Fluorine-free organic silicon lubricant for improving processing performance of polyolefin resin and preparation method of fluorine-free organic silicon lubricant

Abstract

The invention relates to the technical field of organic silicon lubricants, and discloses a fluorine-free organic silicon lubricant for improving the processing performance of polyolefin resin and a preparation method thereof.The preparation method comprises the steps that polyethylene glycol, silicon dioxide, quaternary ammonium salt modified silane, polydimethylsiloxane, modified carbon nanotubes and pentaerythritol stearate are added into a stirrer to be stirred, and a mixture is stirred to be uniform; the fluorine-free organic silicon lubricant capable of improving the processing performance of the polyolefin resin is obtained after the reaction is finished. Hydroxyl in the organic silicon lubricant can form a boundary film on the surface of the polyolefin resin, so that the surface of the polyolefin resin is smoother; quaternary ammonium salt can form a boundary film on the surface of polyolefin resin, so that friction is reduced, and the lubricating effect is improved; the silicon element and the carbon nano tube in the fluorine-free organic silicon lubricant also have a better lubricating effect, so that the processing performance of the polyolefin resin is further improved.

Description

Technical Field

[0001] The invention relates to the technical field of organosilicon lubricants, in particular to a fluorine-free organosilicon lubricant for improving the processing performance of polyolefin resins and a preparation method thereof. Background Art

[0002] Polyolefin resins are widely used in automotive parts, home appliance parts, medical parts and other fields due to their low price, excellent physical properties, good rigidity and heat resistance. However, their molding processability cannot meet the demand. Polyolefins will cause many problems in vacuum molding, blow molding, foam molding, extrusion molding and calendering molding due to their low melt tension during molding. The existing technology uses high molecular weight to increase the melt tension, but its fluidity will decrease. Therefore, how to avoid this phenomenon is the key to solving the problem. For example, the patent CN polyolefin resin processing aid, polyolefin resin composition and molded product provide excellent molding processability, that is, excellent melt tension and eye mucus-like substance suppression effect, but its components are single and the lubrication effect needs to be further improved. Summary of the invention

[0003] 1. Technical issues to be resolved In view of the deficiencies in the prior art, the present invention provides a fluorine-free silicone lubricant for improving the processing performance of polyolefin resin and a preparation method thereof, which has a good lubricating effect and improves the processing performance.

[0004] (II) Technical solution To achieve the above-mentioned purpose, the present invention provides the following technical scheme: a fluorine-free silicone lubricant for improving the processing performance of polyolefin resin, comprising the following components by weight: 10-15 parts by weight of polyethylene glycol, 3-5 parts by weight of silicon dioxide, 2-6 parts by weight of quaternary ammonium salt modified silane, 4-8 parts by weight of polydimethylsiloxane, 8-14 parts by weight of modified carbon nanotubes, and 10-20 parts by weight of pentaerythritol stearate.

[0005] Preferably, the preparation method of the quaternary ammonium salt modified silane is: (1) Add divinyl glycol to chloroform solvent, stir and disperse, then add vinyl trichlorosilane, react at 75-90°C for 8-14h, filter, distill under reduced pressure, wash, and dry to obtain an intermediate; (2) Add the intermediate and hexamethyldisilazane to toluene solvent, stir evenly, continue to add chloroplatinic acid catalyst, raise the temperature to 110-125°C, stir and reflux for 5-10 hours, and after the reaction is completed, filter and dry to obtain tertiary aminosilazane; (3) Add tertiary aminosilazane and vinyl chloride to N,N-dimethylformamide solvent, stir for 3-4 minutes, react at 60-75°C for 3-7 hours, and then perform rotary distillation, filter, wash, and olefinate the silazane; (4) Add the alkenyl silazane to N,N-dimethylformamide solvent, stir evenly, then add hydrogen peroxide aqueous solution, stir and react at 30-40° C. for 4-5 hours. After the reaction is completed, distill under reduced pressure, wash and dry to obtain quaternary ammonium salt modified silane.

[0006] Preferably, the mass ratio of divinyl glycol to vinyltrichlorosilane in (1) is 1.6-2.2:1.

[0007] Preferably, the mass ratio of the intermediate, hexamethyldisilazane and chloroplatinic acid catalyst in (2) is 1:1.1-1.3:0.01-0.02.

[0008] Preferably, the mass ratio of tertiary aminosilazane to vinyl chloride in (3) is 1:1.3-1.5.

[0009] Preferably, the mass ratio of alkenyl silazane to aqueous hydrogen peroxide solution in (4) is 1:2.4-3.2.

[0010] Preferably, the preparation method of the modified carbon nanotubes is: add 4-7 parts by weight of olefinic silazane, 3-5 parts by weight of vinyl carbon nanotubes, 6-8 parts by weight of acrylamide, and 4-7 parts by weight of acryl alcohol to N,N-dimethylformamide solvent, stir and disperse, then add 0.4-0.8 parts by weight of ammonium persulfate initiator, react at 110-130°C for 5-7h, and then rotary distill and wash to obtain modified carbon nanotubes.

[0011] Preferably, the preparation method of the fluorine-free silicone lubricant for improving the processing performance of polyolefin resin is: polyethylene glycol, silicon dioxide, quaternary ammonium salt modified silane, polydimethylsiloxane, modified carbon nanotubes, and pentaerythritol stearate are added to a stirrer and stirred for 20-40 minutes to obtain the fluorine-free silicone lubricant for improving the processing performance of polyolefin resin.

[0012] 3. Beneficial technical effects The invention adds polyethylene glycol, silicon dioxide, quaternary ammonium salt modified silane, polydimethylsiloxane, modified carbon nanotube and pentaerythritol stearate into a stirrer, and stirs to obtain a fluorine-free organic silicon lubricant for improving the processing performance of polyolefin resin.

[0013] The hydroxyl groups in the fluorine-free silicone lubricant can form a boundary film on the surface of the polyolefin resin, making its surface smoother; the quaternary ammonium salt therein can also form a boundary film on the surface of the polyolefin resin, thereby reducing friction and improving the lubrication effect; the silicon element and carbon nanotubes in the fluorine-free silicone lubricant also have a good lubrication effect, further improving the processing performance of the polyolefin resin; during the stirring process, the hydroxyl groups in the modified carbon nanotubes and the epoxy groups in the quaternary ammonium salt-modified silane undergo a ring-opening reaction, which improves their compatibility with each other and produces cross-linking, which allows for better adsorption on the surface of the polyolefin resin and improves its lubrication effect. DETAILED DESCRIPTION

[0014] The preparation process of vinyl carbon nanotubes refers to the journal "Materials Science and Engineering Plastics", Volume 23, Issue 4, "Surface Vinyl Functionalization of Multi-walled Carbon Nanotubes": 0.3g of multi-walled carbon nanotubes were added to 30mL of 98% concentrated sulfuric acid and 10mL of 70% concentrated nitric acid, refluxed at 140°C for 1h, filtered, and washed. 0.1g of the acidified carbon nanotubes obtained were weighed and dispersed in 15mL of acetone and 15mL of chloroform, 2mL of triethylamine and 5mL of acryloyl chloride were added, and the reaction was carried out at 40°C for 24h. Then 10mL of ethanol was added and stirred for 2h, filtered, and washed to obtain vinyl carbon nanotubes.

[0015] Polyethylene glycol: The molecular weight of PEG is 8000.

[0016] Example 1 (1) adding divinyl glycol to chloroform solvent, stirring and dispersing, and then adding vinyl trichlorosilane thereto, wherein the mass ratio of divinyl glycol to vinyl trichlorosilane is 1.6:1, reacting at 75° C. for 8 h, and after completion, filtering, vacuum distilling, washing, and drying to obtain an intermediate; (2) adding the intermediate and hexamethyldisilazane to toluene solvent, stirring evenly, and continuing to add chloroplatinic acid catalyst, wherein the mass ratio of the intermediate, hexamethyldisilazane, and chloroplatinic acid catalyst is 1:1.1:0.01, heating to 110°C, stirring and reflux reaction for 5 hours, after the reaction is completed, filtering and drying to obtain tertiary aminosilazane; (3) Adding tertiary aminosilazane and vinyl chloride to N,N-dimethylformamide solvent, wherein the mass ratio of tertiary aminosilazane to vinyl chloride is 1:1.3, stirring for 3 minutes, reacting at 60°C for 3 hours, and then rotary distilling, filtering, washing, and olefination of silazane; (4) adding alkenyl silazane to N,N-dimethylformamide solvent, stirring evenly, and then adding aqueous hydrogen peroxide solution thereto, wherein the mass ratio of alkenyl silazane to aqueous hydrogen peroxide solution is 1:2.4, stirring and reacting at 30° C. for 4 hours. After the reaction is completed, distilling under reduced pressure, washing, and drying to obtain quaternary ammonium salt modified silane; (5) Add 4 parts by weight of olefinic silazane, 3 parts by weight of vinyl carbon nanotubes, 6 parts by weight of acrylamide, and 4 parts by weight of acryl alcohol to N,N-dimethylformamide solvent, stir and disperse, then add 0.4 parts by weight of ammonium persulfate initiator, react at 110° C. for 5 h, and then perform rotary distillation and wash to obtain modified carbon nanotubes; (6) 10 parts by weight of polyethylene glycol, 3 parts by weight of silicon dioxide, 2 parts by weight of quaternary ammonium salt-modified silane, 4 parts by weight of polydimethylsiloxane, 8 parts by weight of modified carbon nanotubes, and 10 parts by weight of pentaerythritol stearate are added into a stirrer and stirred for 20 minutes to obtain a fluorine-free silicone lubricant for improving the processing performance of polyolefin resin.

[0017] Example 2 (1) adding divinyl glycol to chloroform solvent, stirring and dispersing, and then adding vinyl trichlorosilane thereto, wherein the mass ratio of divinyl glycol to vinyl trichlorosilane is 2.2:1, reacting at 90° C. for 14 h, and after the reaction, filtering, distilling under reduced pressure, washing, and drying to obtain an intermediate; (2) adding the intermediate and hexamethyldisilazane to toluene solvent, stirring evenly, and continuing to add chloroplatinic acid catalyst, wherein the mass ratio of the intermediate, hexamethyldisilazane, and chloroplatinic acid catalyst is 1:1.3:0.02, heating to 125°C, stirring and reflux reaction for 10 hours, after the reaction is completed, filtering and drying to obtain tertiary aminosilazane; (3) Adding tertiary aminosilazane and vinyl chloride to N,N-dimethylformamide solvent, wherein the mass ratio of tertiary aminosilazane to vinyl chloride is 1:1.5, stirring for 4 minutes, reacting at 75°C for 7 hours, and then rotary distilling, filtering, washing, and olefination of silazane; (4) adding alkenyl silazane to N,N-dimethylformamide solvent, stirring evenly, and then adding aqueous hydrogen peroxide solution thereto, wherein the mass ratio of alkenyl silazane to aqueous hydrogen peroxide solution is 1:3.2, stirring and reacting at 40° C. for 5 h. After the reaction is completed, distilling under reduced pressure, washing, and drying to obtain quaternary ammonium salt modified silane; (5) Add 7 parts by weight of olefinic silazane, 5 parts by weight of vinyl carbon nanotubes, 8 parts by weight of acrylamide, and 7 parts by weight of acryl alcohol to N,N-dimethylformamide solvent, stir and disperse, then add 0.8 parts by weight of ammonium persulfate initiator, react at 130° C. for 7 hours, and then perform rotary distillation and washing to obtain modified carbon nanotubes; (6) 15 parts by weight of polyethylene glycol, 5 parts by weight of silicon dioxide, 6 parts by weight of quaternary ammonium salt-modified silane, 8 parts by weight of polydimethylsiloxane, 14 parts by weight of modified carbon nanotubes, and 20 parts by weight of pentaerythritol stearate are added into a stirrer and stirred for 40 minutes to obtain a fluorine-free silicone lubricant for improving the processing performance of polyolefin resin.

[0018] Example 3 (1) adding divinyl glycol to chloroform solvent, stirring and dispersing, and then adding vinyl trichlorosilane thereto, wherein the mass ratio of divinyl glycol to vinyl trichlorosilane is 1.9:1, reacting at 82° C. for 11 h, and after the reaction, filtering, distilling under reduced pressure, washing, and drying to obtain an intermediate; (2) adding the intermediate and hexamethyldisilazane to toluene solvent, stirring evenly, and continuing to add chloroplatinic acid catalyst, wherein the mass ratio of the intermediate, hexamethyldisilazane, and chloroplatinic acid catalyst is 1:1.2:0.015, heating to 117°C, stirring and reflux reaction for 7.5h, after the reaction is completed, filtering and drying to obtain tertiary aminosilazane; (3) Adding tertiary aminosilazane and vinyl chloride to N,N-dimethylformamide solvent, wherein the mass ratio of tertiary aminosilazane to vinyl chloride is 1:1.4, stirring for 3.5 minutes, reacting at 70°C for 5 hours, and then rotary distilling, filtering, washing, and olefination of silazane; (4) adding alkenyl silazane to N,N-dimethylformamide solvent, stirring evenly, and then adding aqueous hydrogen peroxide solution thereto, wherein the mass ratio of alkenyl silazane to aqueous hydrogen peroxide solution is 1:2.8, stirring and reacting at 35° C. for 4.5 hours. After the reaction is completed, distilling under reduced pressure, washing, and drying to obtain quaternary ammonium salt modified silane; (5) Add 5.5 parts by weight of olefinic silazane, 4 parts by weight of vinyl carbon nanotubes, 7 parts by weight of acrylamide, and 5.5 parts by weight of acryl alcohol to N,N-dimethylformamide solvent, stir and disperse, then add 0.6 parts by weight of ammonium persulfate initiator, react at 120° C. for 6 hours, and then perform rotary distillation and wash to obtain modified carbon nanotubes; (6) 12.5 parts by weight of polyethylene glycol, 4 parts by weight of silicon dioxide, 4 parts by weight of quaternary ammonium salt-modified silane, 6 parts by weight of polydimethylsiloxane, 11 parts by weight of modified carbon nanotubes, and 15 parts by weight of pentaerythritol stearate are added into a stirrer and stirred for 30 minutes to obtain a fluorine-free silicone lubricant for improving the processing performance of polyolefin resin.

[0019] Example 4 (1) adding divinyl glycol to chloroform solvent, stirring and dispersing, and then adding vinyl trichlorosilane thereto, wherein the mass ratio of divinyl glycol to vinyl trichlorosilane is 1.6:1, reacting at 75° C. for 8 h, and after completion, filtering, vacuum distilling, washing, and drying to obtain an intermediate; (2) adding the intermediate and hexamethyldisilazane to toluene solvent, stirring evenly, and continuing to add chloroplatinic acid catalyst, wherein the mass ratio of the intermediate, hexamethyldisilazane, and chloroplatinic acid catalyst is 1:1.1:0.01, heating to 110°C, stirring and reflux reaction for 5 hours, after the reaction is completed, filtering and drying to obtain tertiary aminosilazane; (3) Adding tertiary aminosilazane and vinyl chloride to N,N-dimethylformamide solvent, wherein the mass ratio of tertiary aminosilazane to vinyl chloride is 1:1.5, stirring for 4 minutes, reacting at 75°C for 7 hours, and then rotary distilling, filtering, washing, and olefination of silazane; (4) adding alkenyl silazane to N,N-dimethylformamide solvent, stirring evenly, and then adding aqueous hydrogen peroxide solution thereto, wherein the mass ratio of alkenyl silazane to aqueous hydrogen peroxide solution is 1:3.2, stirring and reacting at 40° C. for 5 h. After the reaction is completed, distilling under reduced pressure, washing, and drying to obtain quaternary ammonium salt modified silane; (4) adding alkenyl silazane to N,N-dimethylformamide solvent, stirring evenly, and then adding aqueous hydrogen peroxide solution thereto, wherein the mass ratio of alkenyl silazane to aqueous hydrogen peroxide solution is 1:2.8, stirring and reacting at 35° C. for 4.5 hours. After the reaction is completed, distilling under reduced pressure, washing, and drying to obtain quaternary ammonium salt modified silane; (5) Add 5.5 parts by weight of olefinated silazane, 4 parts by weight of vinyl carbon nanotubes, 7 parts by weight of acrylamide, and 4 parts by weight of acryl alcohol to N,N-dimethylformamide solvent, stir and disperse, then add 0.6 parts by weight of ammonium persulfate initiator, react at 120° C. for 6 hours, and then perform rotary distillation and wash to obtain modified carbon nanotubes; (6) 12.5 parts by weight of polyethylene glycol, 4 parts by weight of silicon dioxide, 4 parts by weight of quaternary ammonium salt-modified silane, 6 parts by weight of polydimethylsiloxane, 11 parts by weight of modified carbon nanotubes, and 15 parts by weight of pentaerythritol stearate are added into a stirrer and stirred for 30 minutes to obtain a fluorine-free silicone lubricant for improving the processing performance of polyolefin resin.

[0020] Comparative Example 1 Compared with Example 4, this comparative example does not add modified carbon nanotubes.

[0021] Comparative Example 2 Compared with Example 4, this comparative example does not add quaternary ammonium salt-modified silane.

[0022] The fluorine-free silicone lubricants of Examples 1-4 and Comparative Examples 1-2 were mixed with polyolefin resins and extrusion tests were carried out on a Haake rheometer. The test results of extrusion time, extrusion torque, die pressure, and melt fracture are shown in Table 1.

[0023] Table 1: Fluorine-free silicone lubricant performance test.

[0024] project Melt fracture elimination time (min) Head pressure reduction (%) Torque reduction (%) Example 1 10 9.3 14.1 Example 2 9 9.7 16.3 Example 3 12 9.6 15.4 Example 4 9 9.4 15.6 Comparative Example 1 20 6.5 11.3 Comparative Example 2 21 5.8 10.6 As can be seen from Table 1, compared with the fluorine-free silicone lubricant prepared in Comparative Examples 1-2, the melt fracture elimination time is shortened, and the die pressure and torque are greatly reduced in Examples 1-4 of the present invention, indicating that the lubrication effect is better and the material flow rate is increased, the lubrication effect is improved, and the processing performance is improved.

[0025] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A fluorine-free silicone lubricant for improving the processing performance of polyolefin resins, characterized in that: The invention comprises the following components by weight: 10-15 parts by weight of polyethylene glycol, 3-5 parts by weight of silicon dioxide, 2-6 parts by weight of quaternary ammonium salt modified silane, 4-8 parts by weight of polydimethylsiloxane, 8-14 parts by weight of modified carbon nanotubes and 10-20 parts by weight of pentaerythritol stearate.

2. The fluorine-free silicone lubricant for improving the processing performance of polyolefin resin according to claim 1, characterized in that: The preparation method of the quaternary ammonium salt modified silane is: (1) Add divinyl glycol to chloroform solvent, stir and disperse, then add vinyl trichlorosilane, react at 75-90°C for 8-14h, filter, distill under reduced pressure, wash, and dry to obtain an intermediate; (2) Add the intermediate and hexamethyldisilazane to toluene solvent, stir evenly, continue to add chloroplatinic acid catalyst, raise the temperature to 110-125°C, stir and reflux for 5-10 hours, and after the reaction is completed, filter and dry to obtain tertiary aminosilazane; (3) Add tertiary aminosilazane and vinyl chloride to N,N-dimethylformamide solvent, stir for 3-4 minutes, react at 60-75°C for 3-7 hours, and then perform rotary distillation, filter, wash, and olefinate the silazane; (4) Add the alkenyl silazane to N,N-dimethylformamide solvent, stir evenly, then add hydrogen peroxide aqueous solution, stir and react at 30-40° C. for 4-5 hours. After the reaction is completed, distill under reduced pressure, wash and dry to obtain quaternary ammonium salt modified silane.

3. The fluorine-free silicone lubricant for improving the processing performance of polyolefin resin according to claim 2, characterized in that: The mass ratio of divinyl glycol to vinyl trichlorosilane in (1) is 1.6-2.2:

1.

4. The fluorine-free silicone lubricant for improving the processing performance of polyolefin resin according to claim 2, characterized in that: The mass ratio of the intermediate, hexamethyldisilazane and chloroplatinic acid catalyst in (2) is 1:1.1-1.3:0.01-0.

02.

5. The fluorine-free silicone lubricant for improving the processing performance of polyolefin resin according to claim 2, characterized in that: The mass ratio of tertiary aminosilazane to vinyl chloride in (3) is 1:1.3-1.

5.

6. The fluorine-free silicone lubricant for improving the processing performance of polyolefin resin according to claim 2, characterized in that: The mass ratio of alkenyl silazane to aqueous hydrogen peroxide solution in (4) is 1:2.4-3.

2.

7. The fluorine-free silicone lubricant for improving the processing performance of polyolefin resin according to claim 1, characterized in that: The preparation method of the modified carbon nanotubes comprises: adding 4-7 parts by weight of olefinic silazane, 3-5 parts by weight of vinyl carbon nanotubes, 6-8 parts by weight of acrylamide, and 4-7 parts by weight of acryl alcohol to N,N-dimethylformamide solvent, stirring and dispersing, then adding 0.4-0.8 parts by weight of ammonium persulfate initiator, reacting at 110-130° C. for 5-7 hours, and then performing rotary distillation and washing to obtain the modified carbon nanotubes.

8. A method for preparing a fluorine-free silicone lubricant for improving the processing performance of polyolefin resins as claimed in any one of claims 1 to 7, characterized in that: The preparation method of the fluorine-free organosilicon lubricant for improving the processing performance of polyolefin resin is as follows: polyethylene glycol, silicon dioxide, quaternary ammonium salt modified silane, polydimethylsiloxane, modified carbon nanotubes, and pentaerythritol stearate are added into a stirrer, and stirred for 20-40 minutes, and then the fluorine-free organosilicon lubricant for improving the processing performance of polyolefin resin is obtained.