A functional liquid rubber, a method for preparing the same and applications thereof

Abstract

The application discloses a kind of functional liquid rubber and its preparation method and application.The preparation method described in the application compared with prior art, the preparation method significantly improves yield and reduces preparation cost, can satisfy the demand of industrial production;The preparation method is by using polymerization regulator to regulate polymerization process, avoids crosslinking reaction, so that the molecular weight of the obtained polymer is kept in the range of thousands, and thiazole group is reasonably integrated in polymer molecule, and then can form co-vulcanization network with rubber matrix in subsequent process, and form coordination bond on the surface of inorganic filler, so as to improve the dispersity of inorganic filler and the interface interaction with rubber matrix.The application also uses the prepared functional liquid rubber to treat inorganic filler, uses it as rubber material filler, and the prepared rubber material has obvious advantages in tensile strength, tear strength, elongation at break and permanent compression deformation reduction.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high molecular materials, in particular to a functional liquid rubber, a preparation method and application thereof. BACKGROUND

[0002] In recent years, the performance requirements of rubber and plastic materials in modern industry are increasing. In order to enhance the mechanical properties and wear resistance, inorganic fillers are usually added to rubber and plastic materials. Commonly used inorganic fillers include kaolin, talc, clay, talc, white carbon black and mica. However, most of the inorganic fillers have a polar surface, while the rubber and plastic materials are usually non-polar and hydrophobic materials, and the compatibility between them is poor. In order to enhance the interfacial action between inorganic fillers and rubber and plastic matrix, the surface of the fillers needs to be modified by a suitable method. Surface modification of inorganic fillers is crucial to improve the performance of polymer composites.

[0003] The activity and properties of the surface of inorganic fillers are the basis of modification. The inventor's previous application of Chinese patent 2024205765.9 provides a preparation device for modifying inorganic fillers, which obtains a functional modifier containing thiazole by RAFT or traditional free radical polymerization of functional monomer containing thiazole group and isoprene. The inventor found in further research that the traditional free radical polymerization method has lower preparation cost and higher product yield, which is expected to be scaled up. SUMMARY

[0004] The purpose of the present application is to provide a functional liquid rubber.

[0005] Another purpose of the present application is to provide a preparation method of a functional liquid rubber.

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

[0007] To solve the above technical problems, the present application adopts the following technical solutions:

[0008] The present application provides a preparation method of a functional liquid rubber, characterized in that it comprises the following steps:

[0009] (1) dissolving the polymerization regulator and the monomer composition by free radical in an organic medium;

[0010] (2) after dissolving, adding an initiator to occur a polymerization reaction;

[0011] (3) after the reaction is completed, removing the unreacted reactants and the organic medium, and then treating the precipitate obtained by using a precipitant, washing and drying the precipitate to obtain the functional liquid rubber.

[0012] Further, the condition of the polymerization reaction is 125℃ for 10-24h.

[0013] Further, the monomer composition is 4-methyl-5-vinylthiazole and isoprene; the polymerization regulator is at least one of diisopropyl xanthate disulfide, 2-(dodecyltrithiocarbonate)-2-methylpropionic acid and alpha-methyl styrene dimer; the initiator is di-t-butyl peroxide; the organic medium is at least one of dichloromethane and 1,4-dioxane; and the precipitant is methanol.

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

[0015] Further, a rotary evaporator is used to remove the unreacted reactants and the organic medium.

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

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

[0018] Further, the molecular weight of the functional liquid rubber is less than 10000, and specifically 500-10000g / mol.

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

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

[0021] Further, 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 modified inorganic filler, and drying to obtain the modified inorganic filler.

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

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

[0024] Further, the drying treatment is vacuum drying treatment, and the vacuum drying treatment is carried out in a vacuum oven, and the temperature is 40-80°C, and the treatment time is 12-36h.

[0025] The application also provides a rubber material, raw materials of which include, by weight parts, rubber material filler 1-50 parts, rubber material 80-150 parts, zinc oxide 1-5 parts, stearic acid 0.1-5 parts, accelerator 0.1-5 parts, vulcanizing agent 1-5 parts.

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

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

[0028] (1) The application provides a new preparation method of poly(isoprene-4-methyl-5-vinylthiazole) functional liquid rubber, which greatly improves the yield and significantly reduces the preparation cost compared with the method in the prior art, and can adapt to the needs of industrial production.

[0029] (2) The application provides a preparation method of functional liquid rubber, which uses a polymerization regulator to regulate the polymerization process, avoids crosslinking reaction, keeps the molecular weight of the obtained polymer in the order of thousands, and reasonably integrates thiazole groups in the polymer molecules. This can form a co-vulcanization network with the rubber matrix in the subsequent process and form a coordination bond on the surface of the inorganic filler, thereby improving the dispersibility of the inorganic filler and the interfacial interaction with the rubber matrix.

[0030] (3) The application optimizes the types of time, monomer / solvent and polymerization regulator, improves the polymerization stability of the functional liquid rubber, and improves the yield.

[0031] (4) The inorganic filler treated by the functional liquid rubber provided by the application is used as a rubber material filler, and the modifier molecules on the surface can produce co-vulcanization with the rubber matrix, shorten the rubber vulcanization time, improve the dispersibility of the inorganic filler in the mixture and improve the interfacial compatibility with the rubber matrix. In addition, the inorganic filler treated by the functional liquid rubber of the application can form metal ligands with zinc oxide and other raw materials, which are beneficial to rubber vulcanization, and further promote the vulcanization reaction.

[0032] (5) The inorganic filler treated by the functional liquid rubber provided by the application is used as a rubber material filler, and the rubber material prepared has obvious advantages in tensile strength, tear strength, elongation at break and permanent compression set reduction. BRIEF DESCRIPTION OF DRAWINGS

[0033] One or more embodiments are illustrated by way of example in the accompanying drawings that are not intended to be limiting of the embodiments.

[0034] Figure 1GPC curves of poly(isoprene-4-methyl-5-vinylthiazole) samples 1 and 2 prepared in Example 1.

[0035] Figure 2 GPC curves of poly(isoprene-4-methyl-5-vinylthiazole) samples 3-5 prepared in Example 2.

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

[0037] Figure 4 GPC curves of poly(isoprene-4-methyl-5-vinylthiazole) samples 8-10 prepared in Example 2.

[0038] Figure 5 GPC curves of poly(isoprene-4-methyl-5-vinylthiazole) samples 11-13 prepared in Example 2.

[0039] Figure 6 GPC curves of poly(isoprene-4-methyl-5-vinylthiazole) samples 14-16 prepared in Example 2.

[0040] Figure 7 GPC curves of poly(isoprene-4-methyl-5-vinylthiazole) samples 17-19 prepared in Example 3.

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

[0042] Figure 9 GPC curves of poly(isoprene-4-methyl-5-vinylthiazole) samples 23-25 prepared in Example 5.

[0043] Figure 10 NMR hydrogen spectrum of poly(isoprene-4-methyl-5-vinylthiazole) samples 1 and 2 prepared in Example 1.

[0044] Figure 11 NMR hydrogen spectrum of poly(isoprene-4-methyl-5-vinylthiazole) samples 15 and 16 prepared in Example 2. DETAILED DESCRIPTION

[0045] In order to make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the present application will be further described below with specific examples. It should be understood that these examples are only used to illustrate but not limit the scope of the present application. The experimental methods in the following examples, if no specific conditions are noted, are generally according to the conventional conditions or the conditions suggested by the manufacturers. Unless otherwise specified, the percentages and parts are weight percentages and weight parts. The experimental materials and reagents used in the following examples, if no specifically mentioned, can be obtained from the commercial channels.

[0046] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. It is to be noted that, as used herein, the terminology of the application is used for the purpose of describing particular embodiments of the application, and is not intended to limit the example embodiments of the present application.

[0047] The term "or" as used herein means the term "and / or" and is used interchangeably therewith unless otherwise indicated.

[0048] As used herein, including the appended claims, the singular forms "a," "an," and "the" include their corresponding plural references 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 living radical polymerization, using 2-(dodecyltrithio carbonate)-2-methylpropionic acid (DDMAT) to control the polymerization, with the specific method as follows:

[0051] 1) According to Table 1, the weighed DDMAT was added in proportion, then 4-methyl-5-vinylthiazole (MVT) and isoprene (IP) were added, and 15 g of 1,4-dioxane was dissolved in a pressure-resistant bottle.

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

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

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

[0055] PIPMVT was analyzed using Waters 2595 Gel Permeation Chromatography (GPC) with standard PS as the calibration agent, tetrahydrofuran (THF) as the eluent, at a flow rate of 1.0 mL / min at 40 °C.

[0056] Table 1 Effect of DDMAT on polymerization

[0057] Group DDM AT / g IP / g MVT / g Initiator / g Yield / g Yield / % M n / Da]]> 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, the regulation of MVT by DDMAT can effectively avoid the crosslinking phenomenon and has a stable product yield. Figure 1 The GPC results of samples 1 and 2 show that the molecular weight dispersity of the polymerization product is small. Figure 10 The NMR results of samples 1 and 2 show that the sample preparation is successful and subsequent experiments can be carried out.

[0059] Example 2

[0060] In this example, a poly(isoprene-4-methyl-5-vinylthiazole) functional liquid rubber was prepared by a conventional free radical polymerization method as follows:

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

[0062] 2) The weighed initiator di-tert-butyl peroxide was added, and then the pressure-resistant bottle was sealed and placed in a 125 °C oil bath for polymerization for a certain time (24 h, 20 h, 10 h);

[0063] 3) After the reaction was completed, the pressure-resistant bottle was placed in an ice water bath to quickly cool to room temperature, 3 mL of dichloromethane was added to dissolve the polymerization product, and the unreacted monomer and solvent were removed by rotary evaporation. The solution after rotary evaporation at 40 °C was slowly added dropwise into 100 mL of methanol to produce precipitation, and the precipitation was repeatedly dissolved and precipitated 3 times.

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

[0065] Table 2 Effect of DIP on polymerization

[0066]

[0067]

[0068] As shown in Table 2, Figure 2 , 3The best time for the polymerization of IP and MVT is about 10h, and the GPC results show that the molecular weight of the polymerization product is controllable and the molecular weight dispersity is small, which is beneficial to the preparation, application and storage of the liquid rubber. The product has good fluidity and is not easy to crosslink. The DIP regulation of the polymerization of the liquid rubber containing pyridine can effectively avoid the crosslinking of the product and stabilize the yield of the polymer. Samples 14, 15 and 16 are the polymerization results of 5%, 10% and 20% molar ratio of MVT and IP, respectively. The nuclear magnetic results Figure 11 ) show that the mass fraction of MVT in samples 14, 15 and 16 is 7.1wt%, 12.1wt% and 20.6wt%, respectively.

[0069] Example 3

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

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

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

[0073] Table 3 Influence of AMSD on polymerization

[0074] Group Time / h AMSD / g IP / g MVT / g Initiator / g Yield / g Yield / g M n / Da]]> 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 the polymerization of MVT and IP regulated by AMSD can effectively avoid the occurrence of crosslinking phenomenon, and the yield of the product is higher; Figure 5 The GPC results of samples 17, 18 and 19 show that the molecular weight dispersity of the polymerization product is large.

[0076] Example 4

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

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

[0079] 2) Polymerization, precipitation and drying operations, i.e. steps 2) - 4) are consistent with 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 M n / Da]]> 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] As can be seen from Table 4, the use of dodecanethiol to regulate MVT and IP polymerization can effectively avoid the occurrence of crosslinking and stabilize the product yield. Figure 8 The GPC results for samples 20 and 22 show that the molecular weight dispersity of the polymerization product is large.

[0083] Example 5

[0084] In this example, the method for preparing the functional liquid rubber is substantially the same as in Example 2, i.e. 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, the weighed 4-methyl-5-vinylthiazole (MVT) and isoprene (IP) are added in proportion and dissolved in a pressure-resistant bottle with 7.5 g of 1,4-dioxane;

[0086] 2) Polymerization, precipitation and drying operations, i.e. steps 2) - 4) are consistent with Example 2.

[0087] Table 5 Effect of conventional free radical polymerization method

[0088] Group Time / h IP / g MVT / g Initiator / g Yield / g Yield / g M n / Da]]> 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] As can be seen from Table 5 and Figure 9 It can be seen that the conventional free radical polymerization method without adding a polymerization regulator can result in a polymer molecular weight much larger than the preset value, a wide molecular weight dispersity, and crosslinking.

[0090] As can be seen from Examples 1-5, DDMAT, DIP and AMSD can all effectively avoid crosslinking and stabilize the product yield. DIP and DDMAT, compared with AMSD, can help regulate the molecular weight of the polymerization product to be below 10,000 (k-level), have a narrow molecular weight distribution, and have a scale-up reaction yield of 50% or more.

[0091] Example 6

[0092] In this example, a ternary ethylene-propylene rubber reinforcing material is prepared. The specific steps are as follows:

[0093] (1) Preparation of modified talc powder

[0094] The poly(isoprene-4-methyl-5-vinylthiazole) functional liquid rubber sample 1 prepared in Example 1 was used to prepare a 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 uniformly sprayed on talc powder (5000 mesh, 250.000 g) by spraying. Then, it was dried at 55°C under normal pressure for 24 h, and then placed in a vacuum drying oven and dried at 50°C for 24 h to obtain modified talc powder.

[0096] (2) Preparation of a ternary ethylene-propylene rubber reinforcing material

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

[0098] The preparation method was as follows: the formula amount of ternary ethylene-propylene rubber, modified talc and talc were placed in an oven, and the oven temperature was set to 55°C; the temperature of the internal mixer was set to 130°C, and when the temperature of the internal mixer reached the preset temperature, the treated ternary ethylene-propylene rubber was plasticized for 8 min; the formula amount of various accelerators was mixed for 6 min; the temperature of the internal mixer was set to 80°C for discharge and cooling; the vulcanization accelerator and sulfur were mixed for 4 min, the front roller and rear roller temperatures of the open mill were set to 45°C, the roller gap was adjusted, and the rubber was thin-passed, and a triangular bag was made after 10 times of thin-passing to obtain the mixed rubber.

[0099] After the mixed rubber was placed for 24 h, it was vulcanized on a flat vulcanizing machine at a vulcanization temperature of 160°C according to t 90 time vulcanization; and a permanent compression set A type standard sample was prepared, with a height of 12.5 mm and a diameter of 29 mm.

[0100] Tensile property test: according to the GB / T 528-2009 standard, the test size of the dumbbell-shaped sample was 2x4x20 mm 3 , and the test speed was 500 mm / min.

[0101] Permanent compression set property: the compression permanent set property was tested according to the ASTM-395 standard. The sample was a type A sample, the compression rate was 25%, and the experimental conditions were 25°C for 2 h, 100°Cx68 h, and after 68 h, the clamp was opened, the sample was cooled for 0.5 h, and then the thickness was measured and the permanent compression set rate was calculated.

[0102] Table 6 vulcanization parameters and mechanical properties of the ethylene propylene diene rubber material

[0103]

[0104] Table 6 is the vulcanization parameters and mechanical properties of the ethylene propylene diene rubber material, the modified talcum powder can make the tensile strength of the ethylene propylene diene rubber material increase by 25.8% at most; the 100% modulus of elongation increases by 22% at most; the tear strength increases by 17.4% at most; the permanent compression set performance decreases by 51% at most, and the maximum deformation is kept below 3%.

[0105] Example 7

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

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

[0108] After the mixed rubber is placed for 24h, it is vulcanized on a flat vulcanizing machine, the vulcanization temperature is 170℃, and the vulcanization is carried out according to t 90 time.

[0109] Tensile property test: according to GB / T 528-2009 standard, the test size of dumbbell-shaped sample is 2x4x20mm 3 , the test speed is 500mm / min.

[0110] Table 7 butadiene styrene rubber vulcanization parameters and mechanical properties

[0111]

[0112]

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

[0114] Example 8

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

[0116] (1) Preparation of modified talc powder

[0117] The poly(isoprene-4-methyl-5-vinylthiazole) functional liquid rubber samples 15, 16 prepared in Example 2 are used to prepare functional liquid rubber for rubber. The specific operation is as follows: each (5.000 g) of sample 15, 16 is dissolved in dichloromethane (250.000 g), and the solution is uniformly sprayed on the talc powder (5000 mesh, 250.000 g) by spraying. Then dry at 55℃ under normal pressure for 24h, then put into vacuum drying oven, dry at 50℃ for 24h, get modified talc powder M1-T and M2-T.

[0118] (2) Preparation of butadiene rubber reinforced material

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

[0120] The preparation method is as follows: the formula amount of styrene butadiene rubber, modified talc and talc are put into an oven, the oven temperature is set to 55°C; the temperature of the internal mixer is set to 90°C, when the temperature of the internal mixer reaches the preset temperature, the treated styrene butadiene rubber is plasticized for 3 min; the temperature of the internal mixer is set to 110°C, the formula amount of zinc oxide and stearic acid is added and mixed for 13 min; the temperature of the internal mixer is set to 120°C, the filler talc or modified talc (M1-T or M2-T) is added and mixed for 15 min, the glue is discharged at 120°C and cooled, and the glue is parked for 24 h; the temperature of the internal mixer is set to 90°C, the vulcanization accelerator and sulfur are mixed for 20 min, the front roller and rear roller temperatures of the open mill are set to 45°C, the roller gap is adjusted, and the glue is added and thin passed, a triangular bag is made, and the mixed rubber is obtained after thin passing for 10 times.

[0121] After the mixed rubber is parked for 24 h, vulcanization is carried out on a flat vulcanization machine, the vulcanization temperature is 160°C, the vulcanization is carried out according to t 90 time vulcanization; and a permanent compression deformation A type standard sample is prepared, the height is 12.5 mm, and the diameter is 29 mm.

[0122] Tensile property test: according to the GB / T 528-2009 standard, the test size of the dumbbell-shaped sample is 2x4x20 mm 3 , the test speed is 500 mm / min.

[0123] Permanent compression deformation property: the compression permanent deformation property is tested according to the ASTM-395 standard. The sample is an A type sample, the compression rate is 25%, and the experimental conditions are 25°C for 2 h, 100°Cx22 h, after 22 h, the sample is taken out and the clamp is opened, the sample is cooled for 0.5 h, then the thickness is measured and the permanent compression deformation rate is calculated.

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

[0125]

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

[0127] Those skilled in the art can understand that the above-mentioned embodiments are specific examples for implementing the present application, and in actual application, various changes can be made in form and details without departing from the spirit and scope of the present application.

Claims

1. A method for producing a functional liquid rubber, characterized by, The method comprises the following steps: (1) dissolving the polymerization regulator and monomer composition by using an organic medium; (2) after dissolving, adding an initiator to initiate the polymerization reaction; (3) after the reaction, removing the unreacted reactants and organic medium, and then treating the obtained precipitate by using a precipitant, washing and drying the precipitate to obtain the functional liquid rubber; The monomer composition is 4-methyl-5-vinylthiazole and isoprene; The polymerization regulator is 2-(dodecyltrithiocarbonate)-2-methylpropionic acid (DDMAT); The initiator is di-t-butyl peroxide; The organic medium is 1,4-dioxane; The precipitant is methanol.

2. The production method according to claim 1, characterized by, The polymerization reaction is carried out at 125℃ for 10-24h.

3. The method of claim 1, wherein, The molar ratio of 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.

4. The functional liquid rubber prepared according to the production method of claim 1, characterized by, The molecular weight of the functional liquid rubber is 500-200000g / mol.

5. The functional liquid rubber of claim 4 is used for preparing a rubber material filler.

6. Use according to claim 5, 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 inorganic filler, and drying to obtain the modified inorganic filler.

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

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

3.

9. A reinforced rubber material, characterized by, The raw materials of the reinforced rubber material include, by weight, 1-50 parts of the rubber material filler of claim 6, 80-150 parts of a rubber material, 1-5 parts of zinc oxide, 0.1-5 parts of stearic acid, 0.1-5 parts of an accelerator, and 1-5 parts of a vulcanizing agent.

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