阅读说明：本技术 一种重质碳酸钙改性剂、改性超细重质碳酸钙及其制备方法和应用、顺丁橡胶复合材料 (Heavy calcium carbonate modifier, modified superfine heavy calcium carbonate, preparation method and application of modified superfine heavy calcium carbonate, and butadiene rubber composite material ) 是由 陈超 袁铭伟 彭鹤松 宋波 李海滨 于 2021-03-12 设计创作，主要内容包括：本发明提供了一种重质碳酸钙改性剂、改性超细重质碳酸钙及其制备方法和应用、顺丁橡胶复合材料,属于矿物材料加工与应用领域技术领域。将本发明的改性剂用于超细重质碳酸钙的改性,可以改善超细重质碳酸钙在高分子材料中的分散性,将本发明的改性超细重质碳酸钙用于制备顺丁橡胶复合材料,得到的顺丁橡胶具有优异的力学性能。实施例的结果显示,改性超细重质碳酸钙与顺丁橡胶复合后得到的顺丁橡胶复合材料的最大载荷＞40N,100％定伸强度＞2.8MPa,300％定伸强度＞3.5MPa,撕裂强度≥3kN/m,DIN磨耗≥120,吸油值≤20。(The invention provides a heavy calcium carbonate modifier, modified superfine heavy calcium carbonate, a preparation method and application thereof, and a butadiene rubber composite material, and belongs to the technical field of mineral material processing and application. The modifier is used for modifying superfine heavy calcium carbonate, can improve the dispersibility of the superfine heavy calcium carbonate in a high polymer material, and the butadiene rubber obtained by using the modified superfine heavy calcium carbonate in the preparation of the butadiene rubber composite material has excellent mechanical property. The results of the examples show that the maximum load of the butadiene rubber composite material obtained by compounding the modified superfine heavy calcium carbonate and the butadiene rubber is more than 40N, the 100% elongation strength is more than 2.8MPa, the 300% elongation strength is more than 3.5MPa, the tear strength is more than or equal to 3kN/m, the DIN abrasion is more than or equal to 120, and the oil absorption value is less than or equal to 20.)

1. The heavy calcium carbonate modifier is characterized by comprising a boric acid ester coupling agent, a surfactant and maleic anhydride grafted polypropylene which are independently packaged; the surfactant is phosphate anionic surfactant.

2. The heavy calcium carbonate modifier of claim 1, wherein the phosphate anionic surfactant is one or more of lauryl alcohol ether phosphate, isooctanol polyoxyethylene ether phosphate, nonylphenol polyoxyethylene ether phosphate, and isotridecyl alcohol ether phosphate.

3. A modified ultrafine ground calcium carbonate, which is characterized by being prepared from ultrafine ground calcium carbonate and the ground calcium carbonate modifier according to claim 1 or 2;

the using amount of the borate coupling agent in the heavy calcium carbonate modifier is 0.5-1.5% of the weight of the superfine heavy calcium carbonate; the amount of the surfactant in the heavy calcium carbonate modifier is 0.5-1.5% of the weight of the superfine heavy calcium carbonate; the amount of the maleic anhydride grafted polypropylene in the heavy calcium carbonate modifier is 1-2% of the mass of the superfine heavy calcium carbonate.

4. The modified ultrafine heavy calcium carbonate according to claim 3, wherein the mesh number of the ultrafine heavy calcium carbonate is not less than 2000 meshes.

5. The process for preparing modified ultrafine ground calcium carbonate according to claim 3 or 4, which comprises the steps of:

and mixing the superfine ground calcium carbonate, a ground calcium carbonate modifier and water, and carrying out modification reaction to obtain the modified superfine ground calcium carbonate.

6. The method according to claim 5, wherein the ultrafine ground calcium carbonate, the ground calcium carbonate modifier and water are mixed by: mixing superfine ground calcium carbonate, a surfactant in a ground calcium carbonate modifier and maleic anhydride grafted polypropylene to obtain an intermediate mixture; and mixing the borate coupling agent in the heavy calcium carbonate modifier with water, and spraying the obtained mixed solution into the intermediate mixture.

7. The method according to claim 5 or 6, wherein the temperature of the modification reaction is 80 to 120 ℃ and the time is 10 to 45 min.

8. Use of the modified ultrafine heavy calcium carbonate according to claim 3 or 4 or the modified ultrafine heavy calcium carbonate prepared by the preparation method according to any one of claims 5 to 6 in the preparation of a butadiene rubber composite material.

9. The butadiene rubber composite material comprises the following preparation raw materials in parts by weight:

100 parts of butadiene rubber, 1.5 parts of an active agent, 3 parts of an antioxidant, 0.9 part of an accelerator, 3 parts of active zinc oxide, 1.5 parts of sulfur and 10-30 parts of modified superfine heavy calcium carbonate; the modified superfine ground calcium carbonate is the modified superfine ground calcium carbonate of claim 3 or 4 or the modified superfine ground calcium carbonate prepared by the preparation method of any one of claims 5 to 6.

10. The butadiene rubber composite material according to claim 9, characterized in that the active agent is stearic acid; the antioxidant is phenyl p-phenylenediamine; the accelerator is 2,2' -dithiodibenzothiazole.

Technical Field

The invention relates to the technical field of mineral material processing and application, in particular to a heavy calcium carbonate modifier, modified superfine heavy calcium carbonate, a preparation method and application thereof, and a butadiene rubber composite material.

Background

Ground Calcium Carbonate (Calcium Carbonate, CaCO)₃) The inorganic filler is an inorganic filler with wide application, is widely applied to industries such as papermaking, plastics, chemical fibers, rubber, adhesives, sealants, cosmetics, building materials, coatings, medicines, foods, feeds and the like, has the advantages of wide sources, stable components, high whiteness, high yield and the like, and is often compounded with a high polymer material as the filler. However, the surface of heavy calcium carbonate has many hydroxyl groups, which makes it hydrophilic and oleophobic and polar, and is difficult to disperse uniformly in nonpolar organic polymers, thus affecting the performance of the composite material. In addition, the ground calcium carbonate needs to have the smallest particle size to achieve the reinforcing effect, but the ground calcium carbonate with the small particle size has extremely large specific surface area and surface energy, is easy to cause agglomeration, becomes large particles to be filled in a polymer matrix, and the large particles become stress concentration points to influence the performance of a product and even make the product unusable. Therefore, in order to improve the interfacial compatibility and the dispersibility of the heavy calcium carbonate in the matrix, increase the addition amount, reduce the cost of the product and improve the added value, surface modification research needs to be carried out on the heavy calcium carbonate powder, and the application field and the development prospect of the heavy calcium carbonate are further expanded, so that the heavy calcium carbonate powder becomes a functional toughening and reinforcing filling material.

Disclosure of Invention

The invention aims to provide a heavy calcium carbonate modifier, modified superfine heavy calcium carbonate, a preparation method and application thereof.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a heavy calcium carbonate modifier, which comprises a boric acid ester coupling agent, a surfactant and maleic anhydride grafted polypropylene which are independently packaged; the surfactant is phosphate anionic surfactant.

Preferably, the phosphate anionic surfactant is one or more of lauryl alcohol ether phosphate, isooctanol polyoxyethylene ether phosphate, nonylphenol polyoxyethylene ether phosphate and isomeric tridecanol ether phosphate.

The invention provides modified superfine heavy calcium carbonate, which is prepared from superfine heavy calcium carbonate and a heavy calcium carbonate modifier in the scheme;

the using amount of the borate coupling agent in the heavy calcium carbonate modifier is 0.5-1.5% of the weight of the superfine heavy calcium carbonate; the amount of the surfactant in the heavy calcium carbonate modifier is 0.5-1.5% of the weight of the superfine heavy calcium carbonate; the amount of the maleic anhydride grafted polypropylene in the heavy calcium carbonate modifier is 1-2% of the mass of the superfine heavy calcium carbonate.

Preferably, the mesh number of the superfine heavy calcium carbonate is more than or equal to 2000 meshes.

The invention provides a preparation method of modified superfine heavy calcium carbonate, which is characterized by comprising the following steps:

and mixing the superfine ground calcium carbonate, a ground calcium carbonate modifier and water, and carrying out modification reaction to obtain the modified superfine ground calcium carbonate.

Preferably, the process of mixing the ultrafine ground calcium carbonate, the ground calcium carbonate modifier and the water is as follows: mixing superfine ground calcium carbonate, a surfactant in a ground calcium carbonate modifier and maleic anhydride grafted polypropylene to obtain an intermediate mixture; and mixing the borate coupling agent in the heavy calcium carbonate modifier with water, and spraying the obtained mixed solution into the intermediate mixture.

Preferably, the temperature of the modification reaction is 80-120 ℃, and the time is 10-45 min.

The invention provides application of the modified superfine heavy calcium carbonate in the scheme or the modified superfine heavy calcium carbonate prepared by the preparation method in the scheme in preparation of a butadiene rubber composite material.

The invention provides a butadiene rubber composite material which comprises the following preparation raw materials in parts by weight:

100 parts of butadiene rubber, 1.5 parts of an active agent, 3 parts of an antioxidant, 0.9 part of an accelerator, 3 parts of active zinc oxide, 1.5 parts of sulfur and 10-30 parts of modified superfine heavy calcium carbonate; the modified superfine heavy calcium carbonate is the modified superfine heavy calcium carbonate in the scheme or the modified superfine heavy calcium carbonate prepared by the preparation method in the scheme.

Preferably, the active agent is stearic acid; the antioxidant is phenyl p-phenylenediamine; the accelerator is 2,2' -dithiodibenzothiazole.

The invention provides a heavy calcium carbonate modifier, which comprises a boric acid ester coupling agent, a surfactant and maleic anhydride grafted polypropylene which are independently packaged; the surfactant is phosphate anionic surfactant.

The heavy calcium carbonate has a large amount of hydroxyl on the surface, the surface property is hydrophilic, the heavy calcium carbonate is lipophilic when being doped in macromolecules, and the dispersibility of the heavy calcium carbonate and the macromolecules is poor, so that RCOO in fatty acid is obtained by adding phosphate ester anionic surfactant^-Ca in calcium carbonate²⁺Or CaHCO₃ ⁺The component generates fatty acid calcium precipitate, and can achieve the effect of calcium carbonate surface lipophilicity. As a part of nonpolar groups in the molecules of the borate coupling agent can generate chemical reaction or winding with organic polymers, and the other part of polar groups in the molecules can form strong chemical bonding, the borate coupling agent is added to firmly combine materials with greatly different properties, such as polymer matrixes and powder (inorganic minerals), together through an interface layer. Maleic anhydride grafted polypropylene molecules can be directionally adsorbed on the surface of calcium carbonate, the calcium carbonate adsorbed by the maleic anhydride grafted polypropylene has charge characteristics, and a physical and chemical adsorption layer is formed on the surface of the calcium carbonate, so that the calcium carbonate particles are prevented from agglomerating, and the maleic anhydride grafted polypropylene is added to prevent agglomeration of the calcium carbonate particlesThe dispersibility of the calcium carbonate particles in the rubber material is improved.

The results of the examples show that the maximum load of the butadiene rubber composite material obtained by compounding the modified superfine heavy calcium carbonate and the butadiene rubber is more than 40N, the 100% elongation strength is more than 2.8MPa, the 300% elongation strength is more than 3.5MPa, the tear strength is more than or equal to 3kN/m, the DIN abrasion is more than or equal to 120, and the oil absorption value is less than or equal to 20.

Detailed Description

The invention provides a heavy calcium carbonate modifier, which comprises a boric acid ester coupling agent, a surfactant and maleic anhydride grafted polypropylene which are independently packaged; the surfactant is phosphate anionic surfactant.

In the present invention, the phosphate anionic surfactant is preferably one or more of lauryl alcohol ether phosphate, isooctanol polyoxyethylene ether phosphate, nonylphenol polyoxyethylene ether phosphate and isotridecyl alcohol ether phosphate. When the phosphate anionic surfactant is a plurality of the above substances, the specific proportion of each phosphate anionic surfactant in the invention has no special requirement, and the proportion can be any.

The invention provides modified superfine heavy calcium carbonate, which is prepared from superfine heavy calcium carbonate and a heavy calcium carbonate modifier in the scheme;

the using amount of the borate coupling agent in the heavy calcium carbonate modifier is 0.5-1.5% of the weight of the superfine heavy calcium carbonate; the amount of the surfactant in the heavy calcium carbonate modifier is 0.5-1.5% of the weight of the superfine heavy calcium carbonate; the amount of the maleic anhydride grafted polypropylene in the heavy calcium carbonate modifier is 1-2% of the mass of the superfine heavy calcium carbonate.

In the invention, the using amount of the borate coupling agent in the heavy calcium carbonate modifier is preferably 0.7-1.3% of the mass of the superfine heavy calcium carbonate, and more preferably 0.9-1.1%.

In the invention, the dosage of the surfactant in the heavy calcium carbonate modifier is preferably 0.7-1.3% of the mass of the superfine heavy calcium carbonate, and more preferably 0.9-1.1%.

In the invention, the amount of the maleic anhydride grafted polypropylene in the heavy calcium carbonate modifier is preferably 1.2-1.8% of the mass of the superfine heavy calcium carbonate, and more preferably 1.4-1.6%.

In the invention, the mesh number of the superfine heavy calcium carbonate is preferably more than or equal to 2000 meshes.

The heavy calcium carbonate has a large amount of hydroxyl on the surface, the surface property is hydrophilic, the doped polymer is lipophilic, and the dispersibility of the heavy calcium carbonate and the doped polymer is poor, so that RCOO in fatty acid is obtained by adding phosphate ester anionic surfactant^-Ca in calcium carbonate²⁺Or CaHCO₃ ⁺The component generates fatty acid calcium precipitate, and can achieve the effect of calcium carbonate surface lipophilicity. As a part of nonpolar groups in the molecules of the borate coupling agent can generate chemical reaction or winding with organic polymers, and the other part of polar groups in the molecules can form strong chemical bonding, the borate coupling agent is added to firmly combine materials with greatly different properties, such as polymer matrixes and powder (inorganic minerals), together through an interface layer. The maleic anhydride grafted polypropylene molecules can be directionally adsorbed on the surface of calcium carbonate, calcium carbonate adsorbed by the maleic anhydride grafted polypropylene has charge characteristics, and a physical and chemical adsorption layer is formed on the surface of the calcium carbonate, so that the calcium carbonate particles are prevented from agglomerating, and the dispersibility of the calcium carbonate particles in the rubber material is improved by adding the maleic anhydride grafted polypropylene. Even the superfine heavy calcium carbonate has good dispersibility under the action of the modifier.

The invention provides a preparation method of the modified superfine heavy calcium carbonate in the scheme, which comprises the following steps:

and mixing the superfine ground calcium carbonate, a ground calcium carbonate modifier and water, and carrying out modification reaction to obtain the modified superfine ground calcium carbonate.

In the present invention, the process of mixing the ultrafine ground calcium carbonate, the ground calcium carbonate modifier and water is preferably: carrying out first mixing on superfine ground calcium carbonate, a surfactant in a ground calcium carbonate modifier and maleic anhydride grafted polypropylene to obtain an intermediate mixture; and mixing the borate coupling agent in the heavy calcium carbonate modifier with water, and spraying the obtained mixed solution into the intermediate mixture.

In the invention, the temperature of the first mixing is preferably 80-120 ℃, and more preferably 90-110 ℃; the invention has no special requirement on the first mixing time, and can ensure that the surfactant in the superfine ground calcium carbonate and the ground calcium carbonate modifier and the maleic anhydride grafted polypropylene are uniformly mixed. In the invention, the first mixing is preferably carried out under stirring conditions, and the stirring speed is preferably 800-1200 rpm.

In the present invention, the mass ratio of the borate coupling agent to water is preferably 1: 3. The invention has no special requirements on the spraying process, and the spraying process known in the field can be adopted.

In the invention, the temperature of the modification reaction is preferably 80-120 ℃, and more preferably 90-110 ℃; the time is preferably 10 to 45min, and more preferably 20 to 30 min. In the invention, the modification reaction is preferably carried out under the condition of stirring, and the stirring speed is preferably 800-1200 rpm.

After the modification reaction is finished, the modified reaction product is preferably cooled and dried to obtain the modified superfine heavy calcium carbonate.

The invention provides application of the modified superfine heavy calcium carbonate in the scheme or the modified superfine heavy calcium carbonate prepared by the preparation method in the scheme in preparation of a butadiene rubber composite material. The modified superfine heavy calcium carbonate can have good dispersibility in rubber materials, so that the prepared butadiene rubber composite material has excellent mechanical properties.

The invention provides a butadiene rubber composite material which comprises the following preparation raw materials in parts by weight: 100 parts of butadiene rubber, 1.5 parts of an active agent, 3 parts of an antioxidant, 0.9 part of an accelerator, 3 parts of active zinc oxide, 1.5 parts of sulfur and 10-30 parts of modified superfine heavy calcium carbonate; the modified superfine heavy calcium carbonate is the modified superfine heavy calcium carbonate in the scheme or the modified superfine heavy calcium carbonate prepared by the preparation method in the scheme.

In the present invention, the butadiene rubber is preferably BR 9000; the active agent is preferably stearic acid; the antioxidant is preferably phenyl p-phenylenediamine; the accelerator is preferably 2,2' -dithiodibenzothiazole.

Based on the mass parts of the butadiene rubber, the preparation raw material of the butadiene rubber composite material provided by the invention comprises 10-30 parts of modified superfine ground calcium carbonate, preferably 12-28 parts, and more preferably 15-25 parts.

The preparation method of the butadiene rubber composite material has no special requirements, and the preparation method well known in the field can be adopted. In the embodiment of the invention, 10-30 parts of modified superfine ground calcium carbonate is added into butadiene rubber, then an active agent, an antioxidant, active zinc oxide, an accelerator and sulfur are sequentially added in sequence for mixing, and finally, the mixture is subjected to sheet discharging and aging for 24 hours and is placed into a flat vulcanizing machine for vulcanization for 15min for molding, so that a butadiene rubber composite material is obtained; the vulcanization temperature is 150-160 ℃, and the vulcanization pressure is 15-16 MPa.

The heavy calcium carbonate modifier, the modified ultrafine heavy calcium carbonate, the preparation method and the application thereof, and the butadiene rubber composite material provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.

Example 1

Uniformly mixing 1000g of superfine ground calcium carbonate (2000 meshes), 5g of lauryl alcohol ether phosphate and 10g of maleic anhydride grafted polypropylene at 800rpm and 80 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 5g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 10min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Example 2

Uniformly mixing 1000g of superfine ground calcium carbonate (2000 meshes), 5g of isooctanol polyoxyethylene ether phosphate and 10g of maleic anhydride grafted polypropylene at 800rpm and 80 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 5g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 10min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Example 3

Uniformly mixing 1000g of superfine ground calcium carbonate (2000 meshes), 5g of nonylphenol polyoxyethylene ether phosphate and 10g of maleic anhydride grafted polypropylene at 800rpm and 80 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 5g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 10min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Example 4

Uniformly mixing 1000g of superfine heavy calcium carbonate (2000 meshes), 5g of isomeric tridecanol ether phosphate and 10g of maleic anhydride grafted polypropylene at 800rpm and 80 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 5g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 10min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Example 5

Uniformly mixing 1000g of superfine ground calcium carbonate (2000 meshes), 10g of lauryl alcohol ether phosphate and 15g of maleic anhydride grafted polypropylene at 800rpm and 80 ℃ to obtain an intermediate mixture; and (3) uniformly mixing the 10 borate ester coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 10min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Example 6

Uniformly mixing 1000g of superfine ground calcium carbonate (2000 meshes), 10g of isooctanol polyoxyethylene ether phosphate and 15g of maleic anhydride grafted polypropylene at 800rpm and 80 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 10g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 10min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Example 7

Uniformly mixing 1000g of superfine ground calcium carbonate (2000 meshes), 10g of nonylphenol polyoxyethylene ether phosphate and 15g of maleic anhydride grafted polypropylene at 800rpm and 80 ℃ to obtain an intermediate mixture; and (3) uniformly mixing the 10 borate ester coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 10min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Example 8

Uniformly mixing 1000g of superfine heavy calcium carbonate (2000 meshes), 10g of isomeric tridecanol ether phosphate and 15g of maleic anhydride grafted polypropylene at 800rpm and 80 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 10g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 10min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Example 9

Uniformly mixing 1000g of superfine ground calcium carbonate (2000 meshes), 5g of lauryl alcohol ether phosphate and 10g of maleic anhydride grafted polypropylene at 1000rpm and 100 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 5g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 10min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Example 10

Uniformly mixing 1000g of superfine ground calcium carbonate (2000 meshes), 5g of lauryl alcohol ether phosphate and 10g of maleic anhydride grafted polypropylene at 1000rpm and 100 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 5g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 25min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Example 11

Uniformly mixing 1000g of superfine ground calcium carbonate (2000 meshes), 5g of lauryl alcohol ether phosphate and 10g of maleic anhydride grafted polypropylene at 1000rpm and 100 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 5g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 35min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Example 12

Uniformly mixing 1000g of superfine ground calcium carbonate (2000 meshes), 5g of lauryl alcohol ether phosphate and 10g of maleic anhydride grafted polypropylene at 1000rpm and 100 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 5g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 45min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Example 13

Uniformly mixing 1000g of superfine ground calcium carbonate (2000 meshes), 5g of lauryl alcohol ether phosphate and 10g of maleic anhydride grafted polypropylene at 1200rpm and 120 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 5g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 35min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Example 14

Uniformly mixing 1000g of superfine ground calcium carbonate (2000 meshes), 15g of lauryl alcohol ether phosphate and 20g of maleic anhydride grafted polypropylene at 1200rpm and 120 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 15g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 35min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Example 15

Uniformly mixing 1000g of superfine ground calcium carbonate (2000 meshes), 15g of isooctanol polyoxyethylene ether phosphate and 20g of maleic anhydride grafted polypropylene at 1200rpm and 120 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 15g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 35min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Example 16

Uniformly mixing 1000g of superfine ground calcium carbonate (2000 meshes), 15g of nonylphenol polyoxyethylene ether phosphate and 20g of maleic anhydride grafted polypropylene at 1200rpm and 120 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 15g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 35min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Example 17

Uniformly mixing 1000g of superfine heavy calcium carbonate (2000 meshes), 15g of isomeric tridecanol ether phosphate and 20g of maleic anhydride grafted polypropylene at 1200rpm and 120 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 15g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 35min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Comparative example 1

Is unmodified superfine ground calcium carbonate (2000 meshes).

Comparative example 2

Uniformly mixing 1000g of superfine heavy calcium carbonate (2000 meshes) with 15g of isomeric tridecanol ether phosphate at 1200rpm and 120 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 15g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 35min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Comparative example 3

Uniformly mixing 1000g of superfine ground calcium carbonate (2000 meshes) and 20g of maleic anhydride grafted polypropylene at 1200rpm and 120 ℃ to obtain an intermediate mixture; and (2) uniformly mixing 15g of borate coupling agent and water according to the mass ratio of 1:3, spraying the obtained mixed solution into the intermediate mixture, carrying out modification reaction for 35min, and cooling and drying to obtain the modified superfine heavy calcium carbonate product.

Comparative example 4

And (3) uniformly mixing 1000g of superfine heavy calcium carbonate (2000 meshes), 15g of isomeric tridecanol ether phosphate and 20g of maleic anhydride grafted polypropylene at 1200rpm and 120 ℃, carrying out modification reaction on the obtained intermediate mixture for 35min, and cooling and drying to obtain a modified superfine heavy calcium carbonate product.

Application examples 1 to 17

Application examples 1 to 17 are respectively prepared into a butadiene rubber composite material by using the modified superfine heavy calcium carbonate obtained in the examples 1 to 17; the butadiene rubber composite material comprises the following preparation raw materials in parts by mass:

the preparation method comprises the following steps:

adding 20 parts of modified superfine ground calcium carbonate into butadiene rubber, sequentially adding stearic acid, phenyl-p-phenylenediamine, active zinc oxide, 2' -dithiodibenzothiazole and a vulcanizing agent in sequence, mixing, finally performing sheet aging (24h), putting into a flat plate vulcanizing machine, vulcanizing at 160 ℃ and 16MPa for 15min, and molding to prepare a sample. And (5) standing for 24 hours, and detecting the performance of the product.

Comparative application examples 1 to 4

The only difference from application example 1 was that the modified ultrafine heavy calcium carbonate of example 1 was replaced with the modified ultrafine heavy calcium carbonate or unmodified ultrafine heavy calcium carbonate of comparative examples 1 to 4.

Table 1 shows the results of mechanical property measurements of the modified ultrafine heavy calcium carbonate samples obtained in the examples and comparative examples in filled butadiene rubber (with a filling mass fraction of 20 wt%). Wherein, the maximum load, the 100% elongation strength and the 300% elongation strength are tested by making dumbbell-shaped splines according to GB/T528-.

TABLE 1 results of mechanical property test of the cis-butadiene rubber composite materials obtained in the examples and comparative examples

From the results in table 1, it is known that the modified ultrafine heavy calcium carbonate has better mechanical properties than the unmodified ultrafine heavy calcium carbonate filled butadiene rubber composite material due to the improved dispersibility in butadiene rubber, and the oil absorption value is reduced due to the replacement of a large amount of hydroxyl groups on the surface of the modified ultrafine heavy calcium carbonate with organic groups (in table 1, the oil absorption value refers to the amount of oil required for the ultrafine heavy calcium carbonate powder to change from dispersion to agglomeration, and the smaller the oil absorption value, the better the lipophilicity of the powder). From the results of examples 14 to 17 and comparative examples 2 to 3, it can be seen that in the case of using a borate coupling agent as a bridge, the mechanical properties of the modified ground calcium carbonate filled in the butadiene rubber are reduced and unstable (as shown by unstable results of multiple measurements, not shown in the table) when the superfine ground calcium carbonate is modified by using a surfactant or maleic anhydride grafted polypropylene alone. From the results of examples 14 to 17 and comparative example 4, it is known that in the case where no borate coupling agent is added (comparative example 4), a "bridge" is lacking between the powder and the organic polymer, and each property after modification is reduced compared with the case where a coupling agent is present, and particularly, the maximum load of the butadiene rubber composite material is significantly reduced.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.