pressure-resistant bottle was sealed and placed in an oil bath at 125°C for polymerization for 24 hours.

[0053] 3) After the reaction is completed, the pressure bottle is placed in an ice-water bath and quickly cooled to room temperature, 3 mL of dichloromethane is added to dissolve the polymer product, and the unreacted monomer and solvent are removed by rotary evaporation. The solution after rotary evaporation at 40°C is slowly added dropwise to 100 mL of methanol to produce a precipitate, and the precipitate is dissolved and precipitated three times.

[0054] 4) Finally, the precipitate was dried under vacuum at 40° C. for 6 h to obtain a viscous liquid product, namely poly(isoprene-4-methyl-5-vinylthiazole).

[0055] PIPMVT was analyzed using a Waters 2595 gel permeation chromatograph (GPC) using standard PS as a calibrant and tetrahydrofuran (THF) as an eluent at 40°C with a flow rate of 1.0 mL / min.

[0056] Table 1 Effect of DDMAT on polymerization

[0057] Group DDMAT / g IP / g MVT / g Initiator / g Yield / g Yield / % <![CDATA[M n / Yes]]> <![CDATA[M w / M n ]]> 1 0.36 10.00 1.75 0.03 5.00 43 8500 1.18 2 0.36 10.00 1.75 0.03 7.00 52 8100 1.36

[0058] As shown in Table 1, DDMAT can effectively avoid the cross-linking phenomenon in the polymerization of MVT and IP, and has a stable product yield. Figure 1 The GPC results of samples 1 and 2 show that the molecular weight dispersity of the polymer products is small. Fig.10 These are the NMR results of samples 1 and 2, indicating that the sample preparation has been successful and subsequent experiments can be carried out.

[0059] Example 2

[0060] In this embodiment, a poly(isoprene-4-methyl-5-vinylthiazole) functional liquid rubber is prepared, and the conventional free radical polymerization preparation method is as follows:

[0061] 1) According to Table 2, 4-methyl-5-vinylthiazole (MVT), isoprene (IP) and diisopropyl xanthate disulfide (DIP) were weighed in proportion and dissolved in a pressure bottle with 7.5 g of 1,4-dioxane;

[0062] 2) Add the weighed initiator di-tert-butyl peroxide, and then seal the pressure-resistant bottle and place it in a 125°C oil bath for polymerization for a certain period of time (24h, 20h, 10h);

[0063] 3) After the reaction is completed, the pressure bottle is placed in an ice-water bath and quickly cooled to room temperature, 3 mL of dichloromethane is added to dissolve the polymer product, and the unreacted monomers and solvent are removed by rotary evaporation. The solution after rotary evaporation at 40°C is slowly added dropwise to 100 mL of methanol to produce a precipitate, and the precipitate is dissolved and precipitated three times.

[0064] 4) Finally, the precipitate was dried under vacuum at 40° C. for 12 h to obtain a viscous liquid product, namely poly(isoprene-4-methyl-5-vinylthiazole).

[0065] Table 2 Effect of DIP on polymerization

[0066]

[0067]

[0068] From Table 2, Figure 2 , 3From 4, it can be seen that the optimal time for the polymerization of IP and MVT is about 10h. The GPC results at this time show that the molecular weight of the polymerization product is controllable and the molecular weight dispersion is small, which is conducive to the preparation, application and storage of liquid rubber. The product has good fluidity and is not easy to cross-link. DIP regulation of the polymerization of pyridine-containing liquid rubber can effectively avoid the occurrence of product cross-linking, and the yield of the polymer is stable. Samples 14, 15 and 16 are the polymerization results of MVT and IP molar ratios of 5%, 10% and 20%, respectively. NMR results ( Fig.11 ) show that the mass fractions of MVT in samples 14, 15 and 16 are 7.1wt%, 12.1wt% and 20.6wt%, respectively.

[0069] Example 3

[0070] In this embodiment, the method for preparing the functional liquid rubber is substantially the same as that in Embodiment 2, except that α-methylstyrene dimer (AMSD) is used to regulate the free radical polymerization of the poly(isoprene-4-methyl-5-vinylthiazole) functional liquid rubber. The specific method is as follows:

[0071] 1) According to Table 3, weighed AMSD was added in proportion, and then 4-methyl-5-vinylthiazole (MVT) and isoprene (IP) were added, and the mixture was dissolved in a pressure bottle with 7.5 g of 1,4-dioxane;

[0072] 2) The polymerization, precipitation and drying operations, i.e. steps 2) to 4) are consistent with those of Example 2.

[0073] Table 3 Effect of AMSD on aggregation

[0074] Group Time / h AMSD / g IP / g MVT / g Initiator / g Yield / g Yield / g <![CDATA[M n / Yes]]> <![CDATA[M w / M n ]]> 17 20 0.59 2.50 0.23 0.18 2.56 94 8800 2.42 18 20 0.59 2.50 0.46 0.18 2.92 98 10000 5.24 19 20 0.59 2.50 0.92 0.18 3.06 89 10000 3.35

[0075] From the results in Table 3, it can be seen that AMSD regulation of MVT and IP polymerization can effectively avoid the occurrence of cross-linking, and the product yield is high; Figure 5 The GPC results of samples 17, 18 and 19 show that the molecular weight dispersion of the polymer products is large.

[0076] Example 4

[0077] In this embodiment, the method for preparing the functional liquid rubber is substantially the same as that in Embodiment 2, except that dodecanethiol is used to regulate the free radical polymerization of the poly(isoprene-4-methyl-5-vinylthiazole) functional liquid rubber. The specific method is as follows:

[0078] 1) According to Table 4, weighed dodecanethiol was added in proportion, and then 4-methyl-5-vinylthiazole (MVT) and isoprene (IP) were added, and the mixture was dissolved in a pressure bottle with 7.5 g of 1,4-dioxane;

[0079] 2) The polymerization, precipitation and drying operations, i.e. steps 2) to 4) are consistent with those of Example 2.

[0080] Table 4 Effect of dodecanethiol on polymerization

[0081] Group Time / h Dodecanethiol / g IP / g MVT / g Initiator / g Yield / g Yield / g <![CDATA[M n / Yes]]> <![CDATA[M w / M n ]]> 20 24 0.50 2.50 0.23 0.36 3.05 94 4300 4.44 21 24 0.50 2.50 0.46 0.36 2.84 82 5500 3.56 22 24 0.50 2.50 0.94 0.36 2.85 72 6700 11.45

[0082] It can be seen from Table 4 that the polymerization of MVT and IP regulated by dodecanethiol can effectively avoid the occurrence of cross-linking and has a stable product yield. Figure 8 The GPC results of samples 20 and 22 show that the molecular weight dispersion of the polymer products is large.

[0083] Example 5

[0084] In this embodiment, the method for preparing the functional liquid rubber is substantially the same as that in embodiment 2, that is, conventional free radical polymerization of poly(isoprene-4-methyl-5-vinylthiazole) functional liquid rubber. The specific method is as follows:

[0085] 1) According to Table 5, weighed 4-methyl-5-vinylthiazole (MVT) and isoprene (IP) were added in proportion, and dissolved in a pressure bottle with 7.5 g of 1,4-dioxane;

[0086] 2) The polymerization, precipitation and drying operations, i.e. steps 2) to 4) are consistent with those of Example 2.

[0087] Table 5 Effect of traditional free radical polymerization

[0088] Group Time / h IP / g MVT / g Initiator / g Yield / g Yield / g <![CDATA[M n / Yes]]> <![CDATA[M w / M n ]]> 23 24 5.00 0.46 0.073 3.50 64 20000 4.74 24 24 5.00 0.92 0.073 5.70 97 19000 4.00 25 24 5.00 1.84 0.073 4.20 56 16000 2.67

[0089] From Table 5 and Fig. 9 It can be seen that the traditional free radical polymerization method without adding a polymerization regulator will make the polymer molecular weight much greater than the preset value, the molecular weight dispersion is wide, and cross-linking occurs.

[0090] As can be seen from Examples 1-5, DDMAT, DIP and AMSD can effectively avoid cross-linking and stabilize the product yield. Compared with AMSD, DIP and DDMAT are helpful in regulating the molecular weight of the polymer product to a level below 10,000 (thousands), and the molecular weight distribution is narrow, and the amplification reaction yield reaches 50% or more.

[0091] Example 6

[0092] In this embodiment, an EPDM rubber reinforced material is prepared. The specific steps are as follows:

[0093] (1) Preparation of modified talc

[0094] The poly(isoprene-4-methyl-5-vinylthiazole) functional liquid rubber sample 1 prepared in Example 1 was used to prepare functional liquid rubber for rubber. The specific operation was as follows:

[0095] Sample 1 (5.000 g) was dissolved in dichloromethane (250.000 g), and the solution was evenly sprayed on talcum powder (5000 mesh, 250.000 g) by spraying. Then, it was dried at 55° C. for 24 h under normal pressure, placed in a vacuum drying oven, and dried at 50° C. for 24 h to obtain modified talcum powder.

[0096] (2) Preparation of EPDM rubber reinforced materials

[0097] The modified talc powder prepared in step (1) is used to reinforce EPDM rubber materials. The specific operation is as follows: according to weight parts: 100 parts of EPDM rubber, 5 parts of zinc oxide, 1 part of zinc stearate, 2.4 parts of BIPB, 1 part of TAIC, 30 parts of paraffin oil, 0.16 parts of sulfur, 0 parts of talc powder or functional modified talc powder (PM1-Talc), 10 parts, 20 parts, 30 parts and 50 parts respectively, and the raw materials are dried in an oven at 55°C for 2 hours before use.

[0098] The preparation method is as follows: put the formulated amount of EPDM rubber, modified talcum powder and talcum powder into an oven, and set the oven temperature to 55°C; set the temperature of the internal mixer to 130°C, and when the temperature of the internal mixer reaches the preset temperature, add the treated EPDM rubber and plasticize for 8 minutes; add various accelerators in the formulated amount and mix for 6 minutes; set the temperature of the internal mixer to 80°C for rubber discharge and cooling; add vulcanization accelerator and sulfur and mix for 4 minutes, set the temperature of the front roller and the rear roller of the mixer to 45°C, adjust the roller distance and add the rubber to pass it thinly, make a triangle bag, and pass it thinly 10 times to obtain the mixed rubber.

[0099] After the rubber mixture was left standing for 24 hours, it was vulcanized on a flat vulcanizer at a vulcanization temperature of 160°C. 90 vulcanization time; and prepare permanent compression deformation type A standard sample, height: 12.5mm, diameter: 29mm.

[0100] Tensile performance test: According to GB / T 528-2009 standard, the test size of dumbbell specimen is 2×4×20mm 3 , the test speed is 500mm / min.

[0101] Permanent compression set performance: The compression set performance was tested according to ASTM-395 standard. The specimen was type A, with a compression rate of 25%. The experimental conditions were 25°C for 2 hours, 100°C for 68 hours, and after 68 hours, the specimen was taken out and the fixture was opened. The specimen was cooled for 0.5 hours, and then the thickness was measured and the permanent compression set rate was calculated.

[0102] Table 6 Vulcanization parameters and mechanical properties of EPDM rubber materials

[0103]

[0104] Table 6 shows the vulcanization parameters and mechanical properties of EPDM rubber materials. Modified talcum powder can increase the tensile strength of EPDM rubber materials by up to 25.8%; 100% elongation stress can be increased by up to 22%; tear strength can be increased by up to 17.4%; permanent compression deformation performance can be reduced by up to 51%, and the maximum deformation can be kept below 3%.

[0105] Example 7

[0106] In this embodiment, a styrene-butadiene rubber reinforcement material was prepared, and poly(isoprene-4-methyl-5-vinylthiazole) functional liquid rubber was used to reinforce the styrene-butadiene rubber material. The specific method is as follows:

[0107] According to weight parts: 100 parts of styrene-butadiene rubber SBR, 3 parts of zinc oxide, 1 part of stearic acid, 1.2 parts of accelerator (DM), 1.75 parts of sulfur, 50 parts of 5000 mesh talc and 50 parts of kaolin, and 2 parts of the liquid rubber sample 13 prepared in Example 2 (the functional liquid rubber is applied by dissolving the liquid rubber and spraying). The raw materials in the formula are put into a KY-3220C-0.5L type internal mixer for internal mixing. After the internal mixing is completed, the rubber is placed on an open mill and thinned 15 times to obtain a mixed rubber.

[0108] After the mixed rubber was left for 24 hours, it was vulcanized on a flat vulcanizer at a vulcanization temperature of 170°C. 90 Time vulcanization.

[0109] Tensile performance test: According to GB / T 528-2009 standard, the test size of dumbbell specimen is 2×4×20mm 3 , the test speed is 500mm / min.

[0110] Table 7 Vulcanization parameters and mechanical properties of styrene-butadiene rubber

[0111]

[0112]

[0113] Table 7 shows the vulcanization parameters and mechanical properties of styrene-butadiene rubber. The modified talc added to sample 13 can accelerate the vulcanization rate of styrene-butadiene rubber by 28.5%, and the tensile strength can be increased by 58.8%; the 100% and 300% elongation stress can be increased by 9% and 10% respectively; the elongation at break is increased to 790%; and the tear strength can be increased by 19.6% at most. The modified kaolin added to sample 13 can accelerate the vulcanization rate of styrene-butadiene rubber by 12.7%, and the tensile strength can be increased by 28.2%; the 100% and 300% elongation stress can be increased by 6% and 14.2% respectively; and the elongation at break is increased by 24.8%.

[0114] Example 8

[0115] In this embodiment, a styrene-butadiene rubber reinforced material is prepared.

[0116] (1) Preparation of modified talc

[0117] The poly(isoprene-4-methyl-5-vinylthiazole) functional liquid rubber samples 15 and 16 prepared in Example 2 were used to prepare functional liquid rubber for rubber. The specific operation was as follows: each sample 15 and 16 (5.000 g) was dissolved in dichloromethane (250.000 g), and the solution was evenly sprayed on talcum powder (5000 mesh, 250.000 g) by spraying. Then, it was dried at 55°C for 24 hours under normal pressure, and then placed in a vacuum drying oven and dried at 50°C for 24 hours to obtain modified talcum powder M1-T and M2-T.

[0118] (2) Preparation of styrene-butadiene rubber reinforced materials

[0119] The modified talc powder prepared in step (1) is used to reinforce styrene-butadiene rubber materials. The specific operation is as follows: according to weight parts: 100 parts of styrene-butadiene rubber SBR, 3 parts of zinc oxide, 1 part of stearic acid, 1.2 parts of accelerator DM, 1.75 parts of sulfur, 0 parts, 10 parts, 20 parts, 30 parts and 50 parts of talc powder or functional modified talc powder (M1-T and M2-T), respectively, and the raw materials are dried in an oven at 55°C for 2 hours before use.

[0120] The preparation method is as follows: put the formulated amount of styrene-butadiene rubber, modified talcum powder and talcum powder into an oven, and set the oven temperature to 55°C; set the temperature of the internal mixer to 90°C, and when the temperature of the internal mixer reaches the preset temperature, add the treated styrene-butadiene rubber and plasticize for 3 minutes; set the temperature of the internal mixer to 110°C, add the formulated amount of zinc oxide and stearic acid and mix for 13 minutes; set the temperature of the internal mixer to 120°C, add filler talcum powder or modified talcum powder (M1-T or M2-T) and mix for 15 minutes, discharge the rubber at 120°C and cool, and park for 24 hours; set the temperature of the internal mixer to 90°C, add vulcanization accelerator and sulfur and mix for 20 minutes, set the temperature of the front roller and the rear roller of the open mixer to 45°C, adjust the roller distance and add the rubber to thinly pass, make a triangle bag, and obtain the mixed rubber after thinly passing 10 times.

[0121] After the rubber mixture was left standing for 24 hours, it was vulcanized on a flat vulcanizer at a vulcanization temperature of 160°C. 90 vulcanization time; and prepare permanent compression deformation type A standard sample, height: 12.5mm, diameter: 29mm.

[0122] Tensile performance test: According to GB / T 528-2009 standard, the test size of dumbbell specimen is 2×4×20mm 3 , the test speed is 500mm / min.

[0123] Permanent compression deformation performance: The compression deformation performance was tested according to ASTM-395 standard. The specimen was type A specimen, the compression rate was 25%, and the experimental conditions were 25℃ for 2h, 100℃×22h, and after 22h, the specimen was taken out and the fixture was opened. The thickness was measured and the permanent compression deformation rate was calculated after the specimen was cooled for 0.5h.

[0124] Table 8 Vulcanization parameters and mechanical properties of styrene-butadiene rubber materials

[0125]

[0126] Table 8 shows the vulcanization parameters and mechanical properties of styrene-butadiene rubber. The modified talc added to samples 15 and 16 can accelerate the vulcanization rate of styrene-butadiene rubber materials by 35.6%, and increase the tensile strength by 78.1%. The 100% and 300% elongation stresses are increased by 35% and 21.8% respectively; the elongation at break is increased to 930%; the tear strength is increased by 13.8% at most: the deformation rates of SBR / M1-T and SBR / M2-T composite materials are reduced by 18.4% and 24.4% at most compared with SBR / T.

[0127] Those skilled in the art will appreciate that the above-mentioned embodiments are specific examples for implementing the present invention, and in actual applications, various changes may be made thereto in form and detail without departing from the spirit and scope of the present invention.

Claims

1. A method for preparing a functional liquid rubber, characterized in that: The following steps are involved: (1) dissolving the polymerization regulator and the monomer composition free radicals using an organic medium; (2) After dissolution, an initiator is added to initiate a polymerization reaction; (3) After the reaction is completed, unreacted reactants and organic medium are removed, and then a precipitant is used to obtain a precipitate, and the precipitate is washed and dried to obtain a functional liquid rubber.

2. The preparation method according to claim 1, characterized in that: The polymerization reaction conditions are 125° C. for 10-24 hours.

3. The preparation method according to claim 1, characterized in that: The monomer composition is 4-methyl-5-vinylthiazole and isoprene; the polymerization regulator is at least one of diisopropyl xanthate disulfide, 2-(dodecyl trithiocarbonate)-2-methylpropionic acid and α-methylstyrene dimer; the initiator is di-tert-butyl peroxide; the organic medium is at least one of dichloromethane and 1,4-dioxane; and the precipitant is methanol.

4. The preparation method according to claim 1, characterized in that: The molar ratio of the 4-methyl-5-vinylthiazole to isoprene is 5%-20%; the mass ratio of the initiator to 4-methyl-5-vinylthiazole is 2:1-1:

85.

5. The functional liquid rubber prepared by the preparation method according to any one of claims 1 to 4, characterized in that: The molecular weight of the functional liquid rubber is 500-200000 g / mol.

6. Use of the functional liquid rubber according to claim 5 in preparing a rubber material filler.

7. The use according to claim 6, characterized in that: The rubber material filler is a modified inorganic filler, and the preparation steps are as follows: dissolving the functional liquid rubber in an organic solvent, spraying the solvent on the inorganic filler, and drying the solvent to obtain the modified inorganic filler.

8. The use according to claim 6, characterized in that: The inorganic filler is at least one of mica powder, slag, kaolin, clay, white carbon black, talcum powder, hydrated magnesium carbonate, calcium magnesium carbonate, albite, calcium carbonate and montmorillonite.

9. The use according to claim 6, characterized in that: The concentration mass percentage of the functional liquid rubber is 0.5wt%-10wt%; the mass ratio of the functional liquid rubber to the inorganic filler is 3:1-1:

3.

10. A reinforced rubber material, characterized in that: In parts by weight, the raw materials of the reinforced rubber material include: 1-50 parts of the rubber material filler according to claim 6, 80-150 parts of rubber material, 1-5 parts of zinc oxide, 0.1-5 parts of stearic acid, 0.1-5 parts of accelerator, and 1-5 parts of vulcanizer.

Images