Mineral oil defoaming agent for water-based paint printing ink and preparation method of mineral oil defoaming agent

Abstract

The invention discloses a mineral oil defoaming agent for water-based paint ink and a preparation method of the mineral oil defoaming agent, and belongs to the technical field of defoaming agents. A hydroxyl-terminated butenyl polymer and hydrogen-containing silicone oil are used for preparing a modified butenyl polymer under the condition of a platinum catalyst; and preparing the mineral oil defoaming agent from the obtained modified butenyl polymer, mineral oil, white carbon black, fatty acid metal soap and wax under the action of an emulsifier. The mineral oil defoaming agent prepared by the invention not only has the advantage of high defoaming speed of a conventional mineral oil defoaming agent, but also has improved compatibility and stability, is a defoaming agent with strong defoaming ability, good foam inhibition performance, good compatibility with paint and ink and reduced coating shrinkage phenomenon, and has good application prospects in the fields of paint and ink. The method has a wide application prospect especially in the field of home decoration water-based paint ink.

Description

Technical Field

[0001] The invention belongs to the technical field of defoamers, and particularly relates to a mineral oil defoamer used in the fields of water-based coatings and inks and a preparation method thereof. Background Art

[0002] In recent years, with the gradual advancement of urbanization in my country and the booming real estate markets in first- and second-tier cities, the output of architectural coatings has shown an annual growth trend.

[0003] Defoamers are essential additives in the production of architectural coatings. Their use requires not only stability and excellent foam suppression performance, but also good compatibility with the foaming system. Currently, defoamers used in the water-based architectural coatings industry are primarily divided into two categories: silicones and mineral oils. However, silicone products are not compatible with water-based systems and can easily cause problems such as cratering and edge shrinkage in the coating. Mineral oil defoamers, primarily composed of mineral oil, fatty acid metal soaps, fatty acid amides, fatty alcohols, and polyethers, have good dispersibility in water-based systems. While their compatibility is better than silicone defoamers, they lack certain deficiencies in foam suppression performance.

[0004] Patent CN200510088437.6 introduces a coating defoamer with three different hydrocarbon structures as carriers, fatty acid aluminum and silicon dioxide as main defoaming substances. However, when some alkyl-modified silicone oils with substituents of 2 to 6 carbon atoms are introduced, coating defects are easily caused. CN201010584403.7 introduces a processing method for a defoamer containing fatty acid aluminum and fatty acid amide. CN200910232532.7, CN201010550336.7, and CN201010549369 all describe defoamers containing silica, but none mention the poor stability and coating defects associated with silica-based defoamers, nor the insufficient foam removal and suppression capabilities of silica- and mineral oil-based defoamers. CN101310814 describes a defoaming system combining mineral oil and silicone grease, which improves foam removal and suppression capabilities but can cause severe cratering and edge shrinkage issues when used in water-based coatings. CN109589653A provides a low-molecular-weight polymer with a molecular weight of 200-1300, which does not achieve ideal results in terms of rapid defoaming and compatibility. The document "Modification of Soybean Oil and Its Application in Defoaming Agents" introduces that the compounding of mineral oil and soybean oil within a certain range improves the stability of the defoaming agent system, but fails to solve a series of problems brought about by the defoaming system with alkyl silicone oil and hydrophobic silica as active components, such as poor compatibility, poor stability, poor defoaming and suppression performance, and poor coating quality. Summary of the Invention

[0005] In view of this, the present invention aims to develop a mineral oil defoamer with good compatibility and high stability. The obtained defoamer can quickly eliminate foam and effectively inhibit foam in the water-based coating and ink industry.

[0006] The present invention provides a method for preparing a mineral oil defoamer, comprising the following steps:

[0007] S1. Under the protection of inert gas N2, add the butene-based polymer and hydrogenated silicone oil into a reaction vessel, stir evenly, increase the temperature to 70-90°C, add a platinum catalyst, continue to increase the temperature to 120-140°C, and keep warm for 2 hours to obtain a modified butene-based polymer;

[0008] S2. Mix mineral oil and white carbon black in a container and disperse at high speed at a speed of 2500-3000 rpm for 1.5-2 hours to obtain a mixture A;

[0009] S3, adding fatty acid metal soap and wax to mixture A in order, starting stirring and heating, raising the temperature to 90-110° C. at a speed of 200-500 rpm, and keeping warm for 0.5-1 hour to obtain mixture B;

[0010] S4, adding the modified butene-based polymer prepared in advance to mixture B, continuing to raise the temperature to 90-110° C., and keeping the temperature for 0.5-1 hour;

[0011] S5. After the heat preservation is completed, the temperature is quickly lowered to 50-60°C, and a nonionic emulsifier is added, and the temperature is kept at 50-60°C for 0.5-1h;

[0012] S6. After the heat preservation is completed, the temperature is rapidly cooled again to below 20° C., and the mixture is passed through a high-pressure homogenizer and degassed for 1-2 hours to obtain the mineral oil defoaming agent of the present invention.

[0013] In the preparation method described in the present invention, the mineral oil defoamer includes the following components in parts by weight: 70%-90% mineral oil, 2%-6% white carbon black, 2%-5% fatty acid metal soap, 0.5%-3% wax, 3%-8% nonionic emulsifier, and 2%-10% modified butene-based polymer.

[0014] In the preparation method of the present invention, the mineral oil is one or more of low-viscosity white oil and naphthenic oil. Specifically, the viscosity of the mineral oil is 5-30 mPa·s.

[0015] In the preparation method of the present invention, the white carbon black is selected from hydrophilic white carbon black, specifically a white carbon black with a specific surface area of 130-180m 2 / g of hydrophilic fumed silica and / or hydrophilic precipitated silica.

[0016] In the preparation method of the present invention, the fatty acid metal soap includes but is not limited to one of magnesium salt, aluminum salt, calcium salt, and zinc salt, or a mixture of any two or more thereof; preferably fatty acid aluminum.

[0017] In the preparation method of the present invention, the wax is wax powder, including one or more of polyethylene wax, oxidized polyethylene wax, Fischer-Tropsch wax, and polyamide wax.

[0018] In the preparation method described in the present invention, the nonionic emulsifier includes one or more of polyoxyethylene sorbitan monostearate (Tween 60), polyoxyethylene sorbitan monooleate (Tween 80), polyoxyethylene sorbitan trioleate (Tween 85), sorbitan monolaurate (Span 20), sorbitan monopalmitate (Span 40), sorbitan monostearate (Span 60), glyceryl tristearate, glyceryl monostearate, pentaerythritol glyceryl stearate, ethylene glycol monostearate, ethylene glycol distearate, diethylene glycol monostearate, and diethylene glycol distearate.

[0019] In the preparation method of the present invention, the butene-based polymer in the modified butene-based polymer is selected from hydroxyl-terminated polyisobutylene or hydroxyl-terminated polybutadiene, preferably hydroxyl-terminated polybutadiene. The structural formula of the hydroxyl-terminated polyisobutylene is HO-[CH2-C(CH3)2] m -OH, molecular weight is 500-5000; the molecular formula of the hydroxy-terminated polybutadiene is HO-(CH2-CH=CH-CH2) n -OH is a telechelic polymer terminated with hydroxyl groups at both ends. The polybutadiene of the present invention is selected from a group with a molecular weight of 500-5000.

[0020] In the preparation method of the present invention, the hydrogenated silicone oil in the modified butene-based polymer is selected from a silicone oil having a viscosity of 10-200 mPa·s and a hydrogen content of 0.05-0.3%.

[0021] In the preparation method of the present invention, the mass ratio of hydrogenated silicone oil to polybutadiene in the modified butene-based polymer is 1:1.1-1.3.

[0022] In the preparation method of the present invention, the platinum catalyst in the modified butene-based polymer is a chloroplatinic acid catalyst with an amount of 40-80 ppm.

[0023] The present invention is different from conventional low molecular weight polymers and mineral oil patents. It uses high molecular weight terminal hydroxyl butene polymers to perform modification treatment. High molecular weight terminal hydroxyl polyisobutylene or polybutadiene can provide excellent fast defoaming performance and excellent stability due to its special network structure. DETAILED DESCRIPTION

[0024] Example 1

[0025] S1. Under the protection of inert gas N2, 2.4 parts of hydroxy-terminated polybutadiene with a molecular weight of 800 and 2.6 parts of hydrogen-containing silicone oil with a viscosity of 20 mPa·s and a hydrogen content of 0.05% were added to a reaction vessel, stirred evenly, and the temperature was raised to 80°C. 50 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 125°C. After keeping the temperature for 2 hours, a modified butene-based polymer 1 was obtained.

[0026] S2, 81 parts of white oil with a viscosity of 20 mPa·s and 5 parts of a specific surface area of 130m 2 / g of hydrophilic precipitated silica was mixed and placed in a container, and dispersed at a high speed of 3000 rpm for 2 h to obtain a mixture A1;

[0027] S3, adding 4 parts of aluminum butyrate and 1.8 parts of polyethylene wax to mixture A1 in sequence, starting stirring and heating, raising the temperature to 100° C. at a speed of 500 rpm, and keeping the temperature for 0.5 h to obtain mixture B1;

[0028] S4, adding the modified butene-based polymer 1 prepared in advance to the mixture B1, and continuing to raise the temperature to 100° C. and keep warm for 0.5 h;

[0029] S5. After the heat preservation is completed, the temperature is quickly lowered to 55°C, 3.2 parts of polyoxyethylene sorbitan monostearate (Tween 60) are added, and the temperature is kept at 55°C for 0.5 h.

[0030] S6. After the heat preservation is completed, the temperature is rapidly cooled again to 20° C., and the mixture is passed through a high-pressure homogenizer and degassed for 1 hour to obtain the mineral oil defoaming agent of the present invention.

[0031] Example 2

[0032] S1. Under the protection of inert gas N2, 4.1 parts of hydroxy-terminated polybutadiene with a molecular weight of 2000 and 4.9 parts of hydrogen-containing silicone oil with a viscosity of 60 mPa·s and a hydrogen content of 0.1% were added to a reaction vessel, stirred evenly, and the temperature was raised to 90°C. 70 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 130°C. After keeping the temperature for 2 hours, a modified butene-based polymer 2 was obtained.

[0033] S2, 70 parts of naphthenic oil with a viscosity of 30 mPa·s and 6 parts of a specific surface area of 180m 2 / g of hydrophilic precipitated silica was mixed and placed in a container, and dispersed at a high speed of 2500 rpm for 2 hours to obtain a mixture A2;

[0034] S3, adding 5 parts of aluminum stearate, 2 parts of Fischer-Tropsch wax and oxidized polyethylene wax to mixture A2 in order, starting stirring and heating, raising the temperature to 110° C. at a speed of 200 rpm, and keeping the temperature for 0.5 h to obtain mixture B2;

[0035] S4, adding the modified butene-based polymer 2 prepared in advance to the mixture B2, and continuing to raise the temperature to 110° C. and keep warm for 0.5 h;

[0036] S5. After the heat preservation is completed, the temperature is quickly lowered to 60°C, 8 parts of sorbitan monolaurate (Span20) are added, and the temperature is kept at 60°C for 1 hour;

[0037] S6. After the heat preservation is completed, the temperature is rapidly cooled again to 18° C., and the mixture is passed through a high-pressure homogenizer and degassed for 1 hour to obtain the mineral oil defoaming agent of the present invention.

[0038] Example 3

[0039] S1. Under the protection of inert gas N2, 2.6 parts of hydroxy-terminated polybutadiene with a molecular weight of 3000 and 3.4 parts of hydrogen-containing silicone oil with a viscosity of 10 mPa·s and a hydrogen content of 0.05% were added to a reaction vessel, stirred evenly, and the temperature was raised to 70°C. 60 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 130°C. After keeping the temperature for 2 hours, a modified butene-based polymer 3 was obtained.

[0040] S2, 85 parts of naphthenic oil with a viscosity of 5 mPa·s and 2 parts of a specific surface area of 180m 2 / g of hydrophilic fumed silica was mixed and placed in a container, and dispersed at a high speed of 2500 rpm for 2 hours to obtain a mixture A3;

[0041] S3, adding 2.5 parts of zinc stearate, 0.5 parts of Fischer-Tropsch wax and oxidized polyethylene wax to mixture A3 in order, stirring and heating, raising the temperature to 105° C. at a speed of 500 rpm, and keeping the temperature for 1 hour to obtain mixture B3;

[0042] S4, adding the modified butene-based polymer 3 prepared in advance to the mixture B3, and continuing to raise the temperature to 105° C. and keep warm for 1 hour;

[0043] S5. After the heat preservation is completed, the temperature is quickly lowered to 55°C, 4 parts of tristearin are added, and the temperature is kept at 55°C for 1 hour;

[0044] S6. After the heat preservation is completed, the temperature is rapidly cooled again to 18° C., and the mixture is passed through a high-pressure homogenizer and degassed for 1 hour to obtain the mineral oil defoaming agent of the present invention.

[0045] Example 4

[0046] S1. Under the protection of inert gas N2, 4.3 parts of hydroxy-terminated polybutadiene with a molecular weight of 5000 and 5.7 parts of hydrogen-containing silicone oil with a viscosity of 50 mPa·s and a hydrogen content of 0.1% were added to a reaction vessel, stirred evenly, and the temperature was raised to 70°C. 80 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 140°C. After keeping the temperature for 2 hours, a modified butene-based polymer 4 was obtained.

[0047] S2, 73 parts of white oil with a viscosity of 15 mPa·s and 3 parts of a specific surface area of 150m 2 / g of hydrophilic fumed silica was mixed and placed in a container, and dispersed at a high speed of 3000 rpm for 1.8 hours to obtain a mixture A4;

[0048] S3, adding 3 parts of calcium stearate, 3 parts of a mixture of Fischer-Tropsch wax and polyamide wax to mixture A4 in sequence, starting stirring and heating, raising the temperature to 100° C. at a speed of 300 rpm, and keeping the temperature for 0.8 h to obtain mixture B4;

[0049] S4, adding the modified butene-based polymer 4 prepared in advance to the mixture B4, and continuing to raise the temperature to 100° C. and keep warm for 0.8 h;

[0050] S5. After the heat preservation is completed, the temperature is quickly lowered to 55°C, 8 parts of diethylene glycol monostearate are added, and the temperature is kept at 55°C for 1 hour;

[0051] S6. After the heat preservation is completed, the temperature is rapidly cooled again to 18° C., and the mixture is passed through a high-pressure homogenizer and degassed for 2 hours to obtain the mineral oil defoaming agent of the present invention.

[0052] Example 5

[0053] S1. Under the protection of inert gas N2, 1.3 parts of hydroxy-terminated polybutadiene with a molecular weight of 4000 and 1.7 parts of hydrogen-containing silicone oil with a viscosity of 100 mPa·s and a hydrogen content of 0.2% were added to a reaction vessel, stirred evenly, and the temperature was raised to 90°C. 42 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 120°C. After keeping the temperature for 2 hours, a modified butene-based polymer 5 was obtained.

[0054] S2, 85 parts of white oil with a viscosity of 25 mPa·s and 4 parts of a specific surface area of 140m 2 / g of hydrophilic fumed silica was mixed and placed in a container, and dispersed at a high speed of 2800 rpm for 1.7 hours to obtain a mixture A5;

[0055] S3, adding 2 parts of magnesium stearate and 0.5 parts of Fischer-Tropsch wax to mixture A5 in sequence, starting stirring and heating, raising the temperature to 90° C. at a speed of 400 rpm, and keeping the temperature for 0.6 h to obtain mixture B5;

[0056] S4, adding the modified butene-based polymer 5 prepared in advance to the mixture B5, and continuing to raise the temperature to 90° C. and keep the temperature for 0.6 h;

[0057] S5, after the end of the heat preservation, quickly cool to 50 ° C, add 5.5 parts of ethylene glycol monostearate, and keep at 50 ° C for 0.5 h;

[0058] S6. After the heat preservation is completed, the temperature is rapidly cooled again to 20° C., and the mixture is passed through a high-pressure homogenizer and degassed for 2 hours to obtain the mineral oil defoaming agent of the present invention.

[0059] Example 6

[0060] S1. Under the protection of inert gas N2, 0.9 parts of hydroxy-terminated polybutadiene with a molecular weight of 1000 and 1.1 parts of hydrogen-containing silicone oil with a viscosity of 200 mPa·s and a hydrogen content of 0.3% were added to a reaction vessel, stirred evenly, and the temperature was raised to 80°C. 40 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 120°C. After keeping the temperature for 2 hours, a modified butene-based polymer 6 was obtained.

[0061] S2, 90 parts of a mixture of white oil with a viscosity of 20 mPa·s and naphthenic oil with a viscosity of 30 mPa·s and 2 parts of a 2 / g of hydrophilic fumed silica was placed in a container and dispersed at a high speed of 2600 rpm for 1.6 h to obtain a mixture A6;

[0062] S3. Add 2 parts of a mixture of magnesium stearate and aluminum stearate and 1 part of Fischer-Tropsch wax to mixture A6 in this order, start stirring and heating, raise the temperature to 90° C. at 400 rpm, and keep warm for 0.6 h to obtain mixture B6;

[0063] S4, adding the modified butene-based polymer 6 prepared in advance to the mixture B6, and continuing to raise the temperature to 90° C. and keep the temperature for 0.6 h;

[0064] S5. After the heat preservation is completed, the temperature is quickly lowered to 50°C, and a mixture of 3 parts of diethylene glycol monostearate and polyoxyethylene sorbitan monooleate (Tween 80) is added, and the mixture is kept at 50°C for 0.5 h.

[0065] S6. After the heat preservation is completed, the temperature is rapidly cooled again to 15° C., and the mixture is passed through a high-pressure homogenizer and degassed for 2 hours to obtain the mineral oil defoaming agent of the present invention.

[0066] Example 7

[0067] S1. Under the protection of inert gas N2, 3.6 parts of hydroxy-terminated polyisobutylene with a molecular weight of 500 and 4.4 parts of hydrogen-containing silicone oil with a viscosity of 110 mPa·s and a hydrogen content of 0.2% were added to a reaction vessel, stirred evenly, and the temperature was raised to 75°C. 75 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 135°C. After keeping the temperature for 2 hours, a modified butene-based polymer 7 was obtained.

[0068] S2, 81 parts of a mixture of white oil with a viscosity of 5 mPa·s and naphthenic oil with a viscosity of 10 mPa·s and 2 parts of a 2 / g of hydrophilic fumed silica was mixed in a container and dispersed at a high speed of 2600 rpm for 1.5 h to obtain a mixture A7;

[0069] S3, adding 2.2 parts of a mixture of calcium stearate and zinc stearate and 1.8 parts of oxidized polyethylene wax to mixture A7 in sequence, starting stirring and heating, raising the temperature to 95° C. at a speed of 350 rpm, and keeping the temperature for 0.6 h to obtain mixture B7;

[0070] S4, adding the modified butene-based polymer 7 prepared in advance to the mixture B7, and continuing to raise the temperature to 95° C. and keep the temperature for 0.6 h;

[0071] S5. After the heat preservation is completed, the temperature is quickly lowered to 60°C, and 5 parts of a mixture of polyoxyethylene sorbitan trioleate (Tween85) and sorbitan monopalmitate (Span40) are added, and the mixture is kept at 60°C for 0.5 h.

[0072] S6. After the heat preservation is completed, the temperature is rapidly cooled again to 15° C., and the mixture is passed through a high-pressure homogenizer and degassed for 2 hours to obtain the mineral oil defoaming agent of the present invention.

[0073] Example 8

[0074] S1. Under the protection of inert gas N2, 3.9 parts of hydroxy-terminated polyisobutylene with a molecular weight of 1500 and 5.1 parts of hydrogen-containing silicone oil with a viscosity of 30 mPa·s and a hydrogen content of 0.05% were added to a reaction vessel, stirred evenly, and the temperature was raised to 75°C. 80 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 140°C. After keeping the temperature for 2 hours, a modified butene-based polymer 8 was obtained.

[0075] S2, 82 parts of a mixture of white oil with a viscosity of 15 mPa·s and naphthenic oil with a viscosity of 30 mPa·s and 2 parts of a 2 / g of hydrophilic fumed silica was mixed and placed in a container, and dispersed at a high speed of 2600 rpm for 1.5 hours to obtain a mixture A8;

[0076] S3, adding 3.5 parts of a mixture of calcium stearate and aluminum butyrate and 0.5 parts of a mixture of oxidized polyethylene wax and polyamide wax to mixture A8 in that order, stirring and heating, raising the temperature to 105° C. at a speed of 350 rpm, and keeping the temperature for 0.8 h to obtain mixture B8;

[0077] S4, adding the modified butene-based polymer 8 prepared in advance to the mixture B8, and continuing to raise the temperature to 105° C. and keep warm for 0.8 h;

[0078] S5. After the heat preservation is completed, the temperature is quickly lowered to 60°C, and a mixture of 3 parts of sorbitan monostearate (Span60) and glyceryl monostearate is added, and the mixture is kept at 60°C for 0.8h.

[0079] S6. After the heat preservation is completed, the temperature is rapidly cooled again to 15° C., and the mixture is passed through a high-pressure homogenizer and degassed for 1.5 hours to obtain the mineral oil defoaming agent of the present invention.

[0080] Example 9

[0081] S1. Under the protection of inert gas N2, 0.9 parts of hydroxy-terminated polybutadiene with a molecular weight of 3500 and 1.1 parts of hydrogen-containing silicone oil with a viscosity of 120 mPa·s and a hydrogen content of 0.25% were added to a reaction vessel, stirred evenly, and the temperature was raised to 70°C. 40 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 120°C. After keeping the temperature for 2 hours, a modified butene-based polymer 9 was obtained.

[0082] S2, 80 parts of a mixture of white oil with a viscosity of 30 mPa·s and naphthenic oil with a viscosity of 5 mPa·s and 5 parts of a 2 / g of hydrophilic precipitated silica was mixed and placed in a container, and dispersed at a high speed of 2800 rpm for 1.6 hours to obtain a mixture A9;

[0083] S3, adding 4 parts of a mixture of calcium stearate and calcium stearate, and 3 parts of a mixture of polyethylene wax and polyamide wax to mixture A9 in sequence, starting stirring and heating, raising the temperature to 110° C. at a speed of 250 rpm, and keeping warm for 0.8 h to obtain mixture B9;

[0084] S4, adding the modified butene-based polymer 9 prepared in advance to the mixture B9, and continuing to raise the temperature to 110° C. and keep the temperature for 0.8 h;

[0085] S5. After the heat preservation is completed, the temperature is quickly lowered to 55°C, and a mixture of 6 parts of polyoxyethylene sorbitan monooleate (Tween 80) and ethylene glycol monostearate is added, and the mixture is kept at 55°C for 0.8h.

[0086] S6. After the heat preservation is completed, the temperature is rapidly cooled again to 18° C., and the mixture is passed through a high-pressure homogenizer and degassed for 1.5 hours to obtain the mineral oil defoaming agent of the present invention.

[0087] Example 10

[0088] S1. Under the protection of inert gas N2, 2.4 parts of hydroxy-terminated polyisobutylene with a molecular weight of 2500 and 2.6 parts of hydrogen-containing silicone oil with a viscosity of 180 mPa·s and a hydrogen content of 0.28% were added to a reaction vessel, stirred evenly, and the temperature was raised to 85°C. 45 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 120°C. After maintaining the temperature for 2 hours, a modified butene-based polymer 10 was obtained.

[0089] S2, 78 parts of a mixture of white oil with a viscosity of 25 mPa·s and naphthenic oil with a viscosity of 10 mPa·s and 6 parts of a 2 A mixture of hydrophilic fumed silica and hydrophilic precipitated silica of 100 g / g was placed in a container and dispersed at a high speed of 2800 rpm for 1.8 h to obtain a mixture A10.

[0090] S3. Add 5 parts of aluminum dioctoate and 0.5 parts of polyamide wax to mixture A10 in sequence, start stirring and heating, raise the temperature to 100° C. at a speed of 250 rpm, and keep warm for 1 hour to obtain mixture B10;

[0091] S4, adding the modified butene-based polymer 10 prepared in advance to the mixture B10, and continuing to heat to 100° C. and keep warm for 1 hour;

[0092] S5, after the insulation is completed, the temperature is quickly lowered to 60°C, 5.5 parts of a mixture of diethylene glycol monostearate and tristearin are added, and the mixture is kept at 60°C for 0.7h;

[0093] S6. After the heat preservation is completed, the temperature is rapidly cooled again to 15° C., and the mixture is passed through a high-pressure homogenizer and degassed for 1.5 hours to obtain the mineral oil defoaming agent of the present invention.

[0094] Example 11

[0095] S1. Under the protection of inert gas N2, 3.8 parts of hydroxy-terminated polyisobutylene with a molecular weight of 2500 and 4.2 parts of hydrogen-containing silicone oil with a viscosity of 150 mPa·s and a hydrogen content of 0.26% were added to a reaction vessel, stirred evenly, and the temperature was raised to 85°C. 65 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 125°C. After maintaining the temperature for 2 hours, a modified butene-based polymer 11 was obtained.

[0096] S2, 72 parts of a mixture of white oil with a viscosity of 5 mPa·s and naphthenic oil with a viscosity of 20 mPa·s and 4 parts of a 2 A mixture of hydrophilic precipitated silica and hydrophilic fumed silica of 100 g / g was placed in a container and dispersed at a high speed of 2500 rpm for 2 h to obtain a mixture A11.

[0097] S3. Add 5 parts of a mixture of aluminum dioctoate and aluminum stearate and 3 parts of a mixture of polyamide wax and oxidized polyethylene wax to mixture A11 in that order, start stirring and heating, raise the temperature to 100° C. at 200 rpm, and keep warm for 1 hour to obtain mixture B11;

[0098] S4, adding the modified butene-based polymer 11 prepared in advance to the mixture B11, and continuing to raise the temperature to 100° C. and keep warm for 1 hour;

[0099] S5. After the heat preservation is completed, the temperature is quickly lowered to 60°C, and then 8 parts of a mixture of polyoxyethylene sorbitan monostearate (Tween 60) and diethylene glycol distearate are added, and the mixture is kept at 60°C for 0.7h.

[0100] S6. After the heat preservation is completed, the temperature is rapidly cooled again to 16° C., and the mixture is passed through a high-pressure homogenizer and degassed for 1.5 hours to obtain the mineral oil defoaming agent of the present invention.

[0101] Example 12

[0102] S1. Under the protection of inert gas N2, 2.9 parts of hydroxy-terminated polyisobutylene with a molecular weight of 1000 and 3.1 parts of hydrogen-containing silicone oil with a viscosity of 80 mPa·s and a hydrogen content of 0.15% were added to a reaction vessel, stirred evenly, and the temperature was raised to 90°C. 60 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 130°C. After maintaining the temperature for 2 hours, the modified butene-based polymer 12 was obtained.

[0103] S2, 86 parts of naphthenic oil with a viscosity of 10 mPa·s and 2 parts of a specific surface area of 140m 2 A mixture of hydrophilic fumed silica and hydrophilic precipitated silica of 100 g / g was placed in a container and dispersed at a high speed of 3000 rpm for 1.6 h to obtain a mixture A12.

[0104] S3. Add 2.5 parts of a mixture of aluminum dioctoate and aluminum butyrate and 0.5 parts of a mixture of polyamide wax and oxidized polyethylene wax to mixture A12 in that order, start stirring and heating, raise the temperature to 105° C. at a speed of 450 rpm, and keep warm for 1.7 hours to obtain mixture B12;

[0105] S4, adding the modified butene-based polymer 12 prepared in advance to the mixture B12, and continuing to raise the temperature to 105° C. and keep warm for 1.7 hours;

[0106] S5, after the heat preservation is completed, the temperature is quickly lowered to 50°C, 3 parts of a mixture of glyceryl monostearate and diethylene glycol distearate are added, and the mixture is kept at 50°C for 0.8h;

[0107] S6. After the heat preservation is completed, the temperature is rapidly cooled again to 16° C., and the mixture is passed through a high-pressure homogenizer and degassed for 1.5 hours to obtain the mineral oil defoaming agent of the present invention.

[0108] Comparative Example 1

[0109] S1, 81 parts of white oil with a viscosity of 20 mPa·s and 5 parts of a specific surface area of 130m 2 / g of hydrophilic precipitated silica was mixed and placed in a container, and dispersed at a high speed of 3000 rpm for 2 h to obtain a mixture A13;

[0110] S2. 4 parts of aluminum butyrate and 1.8 parts of polyethylene wax were added to mixture A13 in sequence, and the mixture was stirred and heated. The temperature was raised to 100° C. at a speed of 500 rpm and kept warm for 0.5 h to obtain mixture B13.

[0111] S3, adding 2.6 parts of a polyisobutylene polymer with a molecular weight of 1100 to the mixture B13, and continuing to raise the temperature to 100°C and keep warm for 0.5h;

[0112] S4, after the heat preservation is completed, the temperature is quickly lowered to 55°C, 3.2 parts of polyoxyethylene sorbitan monostearate (Tween 60) are added, and the temperature is kept at 55°C for 0.5h;

[0113] S5. After the heat preservation is completed, the temperature is rapidly cooled again to 20° C., and the mixture is passed through a high-pressure homogenizer and degassed for 1 hour to obtain the mineral oil defoaming agent of the present invention.

[0114] Comparative Example 2

[0115] S1. Under the protection of inert gas N2, 4.1 parts of hydroxy-terminated polybutadiene with a molecular weight of 2000 and 4.9 parts of hydrogen-containing silicone oil with a viscosity of 60 mPa·s and a hydrogen content of 0.1% were added to a reaction vessel, stirred evenly, and the temperature was raised to 90°C. 70 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 130°C. After maintaining the temperature for 2 hours, a modified butene-based polymer 14 was obtained.

[0116] S2, in order to mix 70 parts of cyclohexane oil with a viscosity of 30 mPa·s and 6 parts of a specific surface area of 180m 2A mixture of 100 g of hydrophilic precipitated silica, 5 parts of aluminum stearate, 2 parts of Fischer-Tropsch wax and oxidized polyethylene wax was added to the modified butene-based polymer 14, and the temperature was raised to 110° C. and kept warm for 0.5 h.

[0117] S3. After the heat preservation is completed, the temperature is quickly lowered to 60°C, 8 parts of sorbitan monolaurate (Span20) are added, and the temperature is kept at 60°C for 1 hour;

[0118] S4. After the heat preservation is completed, the temperature is rapidly cooled again to 18° C., and the mixture is passed through a high-pressure homogenizer and degassed for 1 hour to obtain the mineral oil defoaming agent of the present invention.

[0119] Comparative Example 3

[0120] S1. Under the protection of inert gas N2, 2.6 parts of hydroxy-terminated polybutadiene with a molecular weight of 3000 and 3.4 parts of hydrogen-containing silicone oil with a viscosity of 10 mPa·s and a hydrogen content of 0.05% were added to a reaction vessel, stirred evenly, and the temperature was raised to 70°C. 60 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 130°C. After keeping the temperature for 2 hours, a modified butene-based polymer 3 was obtained.

[0121] S2, 85 parts of naphthenic oil with a viscosity of 5 mPa·s and 2 parts of a specific surface area of 180m 2 / g of hydrophilic fumed silica was mixed and placed in a container, and dispersed at a high speed of 2500 rpm for 2 hours to obtain a mixture A3;

[0122] S3, adding 2.5 parts of zinc stearate, 0.5 parts of Fischer-Tropsch wax and oxidized polyethylene wax to mixture A3 in order, stirring and heating, raising the temperature to 105° C. at a speed of 500 rpm, and keeping the temperature for 1 hour to obtain mixture B3;

[0123] S4, adding the modified butene-based polymer 3 prepared in advance to the mixture B3, and continuing to raise the temperature to 105° C. and keep warm for 1 hour;

[0124] S5. After the heat preservation is completed, the temperature is quickly lowered to 18° C., and the mixture is passed through a high-pressure homogenizer and degassed for 1 hour to obtain the mineral oil defoaming agent of the present invention.

[0125] Comparative Example 4

[0126] S1. Under the protection of inert gas N2, 4.3 parts of hydroxy-terminated polybutadiene with a molecular weight of 5000 and 5.7 parts of hydrogen-containing silicone oil with a viscosity of 50 mPa·s and a hydrogen content of 0.1% were added to a reaction vessel, stirred evenly, and the temperature was raised to 70°C. 80 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 140°C. After keeping the temperature for 2 hours, a modified butene-based polymer 4 was obtained.

[0127] S2, 73 parts of white oil with a viscosity of 15 mPa·s and 3 parts of a specific surface area of 150m 2 / g of hydrophilic fumed silica was mixed and placed in a container, and dispersed at a high speed of 3000 rpm for 1.8 hours to obtain a mixture A4;

[0128] S3, adding 3 parts of calcium stearate, 3 parts of a mixture of Fischer-Tropsch wax and polyamide wax to mixture A4 in sequence, starting stirring and heating, raising the temperature to 100° C. at a speed of 300 rpm, and keeping the temperature for 0.8 h to obtain mixture B4;

[0129] S4, adding the modified butene-based polymer 4 prepared in advance to the mixture B4, and continuing to raise the temperature to 100° C. and keep warm for 0.8 h;

[0130] S5. After the heat preservation is completed, the temperature is quickly lowered to 55°C, 8 parts of diethylene glycol monostearate are added, and the temperature is kept at 55°C for 1 hour;

[0131] S6. After the heat preservation is completed, the temperature is rapidly cooled again to 28° C., and the mixture is passed through a high-pressure homogenizer and degassed for 2 hours to obtain the mineral oil defoaming agent of the present invention.

[0132] Comparative Example 5

[0133] S1. Under the protection of inert gas N2, 1.3 parts of hydroxy-terminated polybutadiene with a molecular weight of 4000 and 1.7 parts of hydrogen-containing silicone oil with a viscosity of 100 mPa·s and a hydrogen content of 0.2% were added to a reaction vessel, stirred evenly, and the temperature was raised to 90°C. 42 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 120°C. After keeping the temperature for 2 hours, a modified butene-based polymer 5 was obtained.

[0134] S2, 85 parts of mechanical oil with a viscosity of 60 mPa·s and 4 parts of a specific surface area of 140m 2 / g of hydrophilic fumed silica was mixed and placed in a container, and dispersed at a high speed of 2800 rpm for 1.7 hours to obtain a mixture A5;

[0135] S3, adding 2 parts of magnesium stearate and 0.5 parts of Fischer-Tropsch wax to mixture A5 in sequence, starting stirring and heating, raising the temperature to 90° C. at a speed of 400 rpm, and keeping the temperature for 0.6 h to obtain mixture B5;

[0136] S4, adding the modified butene-based polymer 5 prepared in advance to the mixture B5, and continuing to raise the temperature to 90° C. and keep the temperature for 0.6 h;

[0137] S5, after the end of the heat preservation, quickly cool to 50 ° C, add 5.5 parts of ethylene glycol monostearate, and keep at 50 ° C for 0.5 h;

[0138] S6. After the heat preservation is completed, the temperature is rapidly cooled again to 20° C., and the mixture is passed through a high-pressure homogenizer and degassed for 2 hours to obtain the mineral oil defoaming agent of the present invention.

[0139] Comparative Example 6

[0140] S1. Under the protection of inert gas N2, 1.5 parts of hydroxy-terminated polybutadiene with a molecular weight of 1000 and 0.5 parts of hydrogen-containing silicone oil with a viscosity of 200 mPa·s and a hydrogen content of 0.3% were added to a reaction vessel, stirred evenly, and the temperature was raised to 80°C. 40 ppm of chloroplatinic acid catalyst was added, and the temperature was further raised to 120°C. After keeping the temperature for 2 hours, a modified butene-based polymer 6 was obtained.

[0141] S2, 90 parts of a mixture of white oil with a viscosity of 20 mPa·s and naphthenic oil with a viscosity of 30 mPa·s and 2 parts of a 2 / g of hydrophilic fumed silica was placed in a container and dispersed at a high speed of 2600 rpm for 1.6 h to obtain a mixture A6;

[0142] S3. Add 2 parts of a mixture of magnesium stearate and aluminum stearate and 1 part of Fischer-Tropsch wax to mixture A6 in this order, start stirring and heating, raise the temperature to 90° C. at 400 rpm, and keep warm for 0.6 h to obtain mixture B6;

[0143] S4, adding the modified butene-based polymer 6 prepared in advance to the mixture B6, and continuing to raise the temperature to 90° C. and keep the temperature for 0.6 h;

[0144] S5. After the heat preservation is completed, the temperature is quickly lowered to 50°C, and a mixture of 3 parts of diethylene glycol monostearate and polyoxyethylene sorbitan monooleate (Tween 80) is added, and the mixture is kept at 50°C for 0.5 h.

[0145] S6. After the heat preservation is completed, the temperature is rapidly cooled again to 15° C., and the mixture is passed through a high-pressure homogenizer and degassed for 2 hours to obtain the mineral oil defoaming agent of the present invention.

[0146] Performance test of defoaming agent

[0147] (1) Thermal stability test:

[0148] Test method: Place the defoamer sample in a 55°C oven for 48 hours and observe the stratification. The test results are shown in the following table:

[0149] (2) Centrifugal stability

[0150] Test method: Take 10ml of sample and put it into a centrifuge tube. Place it in a centrifuge and start the centrifuge at 3000rpm / min. Centrifuge for 15min and check the defoaming agent stratification and precipitation status.

[0151] The stability test results are as follows:

[0152]

[0153] (3) Foam suppression performance test - coating

[0154] Test method: In a 500ml stainless steel cup, add 135g of the prepared paint, then add 15g of styrene acrylic emulsion, use a high-speed disperser to stir at 600rpm for 1min to evenly mix the paint and styrene acrylic emulsion, then add 1% thickener and 0.2% 2-amino-2-methyl-1-propanol, continue stirring at 600rpm for 1min, finally add 0.3% defoamer, stir at 600rpm for 6min, stop stirring and immediately pour it into a 100Ml graduated cylinder, record the mass m and volume V, calculate the specific gravity = m / V, the larger the value, the better the defoamer performance.

[0155] (4) Compatibility test - coating

[0156] Test method: After the high-speed dispersed paint is placed for 10 minutes, take out a small amount and place it on a glass plate. Use a 75um wet film preparation device to scrape the paint evenly at a constant speed. Observe the state of the coating and express it with a grade. The higher the grade, the better the compatibility.

[0157]

[0158] The performance test results are shown in the following table:

[0159]

[0160] (5) Compatibility test - ink

[0161] Take 100g of water-based ink, add 0.3g of defoamer, and then disperse it in a high-speed disperser at 1000rpm for 5 minutes. Then transfer it to a 500ml beaker and let it stand for 1 hour. Use an 8-micron wire rod to perform a scraping test on black and white cardboard to observe the number of shrinkage holes and classify them into grades: no shrinkage holes - ①; 1-5 shrinkage holes - ②; 5-10 shrinkage holes - ③; more than 10 shrinkage holes - ④; very serious shrinkage holes - ⑤;

[0162] The test results are as follows:

[0163]

Claims

1. A method for preparing a mineral oil defoamer for water-based coating ink, characterized in that: The raw materials of the mineral oil defoamer are mixed according to the following mass proportions: 70%-90% mineral oil, 2%-6% white carbon black, 2%-5% fatty acid metal soap, 0.5%-3% wax, 3%-8% nonionic emulsifier, and 2%-10% modified butene-based polymer; specifically comprising the following steps: S1. Under the protection of inert gas N2, add the butene-based polymer and hydrogenated silicone oil into a reaction vessel, stir evenly, increase the temperature to 70-90°C, add a platinum catalyst, continue to increase the temperature to 120-140°C, and keep warm for 2 hours to obtain a modified butene-based polymer; S2. Mix mineral oil and white carbon black in a container and disperse at high speed at a speed of 2500-3000 rpm for 1.5-2 hours to obtain a mixture A; S3, adding fatty acid metal soap and wax to mixture A in order, starting stirring and heating, raising the temperature to 90-110° C. at a speed of 200-500 rpm, and keeping warm for 0.5-1 hour to obtain mixture B; S4, adding the modified butene-based polymer prepared in advance to mixture B, continuing to raise the temperature to 90-110° C., and keeping the temperature for 0.5-1 hour; S5. After the heat preservation is completed, the temperature is quickly lowered to 50-60°C, and a nonionic emulsifier is added, and the temperature is kept at 50-60°C for 0.5-1h; S6. After the heat preservation is completed, the temperature is rapidly cooled again to below 20° C., and the mixture is passed through a high-pressure homogenizer and degassed for 1-2 hours to obtain the mineral oil defoaming agent of the present invention.

2. The method for preparing a mineral oil defoamer for water-based coating ink according to claim 1, characterized in that The mineral oil is one or more combinations of low-viscosity white oil and naphthenic oil; specifically, the viscosity of the mineral oil is 5-30 mPa·s.

3. The method for preparing a mineral oil defoamer for water-based coating ink according to claim 1, characterized in that The white carbon black is selected from hydrophilic white carbon black, specifically having a specific surface area of 130-180m 2 / g of hydrophilic fumed silica and / or hydrophilic precipitated silica.

4. The method for preparing a mineral oil defoamer for water-based coating ink according to claim 1, characterized in that The fatty acid metal soap includes but is not limited to one of magnesium salt, aluminum salt, calcium salt, and zinc salt, or a mixture of any two or more thereof; preferably, fatty acid aluminum.

5. The method for preparing a mineral oil defoamer for water-based coating ink according to claim 1, characterized in that The wax is wax powder, including one or more of polyethylene wax, oxidized polyethylene wax, Fischer-Tropsch wax, and polyamide wax.

6. The method for preparing a mineral oil defoamer for water-based coating ink according to claim 1, characterized in that The nonionic emulsifier includes one or more of polyoxyethylene sorbitan monostearate (Tween 60), polyoxyethylene sorbitan monooleate (Tween 80), polyoxyethylene sorbitan trioleate (Tween 85), sorbitan monolaurate (Span 20), sorbitan monopalmitate (Span 40), sorbitan monostearate (Span 60), glyceryl tristearate, glyceryl monostearate, pentaerythritol glyceryl stearate, ethylene glycol monostearate, ethylene glycol distearate, diethylene glycol monostearate, and diethylene glycol distearate.

7. The method for preparing a mineral oil defoamer for water-based coating ink according to claim 1, characterized in that The butene-based polymer in the modified butene-based polymer is selected from hydroxyl-terminated polyisobutylene or hydroxyl-terminated polybutadiene; the structural formula of the hydroxyl-terminated polyisobutylene is HO-[CH2-C(CH3)2] m -OH, molecular weight is 500-5000; the molecular formula of the hydroxy-terminated polybutadiene is HO-(CH2-CH=CH-CH2) n -OH is a telechelic polymer terminated with hydroxyl groups at both ends. The polybutadiene of the present invention is selected from a group with a molecular weight of 500-5000.

8. The method for preparing a mineral oil defoamer for water-based coating ink according to claim 1, characterized in that The hydrogenated silicone oil in the modified butene-based polymer has a viscosity of 10-200 mPa·s and a hydrogen content of 0.05-0.3%.

9. The method for preparing a mineral oil defoamer for water-based coating ink according to claim 1, characterized in that The mass ratio of hydrogenated silicone oil to butene-based polymer in the modified butene-based polymer is 1:1.1-1.

3.

10. The method for preparing a mineral oil defoamer for water-based coating ink according to claim 1, characterized in that The platinum catalyst in the modified butene-based polymer is a chloroplatinic acid catalyst with a dosage of 40-80 ppm.

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