A pre-dispersed rubber tackifier, its preparation method and application

Abstract

The present application relates to a predispersed rubber tackifier, a preparation method and an application thereof. The predispersed rubber tackifier is prepared from the following components in parts by weight: 18-21 parts of a reinforcing material, 5-8 parts of wollastonite, 2-3 parts of diatomaceous earth, 1-2 parts of an amino silicone resin or an amino siloxane, 0.08-0.15 parts of triethylamine, and 65-75 parts of coumarone resin; the reinforcing material is selected from at least one of silica and hydrotalcite. The predispersed rubber tackifier is in powder form, which is convenient to weigh, and is more easily dispersed uniformly in rubber than the solid block or liquid in the prior art. In addition, through the reasonable selection and compounding of auxiliary materials such as the reinforcing material, wollastonite, diatomaceous earth, and maleic anhydride-modified amino siloxane, the predispersed rubber tackifier has a low mercaptan content, is not easy to agglomerate, and has good light stability. The sole prepared by using the predispersed rubber tackifier has good wear resistance, folding resistance and tensile properties.

Description

Technical Field

[0001] The present application relates to the technical field of rubber additive materials, and in particular, to a pre-dispersed rubber tackifier and its preparation method and application. Background Art

[0002] The tackifying resin is one of the essential tackifying compounding materials in the production of rubber products and tires. Generally speaking, natural series resins include rosin and its derivatives, etc. Although natural series resins are natural and environmentally friendly, they have strong reaction activity and are unstable under the conditions of light, heat, and oxygen, showing poor aging resistance, poor weather resistance, and easy discoloration and other phenomena. Therefore, synthetic series resins such as coumarone resin are often used to improve the adhesion of rubber. When coumarone resin is added to rubber, it can play roles such as softening, reinforcing, tackifying, and dispersing, thereby improving the processing performance of rubber and being widely used in industries such as rubber tires, V-belts, conveyor belts, and rubber hoses.

[0003] However, the current coumarone resin is generally a solid block or liquid in black, dark brown, or light yellow, which is extremely inconvenient for weighing and also has a certain impact on its dispersibility in rubber. Summary of the Invention

[0004] Aiming at the deficiencies of the existing technology, in the first aspect of the present application, the present application provides a pre-dispersed rubber tackifier, which is prepared from components including the following parts by weight: 18 - 21 parts of reinforcing material, 5 - 8 parts of wollastonite, 2 - 3 parts of diatomaceous earth, 1 - 2 parts of amino silicone resin or amino siloxane, 0.08 - 0.15 parts of triethylamine, 65 - 75 parts of coumarone resin; the reinforcing material is selected from at least one of silica and hydrotalcite.

[0005] In a specific embodiment, the amino siloxane is 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, with the CAS number 2469-55-8, and the structural formula is as shown in Formula 1:

[0006]

[0007] In a specific embodiment, the reinforcing material can be 18 - 20 parts, 20 - 21 parts.

[0008] In a specific embodiment, the reinforcing material can be 18 parts, 18.5 parts, 19 parts, 19.5 parts, 20 parts, 20.5 parts, 21 parts.

[0009] In a specific embodiment, the wollastonite can be 5 - 6 parts, 6 - 8 parts.

[0010] In a specific embodiment, the wollastonite can be 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts.

[0011] In a specific embodiment, the diatomaceous earth can be 2 - 2.5 parts, 2.5 - 3 parts.

[0012] In a specific embodiment, the diatomaceous earth can be 2 parts, 2.3 parts, 2.5 parts, 2.8 parts, 3 parts.

[0013] In a specific embodiment, the aminosiloxane can be 1 - 1.4 parts, 1.4 - 2 parts.

[0014] In a specific embodiment, the aminosiloxane can be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts.

[0015] In a specific embodiment, the triethylamine can be 0.08 - 0.1 parts, 0.1 - 0.15 parts.

[0016] In a specific embodiment, the triethylamine can be 0.08 parts, 0.09 parts, 0.1 parts, 0.12 parts, 0.14 parts, 0.15 parts.

[0017] In a specific embodiment, the coumarone resin can be 65 - 70 parts, 70 - 75 parts.

[0018] In a specific embodiment, the coumarone resin can be 65 parts, 68 parts, 70 parts, 72 parts, 73 parts, 75 parts.

[0019] In this application, by adjusting the ratio of each component in the raw materials for preparing the pre - dispersed rubber tackifier and controlling the weight parts of each component within the above - mentioned range, a pre - dispersed rubber tackifier with a mercaptan content of less than 20 ppm and a non - caking days of more than 50 days under visible light irradiation conditions is obtained. When this pre - dispersed rubber tackifier is used to prepare a sole with natural rubber, the abrasion scar length of the sole is less than 5.5 mm, the flexural strength is less than 8 mm, the tensile strength is more than 15 MPa, and after aging, the tensile strength decline rate is less than 25%.

[0020] In one or more embodiments of this application, the weight ratio of the coumarone resin to the aminosiloxane is (35 - 70):1; the weight ratio of the reinforcing material, wollastonite to diatomaceous earth is (21 - 27):(5 - 12):3.

[0021] In a specific embodiment, the weight ratio of the coumarone resin to the aminosiloxane can be (35 - 47):1, (46 - 70):1.

[0022] In a specific embodiment, the weight ratio of the coumarone resin to the amino silicone can be 35:1, 38:1, 40:1, 45:1, 46:1, 46.4:1, 47:1, 50:1, 60:1, 65:1, 70:1.

[0023] In a specific embodiment, the weight ratio of the reinforcing material, wollastonite and diatomaceous earth can be (8 - 9):(2.4 - 4):1, (7 - 8):(1.6 - 2.4):1.

[0024] In a specific embodiment, the weight ratio of the reinforcing material, wollastonite and diatomaceous earth can be 9:4:1, 8:2.4:1, 7:1.67:1, 8.5:3:1, 7.5:1.8:1.

[0025] In one or more embodiments of the present application, the reinforcing material is composed of silica and hydrotalcite in a weight ratio of (2.3 - 4):1.

[0026] In a specific embodiment, the weight ratio of the silica to the hydrotalcite in the reinforcing material can be (2.3 - 3):1, (3 - 4):1.

[0027] In a specific embodiment, the weight ratio of the silica to the hydrotalcite in the reinforcing material can be 2.3:1, 3:1, 4:1, 2.5:1, 2.8:1, 3.5:1, 3.3:1.

[0028] Through the above technical solutions, a pre-dispersed rubber tackifier with a mercaptan content of less than 16 ppm and a non-caking days of more than 75 days under visible light irradiation conditions is obtained. The pre-dispersed rubber tackifier and natural rubber are prepared into a sole, and the abrasion mark length of the sole is less than 4.5 mm, the flexural strength is less than 7.5 mm, the tensile strength is more than 17.5 MPa, and after aging, the tensile strength decline rate is less than 19%.

[0029] In one or more embodiments of the present application, the hydrotalcite is selected from at least one of magnesium-aluminum hydrotalcite, cobalt-aluminum hydrotalcite, cobalt-iron hydrotalcite, calcium-aluminum hydrotalcite, zinc-aluminum hydrotalcite. Preferably, the hydrotalcite is prepared by a coprecipitation method or a hydrothermal method.

[0030] In one or more embodiments of the present application, the hydrotalcite is an acid anhydride-modified hydrotalcite, and the preparation method of the acid anhydride-modified hydrotalcite includes: dispersing the hydrotalcite in an organic solvent, adding maleic anhydride-modified polybutadiene and p-toluenesulfonic acid, reacting, and removing the solvent to obtain the acid anhydride-modified hydrotalcite.

[0031] Through the above technical solutions, a pre-dispersed rubber tackifier with a mercaptan content of less than 10 ppm and a non-caking days of more than 100 days under visible light irradiation conditions is obtained. The pre-dispersed rubber tackifier and natural rubber are made into a sole, and the abrasion mark length of the sole is less than 3.5 mm, the flex resistance strength is less than 6.5 mm, the tensile strength is more than 18.5 MPa, and after aging, the tensile strength decrease rate is less than 12.5%.

[0032] In one or more embodiments of the present application, the particle size of the precipitated silica is 800 - 1200 mesh.

[0033] In a specific embodiment, the particle size of the precipitated silica can be 800 - 1000 mesh, 1000 - 1200 mesh.

[0034] In a specific embodiment, the particle size of the precipitated silica can be 800 mesh, 900 mesh, 1000 mesh, 1100 mesh, 1200 mesh.

[0035] In one or more embodiments of the present application, the wollastonite is acicular wollastonite powder with an aspect ratio of 15:1.

[0036] In one or more embodiments of the present application, the amino silicone is maleic anhydride-modified amino silicone. The preparation method of the maleic anhydride-modified amino silicone includes: acylating reaction of amino silicone and maleic anhydride in a solvent, and then adding an acid catalyst for cyclodehydration reaction to obtain the maleic anhydride-modified amino silicone; the solvent is N,N-dimethylformamide, and the acid catalyst is phosphotungstic acid. Through the above technical solutions, a pre-dispersed rubber tackifier with a mercaptan content of less than 5 ppm and a non-caking days of more than 110 days under visible light irradiation conditions is obtained. The pre-dispersed rubber tackifier and natural rubber are made into a sole, and the abrasion mark length of the sole is less than 3.5 mm, the flex resistance strength is 6.0 mm and below, the tensile strength is more than 19 MPa, and after aging, the tensile strength decrease rate is less than 11%.

[0037] In the second aspect of the present application, the present application provides a preparation method of the pre-dispersed rubber tackifier described in the first aspect of the present application, including the following steps:

[0038] 1) Mix the reinforcing material, wollastonite, and diatomaceous earth, and add amino silicone and triethylamine to obtain a composite pre-dispersed carrier;

[0039] 2) Heat-treat the coumarone resin, atomize it and uniformly spray it into the composite pre-dispersed carrier obtained in step 1) to obtain the pre-dispersed rubber tackifier.

[0040] In one or more embodiments of the present application, in step 1), the mixing includes uniformly mixing the reinforcing material and diatomaceous earth, and then adding wollastonite and mixing uniformly.

[0041] Through the above technical solution, a pre-dispersed rubber tackifier with a mercaptan content of less than 5 ppm and a non-caking days of more than 115 days is obtained. The pre-dispersed rubber tackifier and natural rubber are prepared into a sole. The abrasion mark length of the sole is 3.0 mm or less, the flex resistance strength is 5.5 mm or less, the tensile strength is more than 19.5 MPa, and after aging, the tensile strength decline rate is less than 8%. In one or more embodiments of the present application, in step 2), the temperature of the heat treatment is controlled at 50-60 °C.

[0042] In the third aspect of the present invention, the present invention provides an application of the pre-dispersed rubber tackifier described in the first aspect of the present invention in the preparation of sole materials.

[0043] In one or more embodiments of the present application, the sole is prepared from the following raw materials: 100 parts by weight of natural rubber, 56.25 parts by weight of carbon black, 1 part by weight of accelerator, 2 parts by weight of vulcanizing agent, 10 parts by weight of aromatic oil, 5 parts by weight of zinc oxide, 1.25 parts by weight of stearic acid, 2 parts by weight of antioxidant A, 1 part by weight of paraffin wax, and 12.5 parts by weight of the above-mentioned pre-dispersed rubber tackifier.

[0044] The preparation method of the sole includes:

[0045] Mixing: Add the sole raw materials except the vulcanizing agent and accelerator to a mixer for mixing to obtain masterbatch, cool it, and open it on a two-roll mill. First, thin-pass the masterbatch 3 times, and the masterbatch wraps around the roll. After the rubber layer is smooth, add the vulcanizing agent and accelerator respectively, thin-pass 5 times, and mix evenly to obtain a blank sheet;

[0046] Hot pressing and forming: Discharge the blank sheet obtained by mixing into a film press, slice it according to the sole size after extrusion and vulcanization by the mold; Forming: Cut the cut blank sheet into a sole in a sole molding machine.

[0047] In summary, the present application includes the following beneficial technical effects:

[0048] 1. The present application provides a pre-dispersed rubber tackifier. The pre-dispersed rubber tackifier is in powder form, which is convenient to weigh and is easier to disperse uniformly in rubber than solid blocks or liquids in the prior art, solving many problems such as inconvenient and inaccurate weighing of the liquid tackifier coumarone resin, inaccurate feeding during use, and pollution to the environment and human body. In addition, through the reasonable selection and compounding of auxiliary materials such as reinforcing materials, wollastonite, diatomaceous earth, and maleic anhydride-modified amino silicone, the pre-dispersed rubber tackifier has a low mercaptan content, a small odor, is not easy to cake, and has good light stability.

[0049] 2. The present application also provides a preparation method of the above-mentioned pre-dispersed rubber tackifier, and its preparation method is simple and easy for industrial production.

[0050] 3. The present application also provides the application of the above-mentioned pre-dispersed rubber tackifier in the preparation of sole materials, and the soles prepared therefrom have good wear resistance, folding resistance and tensile properties. Description of the Drawings

[0051] Figure 1 It is a flow chart for preparing the pre-dispersed rubber tackifier of the present application. Detailed Description of the Embodiments

[0052] The present application will be further described in detail below with reference to the embodiments. The following embodiments are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. For those conditions not specified in the following embodiments, they are carried out according to the conventional conditions or the conditions recommended by the manufacturer. For the methods used, unless otherwise specified, they are all conventional methods well known in the art. For the consumables and reagents used, unless otherwise specified, they are all commercially available. Unless otherwise stated, the professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art. In addition, any method or material similar or equivalent to the described content can also be applied to the present invention.

[0053] Preparation Examples 1-7

[0054] Preparation Examples 1-7 respectively provide pre-dispersed rubber tackifiers. The differences among Preparation Examples 1-7 lie in the weight parts of the components for preparing the pre-dispersed rubber tackifier, as specifically shown in Table 1.

[0055] The flow chart for preparing the pre-dispersed rubber tackifier is as Figure 1 shown. The preparation method of the pre-dispersed rubber tackifier includes the following steps:

[0056] 1) Sieving (sieving through a 100-mesh air sieve) and mixing the reinforcing material, wollastonite and diatomaceous earth, adding amino siloxane and triethylamine, and mixing evenly to obtain a composite pre-dispersed carrier;

[0057] 2) Heating the coumarone resin to 55 °C, atomizing and uniformly spraying it into the composite pre-dispersed carrier obtained in step 1), and packaging to obtain a powdery pre-dispersed rubber tackifier.

[0058] Among them, the reinforcing material used is zinc-aluminum hydrotalcite. Zinc-aluminum hydrotalcite is prepared by the following preparation method:

[0059] Dissolve 8.93 parts by weight of analytically pure zinc nitrate in 100 parts by weight of deionized water, and dissolve 3.75 parts by weight of analytically pure aluminum nitrate in 100 parts by weight of deionized water. Mix the above two solutions evenly to form a salt solution. Dissolve 3.2 parts by weight of sodium hydroxide and 2.12 parts by weight of sodium carbonate in 50 parts by weight of deionized water to form an alkali solution. Under stirring, slowly drop the salt solution and the alkali solution into 50 parts by weight of deionized water, control the pH of the solution to be 10.0, continue stirring for 120 min, age for 20 h, and finally filter, wash the precipitate, and dry it at 60 °C for 4 h to obtain zinc-aluminum hydrotalcite.

[0060] The wollastonite is acicular wollastonite powder with an aspect ratio of 15:1. The structure of the amino silicone is shown in Formula 1.

[0061] In the coumarone resin used in the preparation examples and comparative examples, the mercaptan content is 55.8 ppm.

[0062] Table 1 Components and addition amounts of each component in the predispersed rubber tackifier provided by Preparation Examples 1-7

[0063]

[0064] Preparation Example 8

[0065] The difference between Preparation Example 8 and Preparation Example 2 is only that the reinforcing material is replaced by silica. The particle size of the silica is 1000 mesh.

[0066] Preparation Examples 9-11

[0067] Preparation Examples 9-11 respectively provide a predispersed rubber tackifier. The difference between Preparation Examples 9-11 and Preparation Example 2 is only that the components and weight ratios of the components in the reinforcing material are as shown in Table 2 specifically. The particle size of the silica is 1000 mesh.

[0068] Table 2 Components and addition amounts of each component in the reinforcing material of the predispersed rubber tackifier provided by Preparation Example 2 and Preparation Examples 9-11

[0069]

[0070] Preparation Example 12

[0071] Preparation Example 12 provides a predispersed rubber tackifier. The difference between Preparation Example 12 and Preparation Example 10 is only that the zinc-aluminum hydrotalcite is acid-anhydride-modified zinc-aluminum hydrotalcite.

[0072] The preparation method of the acid-anhydride-modified zinc-aluminum hydrotalcite includes the following steps:

[0073] 1) Acid anhydration of hydrotalcite: Take 1 g of zinc-aluminum hydrotalcite and ultrasonically disperse it in 150 mL of acetone. Add 1 g of maleic anhydride-modified polybutadiene and 0.1 g of p-toluenesulfonic acid, and reflux at 80 °C for 12 h. Remove the solvent to obtain light yellow acid-anhydrated hydrotalcite.

[0074] Preparation Example 13

[0075] Preparation Example 13 provides a pre-dispersed rubber tackifier. The difference between Preparation Example 13 and Preparation Example 12 is only that the particle size of the silica is 800 mesh.

[0076] Preparation Example 14

[0077] Preparation Example 14 provides a pre-dispersed rubber tackifier. The difference between Preparation Example 14 and Preparation Example 12 is only that the particle size of the silica is 1200 mesh.

[0078] Preparation Example 15

[0079] Preparation Example 15 provides a pre-dispersed rubber tackifier. The difference between Preparation Example 15 and Preparation Example 12 is only that the amino silicone is maleic anhydride-modified amino silicone, and the synthesis route of maleic anhydride-modified amino silicone is as follows:

[0080] The specific steps for preparing maleic anhydride-modified amino silicone are as follows: Add 10 mol of amino silicone (Compound 1), 22 mol of modifier maleic anhydride (Compound 2), and 100 ml of solvent N,N-dimethylformamide to the reaction flask. Under a nitrogen environment, heat to 90 °C for acylation reaction for 60 min, then add 0.3 mol of phosphotungstic acid, raise the temperature to 145 °C, and carry out cyclization dehydration reaction for 3 h to obtain maleic anhydride-modified amino silicone.

[0081] Preparation Example 16

[0082] Preparation Example 16 provides a pre-dispersed rubber tackifier. The difference between Preparation Example 16 and Preparation Example 15 is only that the mixing is to first mix the reinforcing material and diatomaceous earth evenly, and then add wollastonite and mix evenly.

[0083] Preparation Example 17

[0084] Preparation Example 17 provides a pre-dispersed rubber tackifier. The difference between Preparation Example 17 and Preparation Example 16 is only that the temperature of the heat treatment is 50 °C.

[0085] Preparation Example 18

[0086] Preparation Example 18 provides a pre-dispersed rubber tackifier. The difference between Preparation Example 18 and Preparation Example 16 is only that the temperature of the heat treatment is 60 °C.

[0087] Comparative Preparation Example 1

[0088] Comparative Preparation Example 1 provided a pre-dispersed rubber tackifier. The difference between Comparative Preparation Example 1 and Preparation Example 2 was only that the reinforcing material was replaced from zinc-aluminum hydrotalcite with talcum powder.

[0089] Comparative Preparation Example 2

[0090] Comparative Preparation Example 2 provided a pre-dispersed rubber tackifier. The difference between Comparative Preparation Example 2 and Preparation Example 2 was only that wollastonite was not added.

[0091] Comparative Preparation Example 3

[0092] Comparative Preparation Example 3 provided a pre-dispersed rubber tackifier. The difference between Comparative Preparation Example 3 and Preparation Example 2 was only that diatomaceous earth was not added.

[0093] Comparative Preparation Example 4

[0094] Comparative Preparation Example 4 provided a pre-dispersed rubber tackifier. The difference between Comparative Preparation Example 4 and Preparation Example 2 was only that the amino silicone was replaced with a silicone resin (purchased from Wuhan Hongjingtai Technology Co., Ltd.).

[0095] Performance Detection

[0096] After preparation, the thiol content was detected. Under the conditions of a temperature of 25°C ± 2°C, a relative humidity of 60% ± 5%, and visible light irradiation, the caking situation of the obtained pre-dispersed rubber tackifier was observed every day. Take 200 g of the pre-dispersed rubber tackifier and sieve it with a 10-mm sieve. Do not use external force to break it during sieving. If there is any material that does not pass through the sieve, it is considered caked. The results are shown in Table 3.

[0097] Table 3 Thiol Content and Caking Situation of the Pre-dispersed Rubber Tackifiers Obtained from the Preparation Examples and Comparative Preparation Examples

[0098]

[0099]

[0100] Comparing Preparation Example 2 with Comparative Preparation Examples 1-4 in conjunction with Table 3, it can be seen that when the reinforcing material is replaced from hydrotalcite with talc powder, when wollastonite is not added to the raw materials for preparing the predispersed rubber tackifier, when diatomaceous earth is replaced with organic diatomaceous earth, and when amino silicone is replaced with silicone resin, the mercaptan content of the predispersed rubber tackifier is at a high level, and caking occurs after about 1 month under the conditions of a temperature of 25°C ± 2°C, a relative humidity of 60% ± 5%, and visible light irradiation. This may be because amino silicone has a strong affinity with coumarone resin and the composite predispersed carrier material. The silicon group in amino silicone can form a network cross-linked structure with coumarone resin, and the amino end can form a tight connection with hydrotalcite, wollastonite, diatomaceous earth, etc. Thus, the composite predispersed carrier is tightly connected to coumarone resin. The special selection of inorganic substances such as hydrotalcite, wollastonite, and diatomaceous earth has a certain adsorption effect on the mercaptan in coumarone resin. Thus, on the one hand, it reduces the mercaptan content in coumarone resin, and on the other hand, it forms a complex cross-linked structure, enhancing the stability of coumarone resin and making the predispersed rubber tackifier more stable under light. Further, the special layered structure of hydrotalcite can increase the specific surface area of the predispersed rubber tackifier. Diatomaceous earth and the like adhere to the surface of hydrotalcite, increasing the surface roughness of the predispersed rubber tackifier, reducing the inter-contact area, and reducing the possibility of caking.

[0101] Comparing Preparation Example 2 with Preparation Examples 4 and 5 in conjunction with Table 3, it can be seen that when the addition amounts of amino silicone and triethylamine in Preparation Example 4 are reduced, the mercaptan content slightly increases, and the caking days are significantly shortened, with caking occurring on the 53rd day of storage. When the addition amounts of maleic anhydride-modified amino silicone and triethylamine in Preparation Example 5 are further increased, the caking days slightly increase.

[0102] Comparing Preparation Example 2 with Preparation Examples 6 and 7 in conjunction with Table 3, it can be seen that when the addition amount of coumarone resin is reduced, the mercaptan content decreases, and the non-caking days of storage are slightly extended. When the addition amount of coumarone resin is increased, the mercaptan content increases, and the non-caking days of storage are shortened.

[0103] Comparing Preparation Example 2 with Preparation Example 8 in conjunction with Table 3, it can be seen that when hydrotalcite is replaced with white carbon black, the mercaptan content is relatively high. However, the non-caking days of storage are extended. This may be because, in this system, zinc-aluminum hydrotalcite has a stronger adsorption effect on mercaptan, and white carbon black has better dispersibility.

[0104] Comparing Preparation Example 2 with Preparation Examples 9-11 in conjunction with Table 3, it can be seen that in this system, when the reinforcing material is a compound of hydrotalcite and white carbon black used in a certain proportion, there is a synergistic effect in reducing the mercaptan content and extending the non-caking time of storage. This may be because hydrotalcite is charged and has a layered structure, which synergistically forms a rougher surface with diatomaceous earth, wollastonite, etc., and white carbon black has good dispersibility, making the mercaptan content lower and less likely to cake.

[0105] Comparing Preparation Example 10 with Preparation Example 12 in combination with Table 3, it can be seen that after the hydrotalcite is subjected to acid anhydride treatment, the mercaptan content decreases and the non-caking time during storage is extended. This may be because after the hydrotalcite is subjected to acid anhydride treatment, it can combine more tightly with other raw materials, thereby improving the stability of the predispersed rubber tackifier. In addition, after the treatment, the unsaturated bond of the α,β-unsaturated ketone of maleic anhydride reacts with the mercaptan in the coumarone resin to form a sulfur bond crosslink, thereby reducing the mercaptan content.

[0106] Comparing Preparation Example 12 with Preparation Examples 13 - 14 in combination with Table 3, it can be seen that the particle size of the white carbon black can affect the mercaptan content and the non-caking time during storage of the predispersed rubber tackifier.

[0107] Comparing Preparation Example 12 with Preparation Example 15 in combination with Table 3, it can be seen that when the amino silicone is replaced with maleic anhydride-modified amino silicone, the mercaptan content of the predispersed rubber tackifier is significantly reduced. This may be because the unsaturated bond of the α,β-unsaturated ketone of maleic anhydride reacts with the mercaptan in the coumarone resin to form a sulfur bond crosslink, thereby reducing the mercaptan content, and the complexity of the crosslinking improves the stability of the predispersed rubber tackifier.

[0108] Comparing Preparation Example 12 with Preparation Example 16 in combination with Table 3, it can be seen that during premixing, first mix the reinforcing material and diatomaceous earth evenly, and then add wollastonite and mix evenly, the mercaptan content decreases and the non-caking time during storage is extended.

[0109] Comparing Preparation Example 15 with Preparation Examples 17 - 18 in combination with Table 3, it can be seen that when preparing the predispersed rubber tackifier, the heating treatment temperature can affect the mercaptan content and the non-caking time during storage of the predispersed rubber tackifier.

[0110] Examples

[0111] Examples 1 - 18 and Comparative Examples 1 - 4

[0112] Examples 1 - 18 and Comparative Examples 1 - 4 each provide a sole. The differences between Examples 1 - 18 and Comparative Examples 1 - 4 are as follows: the predispersed rubber tackifier used in preparing the sole. Among them, the predispersed rubber tackifiers provided by Preparation Examples 1 - 18 are respectively used to prepare the soles of Examples 1 - 18, and the predispersed rubber tackifiers provided by Comparative Preparation Examples 1 - 4 are respectively used to prepare the soles of Comparative Examples 1 - 4, as shown in Table 4 below.

[0113] Table 4 Sources of the predispersed rubber tackifiers added to the soles provided by Examples 1 - 18 and Comparative Examples 1 - 4

[0114]

[0115]

[0116] The formula for preparing the sole is shown in Table 5 below:

[0117] Table 5 Sole Formula

[0118]

[0119] The steps for preparing the sole are as follows:

[0120] Mixing: Add the sole raw materials in Table 5 except the vulcanizing agent S-80 and the accelerator CBS-80 into a Banbury mixer for mixing. Mix for 15 minutes at 120 °C to obtain the masterbatch. Cool it and open it on a two-roll mill. First, thin-pass the masterbatch 3 times. The masterbatch wraps around the roll. After the rubber layer is smooth, add the vulcanizing agent S-80 and the accelerator CBS-80 respectively, make a triangular wrap and thin-pass 5 times, and mix evenly to obtain a blank sheet; Hot pressing and forming: Discharge the blank sheet obtained by mixing into a molding press, and slice it according to the sole size after extrusion and vulcanization through the mold; Forming: Cut the cut blank sheet into a sole in a sole molding machine.

[0121] Test the abrasion scar length of the soles prepared in some examples and comparative examples according to the GB / T 2955 2017 standard; Test the flex resistance of the soles prepared in some examples and comparative examples according to GB / T3903.1-1994; Test the tensile properties of the soles prepared in some examples and comparative examples according to the GB / T 528-1998 standard. The results are shown in the following table.

[0122] Place the soles provided by some examples and Comparative Examples 1-4 at a temperature of 25 °C ± 2 °C, a relative humidity of 60% ± 5%, and under visible light (incandescent lamp) irradiation conditions for 3 months. Then test the tensile properties of the soles prepared from the predispersed rubber tackifier and natural rubber in some examples and comparative examples according to the GB / T 528-1998 standard, and calculate the tensile strength reduction rate. The results are shown in Table 6 below.

[0123] Table 6 Results of Abrasion Scar Length, Flex Resistance, Tensile Strength, and Tensile Strength Reduction Rate of Soles Prepared in Examples and Comparative Examples

[0124]

[0125]

[0126] Comparing Example 2 with Comparative Examples 1-4 in combination with Table 6, it can be seen that when the reinforcing material is replaced from hydrotalcite with talc powder, wollastonite is not added to the raw materials for preparing the predispersed rubber tackifier, diatomite is replaced with organic diatomite, and amino silicone is replaced with silicone resin, the wear resistance, folding resistance, and tensile properties of the sole are weak. This may be because the silicon group in amino silicone can form a network cross-linked structure with coumarone resin, and the special needle-like structure of wollastonite and its rich calcium and silicon groups are more likely to form a cross-linked chelation with coumarone resin. In addition, the special selection of inorganic substances such as hydrotalcite, wollastonite, and diatomite plays a good supporting and coordinating role in the densification and stability of the sole.

[0127] Comparing Example 2 with Example 8 in combination with Table 6, it can be seen that when hydrotalcite is replaced with silica, the wear resistance, folding resistance, and tensile properties of the sole deteriorate.

[0128] Comparing Example 2 with Examples 9-11 in combination with Table 6, it can be seen that in this system, when the reinforcing material is a compound of hydrotalcite and silica used in a certain proportion, there is a synergistic effect in improving the wear resistance, folding resistance, and tensile properties of the sole.

[0129] Comparing Example 10 with Example 12 in combination with Table 6, it can be seen that after the acid anhydride treatment of hydrotalcite, the wear resistance, folding resistance, and tensile properties of the sole are improved. This may be because after the acid anhydride treatment of hydrotalcite, it can combine more closely with other raw materials, thereby improving the stability of the predispersed rubber tackifier. The unsaturated bond of the α,β-unsaturated ketone of maleic anhydride reacts with the thiol in coumarone resin to form a sulfur bond cross-linking.

[0130] Comparing Example 12 with Examples 13-14 in combination with Table 6, it can be seen that the particle size of silica can affect the wear resistance, folding resistance, and tensile properties of the sole. This may be because the particle size of silica can affect the dispersibility of the predispersed rubber tackifier.

[0131] Comparing Example 12 with Example 15 in combination with Table 6, it can be seen that when amino silicone is replaced with maleic anhydride-modified amino silicone, the wear resistance, folding resistance, and tensile properties of the sole are improved.

[0132] Comparing Example 12 with Example 16 in combination with Table 6, it can be seen that during premixing, first mix the reinforcing material and diatomite evenly, and then add wollastonite and mix evenly, the wear resistance, folding resistance, and tensile properties of the sole are improved.

[0133] Comparing Example 15 with Examples 17-18 in combination with Table 6, it can be seen that when preparing the predispersed rubber tackifier, the heating treatment temperature affects the wear resistance, folding resistance, and tensile properties of the sole.

[0134] This specific embodiment is only an interpretation of the present application and does not limit the present application. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contributions as needed, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A pre-dispersed rubber tackifier, characterized in that, The pre-dispersed rubber tackifier is prepared from components comprising the following parts by weight: 18 - 21 parts of reinforcing agent, 5 - 8 parts of wollastonite, 2 - 3 parts of diatomaceous earth, 1 - 2 parts of amino siloxane or maleic anhydride-modified amino siloxane, 0.08 - 0.15 parts of triethylamine, and 65 - 75 parts of coumarone resin; the reinforcing agent is selected from at least one of silica and hydrotalcite.

2. The pre-dispersed rubber tackifier according to claim 1, wherein, The weight ratio of the coumarone resin to the amino siloxane is (35 - 70):1; the weight ratio of the reinforcing agent, wollastonite and diatomaceous earth is (21 - 27):(5 - 12):

3.

3. The pre-dispersed rubber tackifier according to claim 1, characterized in that, The reinforcing agent consists of silica and hydrotalcite in a weight ratio of (2.3 - 4):

1.

4. The pre-dispersed rubber tackifier according to claim 1, wherein The hydrotalcite is selected from at least one of magnesium-aluminum hydrotalcite, cobalt-aluminum hydrotalcite, cobalt-iron hydrotalcite, calcium-aluminum hydrotalcite, and zinc-aluminum hydrotalcite; the hydrotalcite is acid-anhydrated hydrotalcite, and the preparation method of the acid-anhydrated hydrotalcite includes: dispersing hydrotalcite in an organic solvent, adding maleic anhydride-modified polybutadiene and p-toluenesulfonic acid, reacting, and removing the solvent to obtain the acid-anhydrated hydrotalcite.

5. The pre-dispersed rubber tackifier according to claim 1, wherein The particle size of the silica is 800 - 1200 mesh.

6. The pre-dispersed rubber tackifier according to claim 1, wherein The preparation method of the maleic anhydride-modified amino siloxane includes: carrying out an acylation reaction on amino siloxane and maleic anhydride in a solvent, and then adding an acid catalyst to carry out a cyclization dehydration reaction to obtain the maleic anhydride-modified amino siloxane; the solvent is N,N-dimethylformamide, and the acid catalyst is phosphotungstic acid.

7. A method for preparing the pre-dispersed rubber tackifier according to any one of claims 1-6, characterized in that, It includes the following steps: 1) Mix the reinforcing agent, wollastonite, and diatomaceous earth, and add amino siloxane and triethylamine to obtain a composite pre-dispersed carrier; 2) Carry out a heat treatment on the coumarone resin, atomize it, and uniformly spray it into the composite pre-dispersed carrier obtained in step 1) to obtain the pre-dispersed rubber tackifier.

8. The preparation method of the pre-dispersed rubber tackifier according to claim 7, wherein, In step 1), the mixing includes mixing the reinforcing agent and diatomaceous earth evenly, and then adding wollastonite and mixing evenly.

9. The preparation method of the pre-dispersed rubber tackifier according to claim 7, characterized in that, In step 2), control the temperature of the heat treatment to be 50 - 60 °C.

10. Use of the pre-dispersed rubber tackifier according to any one of claims 1 - 6 in the preparation of sole materials.

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