阅读说明：本技术 一种酰胺聚合物分子级消泡剂及制备方法 (Amide polymer molecular defoaming agent and preparation method thereof ) 是由 董飞 黄伟 曹添 于 2021-09-17 设计创作，主要内容包括：本发明涉及一种酰胺聚合物分子级消泡剂及制备方法,其特征在于所述酰胺聚合物分子级消泡剂由20-45%的酰胺聚合物,5-15%的载体油,2-6%的气相二氧化硅,3-8%的金属皂类,15-75%的水组成。本发明优势在于采用脂肪多元胺化合物与一元脂肪酸化合物进行脱水缩合反应,最终实现分子结构中多支链化活性物的制备,这种多支链结构化合物形成的消泡剂在起泡液界面膜不致密,一方面从而使得液膜表面极易瞬间破裂,另一方面可以有效破除一些致密性较强的泡,使得其在消泡和抑泡方面都有很强的性能。(The invention relates to an amide polymer molecular defoaming agent and a preparation method thereof, and is characterized in that the amide polymer molecular defoaming agent consists of 20-45% of amide polymer, 5-15% of carrier oil, 2-6% of fumed silica, 3-8% of metal soaps and 15-75% of water. The invention has the advantages that the preparation of the multi-branched active substance in the molecular structure is finally realized by adopting the dehydration condensation reaction of the fatty polyamine compound and the monobasic fatty acid compound, and the defoaming agent formed by the multi-branched compound is not compact in the interfacial film of the foaming liquid, so that the surface of the liquid film is easy to break instantly on one hand, and bubbles with strong compactness can be effectively broken on the other hand, and the defoaming agent has strong performances in the aspects of defoaming and foam inhibition.)

1. An amide polymer molecular scale antifoaming agent, characterized in that the antifoaming agent consists essentially of the following components:

a amide polymers

The amide polymer is prepared from the following raw materials in parts by mass: 24-62% of aliphatic polyamine compound, 37-75% of monobasic fatty acid and 0.2-2% of catalyst, wherein the sum of the raw materials is 100%; the amide polymer accounts for 20-58% of the total mass of the defoaming agent;

b Carrier oil

The carrier oil is selected from mineral oil and vegetable oil; one or more of mineral oil and vegetable oil are selected and mixed according to any proportion; the carrier oil accounts for 5-15% of the total mass of the defoaming agent;

c silicon dioxide

The silicon dioxide is divided into two types of precipitated silicon dioxide and gas phase silicon dioxide according to the manufacturing method, and is divided into hydrophilic silicon dioxide and hydrophobic silicon dioxide according to surface properties, the silicon dioxide is selected from hydrophobic gas phase silicon dioxide, and the silicon dioxide accounts for 2-6% of the total mass of the defoaming agent;

d Metal soaps

The metal soap is one or more of magnesium salt, aluminum salt, calcium salt and zinc salt of fatty acid; the metal soap accounts for 3-8% of the total mass of the defoaming agent;

e water

The water is deionized water and accounts for 15-62% of the total mass of the defoaming agent;

the preparation method of the amide polymer molecular defoaming agent comprises the following steps:

(1) adding a specified amount of monobasic fatty acid and a specified amount of fatty polyamine compound into a reaction kettle, starting a stirrer, heating to 80-200 ℃, uniformly stirring reactants, adding a catalyst, preserving heat for 1-3h, slowly heating to 120 ℃ and 250 ℃, carrying out amide dehydration reaction for 2-8 h, and taking out produced water through inert gas in the reaction process to obtain an amide polymer;

(2) adding an amide polymer, carrier oil, silicon dioxide and metal soaps into a high-speed stirrer, starting stirring, dispersing at a high speed of 500-3000 rpm for 0.5-4 h, and then slowly adding water; stirring is continued for 0.5 to 3 hours to obtain the defoaming agent M.

2. The molecular defoaming agent according to claim 1, wherein the aliphatic polyamine is selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, polyethylenepolyamine, dimethylaminopropylamine, and dihexyltriamine, and any ratio of the above components is selected.

3. The amide polymer molecular defoaming agent according to claim 1, characterized in that the structural formula of the monobasic fatty acid is:

CH₃(CH₂)n-COOH

wherein n is an integer of 1 to 30.

4. The molecular defoaming agent according to claim 1, wherein the catalyst is selected from one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, etc. in any ratio.

5. The amide polymer molecular defoamer of claim 1, wherein said mineral oil is selected from kerosene, diesel oil, white oil, and alkylbenzene.

6. The amide polymer molecular defoamer of claim 1, wherein said vegetable oil is selected from the group consisting of coconut oil, corn oil, castor oil, olive oil, linseed oil, cottonseed oil, peanut oil.

7. The amide polymer molecular defoaming agent according to claim 1, wherein the silica is selected from silica having a specific surface area of 20 to 400m²Per g of hydrophobic fumed silica.

8. An amide polymer molecular defoamer as claimed in claim 1 wherein said metal soap is preferably aluminum stearate.

Technical Field

The invention relates to defoaming agent chemicals, in particular to an amide polymer molecular defoaming agent and a preparation method thereof, belonging to the technical field of fine chemical engineering.

Background

The CN201080043582.1 defoaming Agent patent indicates that a defoaming Agent formed by dispersing bisamide in polyether is adopted, Crystal Form control Agent is added, the particle size of dispersoid is controlled within a proper range (0.1-5 mu m), excellent defoaming property can be exerted, and metal soap, synthetic resin, hydrophobic silicon dioxide, wax and emulsifying dispersant can be added; the structural general formula of the bisamide is as follows: r₁CONH(CH₂)_t-NHCOR¹；R¹Is alkyl, alkenyl, hydroxyalkyl or hydroxyalkenyl having 10 to 22 carbon atoms, and t is an integer of 1 to 6; the patent particularly indicates that the crystal form control agent is a metal compound containing sulfonate, and the crystal form control agent mainly acts for inhibiting the growth of bisamide along a specific direction when the temperature is reduced, so that the viscosity of the defoaming agent can be effectively reduced. CN102300612A defoaming agent DefoThe amer patent teaches the preparation of defoamers using fatty amides, oils, oil thickeners and surfactants, which may also contain water, hydrophobic silica and polyethers. The fatty amide is a reaction product (A1) comprising an alkylene diamine or alkenylene diamine having 1 to 6 carbon atoms and a fatty acid having 10 to 22 carbon atoms, and/or a reaction product (A2) comprising an alkylamine, alkenylamine or ammonia having 1 to 22 carbon atoms and a fatty acid having 10 to 22 carbon atoms; the amides in the patent are primarily limited to mono-and bis-amides and the oil thickener may be a metal soap. The main points of the features of the cn201580015117.x antifoam agent are: comprises a compound represented by the general formula (1) and a hydrocarbon oil, and contains a hydrophobic silica, an amide, a wax and a metal soap.

R (OA) n-OH (1); in the general formula (1), R represents alkyl, alkenyl or aryl with 12-30 carbon atoms, OA represents oxo-alkylene with 3-4 carbon atoms, OH represents hydroxyl, and n represents an integer of 10-100. The amide is a reaction product of an alkylene diamine or alkenylene diamine having 1 to 6 carbon atoms and a fatty acid having 10 to 22 carbon atoms (fatty acid diamide), or a reaction product of an alkylamine, alkenylamine or ammonia having 1 to 22 carbon atoms and a fatty acid having 10 to 22 carbon atoms (fatty acid monoamide).

Most of the amide defoaming agents are reacted through simple amide structures, and the prepared defoaming agent has poor defoaming and foam inhibiting performance. The present invention is directed to amide compounds having a multi-branched structure formed by a polyamine and a monobasic fatty acid. Compared with the traditional straight chain or diamide, the multi-branched amide compound has greatly improved interfacial properties in solution and obviously improved final defoaming performance.

Disclosure of Invention

According to the invention, a dehydration condensation reaction is carried out on a fatty polyamine compound and a monobasic fatty acid compound, and finally the preparation of a multi-branched active substance in a molecular structure is realized, and a defoaming agent formed by the multi-branched compound is not compact in a foaming liquid interface film, so that the surface of a liquid film is easy to break instantly on one hand, and bubbles with strong compactness can be effectively broken on the other hand, therefore, the defoaming agent can remarkably improve the foam inhibition performance of the defoaming agent in the foaming liquid, and the defoaming performance cannot be reduced rapidly due to the fact that the number of branched chains in the molecular structure is large and part of the branched chains are broken; meanwhile, compared with the traditional straight chain structure active matter, the viscosity of the active matter is relatively low, so that the active matter can better exert defoaming performance.

An amide polymer molecular defoaming agent and a preparation method thereof, mainly comprising the following components:

a amide polymers

The amide polymer is prepared from the following raw materials in parts by mass: 24-62% of aliphatic polyamine compound, 37-75% of monobasic fatty acid and 0.2-2% of catalyst; the using amount of the amide polymer accounts for 20-58% of the total mass of the defoaming agent;

the aliphatic polyamine can be one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, dipropylene triamine, polyethylene polyamine, dimethyl aminopropylamine and dihexyl triamine which are mixed according to any ratio.

The structural general formula of the monobasic fatty acid is as follows: CH (CH)₃(CH₂) n-COOH, wherein n is an integer of 1-30;

the catalyst is one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and p-toluenesulfonic acid which are mixed according to any proportion.

B Carrier oil

The carrier oil is selected from mineral oil and vegetable oil; the mineral oil is selected from kerosene, diesel oil, white oil, and alkylbenzene; the vegetable oil is selected from coconut oil, corn oil, castor oil, olive oil, linseed oil, cotton seed oil, peanut oil; one or more carrier oils are selected and mixed according to any proportion; the using amount of the carrier oil accounts for 5-15% of the total mass of the defoaming agent.

C silicon dioxide

The silicon dioxide is divided into two types of precipitated silicon dioxide and gas phase silicon dioxide according to the manufacturing method, and is divided into hydrophilic silicon dioxide and hydrophobic silicon dioxide according to surface properties, the silicon dioxide is selected from hydrophobic gas phase silicon dioxide, and the preferable specific surface area is 20-400 m²(ii) hydrophobic fumed silica per gram; the silicon dioxide accounts for 2-6% of the total mass of the defoaming agent.

D Metal soaps

The metal soap is one or more of magnesium salt, aluminum salt, calcium salt and zinc salt of fatty acid; preferably an aluminum salt of a fatty acid; the metal soap accounts for 3-8% of the total mass of the defoaming agent.

E water

The water is deionized water and accounts for 15-62% of the total mass of the defoaming agent.

The preparation method of the amide polymer molecular defoaming agent comprises the following steps:

(1) adding a specified amount of monobasic fatty acid and a specified amount of fatty polyamine compound into a reaction kettle, starting a stirrer, heating to 80-200 ℃, uniformly stirring reactants, adding a catalyst, preserving heat for 1-3h, slowly heating to 120 ℃ and 250 ℃, carrying out amide dehydration reaction for 2-8 h, and taking out produced water through inert gas in the reaction process to obtain an amide polymer;

(2) adding an amide polymer, carrier oil, silicon dioxide and metal soaps into a high-speed stirrer, starting stirring, dispersing at a high speed of 500-3000 rpm for 0.5-4 h, and then slowly adding water; stirring is continued for 0.5 to 3 hours to obtain the defoaming agent M.

Detailed Description

Example 1

(1) 56g of CH₃CH₂adding-COOH and 42.2g of tetraethylenepentamine into a reaction kettle, starting a stirrer, heating to 120 ℃, uniformly stirring the reactants, adding 1.8g of hydrochloric acid, keeping the temperature for 1 hour, slowly heating to 200 ℃, carrying out amide dehydration reaction for 4 hours, and introducing inert gas in the reaction process to take out generated water to obtain an amide polymer A1;

(2) 20g of amide polymer A1, 13g of kerosene, 4g of a specific surface area of 60m²Adding 3g of hydrophobic fumed silica and 3g of magnesium fatty acid into a high-speed stirrer, starting stirring at the rotating speed of 500rpm, dispersing at a high speed for 2 hours, slowly adding 60g of water, and continuously stirring for 2 hours to obtain the defoaming agent M1.

Example 2

(1) Mixing 37g of CH₃(CH₂)₄adding-COOH and 62g dihexyltriamine into a reaction kettle, starting a stirrer, heating to 160 ℃, uniformly stirring the reactants, and adding 1g of phosphorusAcid, keeping the temperature for 1.2h, then slowly heating to 220 ℃ to perform amide dehydration reaction for 5h, and introducing inert gas in the reaction process to carry out the produced water out to obtain an amide polymer A2;

(2) 58g of amide polymer A2, 9g of white oil, 5g of a specific surface area of 300m²Adding 6g of hydrophobic fumed silica and 6g of fatty acid aluminum into a high-speed stirrer, starting stirring at the rotating speed of 800rpm, dispersing for 1h at a high speed, slowly adding 22g of water, and continuously stirring for 1.5h to obtain the defoaming agent M2.

Example 3

(1) 75g of CH₃(CH₂)₃₀adding-COOH and 24g of diethylenetriamine into a reaction kettle, starting a stirrer to heat to 200 ℃, uniformly stirring reactants, adding 1g of sulfuric acid, preserving heat for 1.5h, slowly heating to 250 ℃, performing amide dehydration reaction for 6h, and introducing inert gas in the reaction process to carry out produced water out to obtain an amide polymer A3;

(2) 39g of amide polymer A3, 7g of corn oil, 2g of a specific surface area of 80m²Adding 8g of fatty acid calcium and 8g of hydrophobic fumed silica into a high-speed stirrer, starting stirring at the rotating speed of 2200rpm, dispersing at a high speed for 2.5h, slowly adding 44g of water, and continuously stirring for 3h to obtain the defoaming agent M3.

Example 4

(1) 42g of CH₃(CH₂)₂₆Adding COOH and 56g of triethylene tetramine into a reaction kettle, starting a stirrer, heating to 150 ℃, uniformly stirring reactants, adding 2g of nitric acid, keeping the temperature for 1.6h, slowly heating to 160 ℃, performing amide dehydration reaction for 8h, and introducing inert gas to carry out the reaction to remove generated water to obtain an amide polymer A4;

(2) 26g of amide polymer A4, 12g of castor oil, 5g of a specific surface area of 350m²Adding 6g of hydrophobic fumed silica and 6g of aluminum fatty acid into a high-speed stirrer, starting stirring at the rotating speed of 3000rpm, dispersing at a high speed for 0.5h, slowly adding 51g of water, and continuously stirring for 1h to obtain the defoaming agent M4.

Example 5

(1) Will be provided with60g CH₃(CH₂)₂₁adding-COOH and 38.5g of triethylene tetramine into a reaction kettle, starting a stirrer, heating to 180 ℃, uniformly stirring reactants, adding 1.5g of hydrochloric acid, keeping the temperature for 2 hours, slowly heating to 200 ℃, performing amide dehydration reaction for 7 hours, and introducing inert gas in the reaction process to take out generated water to obtain an amide polymer A5;

(2) 30g of amide polymer A5, 5g of cottonseed oil, 4g of a specific surface area of 400m²Adding 8g of hydrophobic fumed silica and 8g of fatty acid calcium into a high-speed stirrer, starting stirring at the rotating speed of 2500rpm, dispersing for 3 hours at a high speed, slowly adding 53g of water, and continuously stirring for 3 hours to obtain the defoaming agent M5.

Example 6

(1) 64g of CH₃(CH₂)₁₇adding-COOH and 34.8g of dipropylenetriamine into a reaction kettle, starting a stirrer, heating to 80 ℃, uniformly stirring the reactants, adding 1.2g of p-toluenesulfonic acid, keeping the temperature for 2.2h, slowly heating to 120 ℃, carrying out amide dehydration reaction for 3h, and introducing inert gas in the reaction process to carry out produced water out to obtain an amide polymer A6;

(2) 45g of amide polymer A6, 15g of peanut oil, 6g of a specific surface area of 250m²Adding 4g of hydrophobic fumed silica and 4g of fatty acid zinc into a high-speed stirrer, starting stirring at the rotating speed of 1000rpm, dispersing at a high speed for 2 hours, slowly adding 30g of water, and continuously stirring for 2.5 hours to obtain the defoaming agent M6.

Example 7

(1) 40g of CH₃(CH₂)₁₂adding-COOH, 29g of polyethylene polyamine and 30.2g of dihexyl triamine into a reaction kettle, starting a stirrer, heating to 100 ℃, uniformly stirring the reactants, adding 0.8g of phosphoric acid, keeping the temperature for 2.5 hours, slowly heating to 140 ℃, performing amide dehydration reaction for 2 hours, and introducing inert gas in the reaction process to take out generated water to obtain an amide polymer A7;

(2) 40g of amide polymer A7, 5g of diesel oil and 5g of linseed oil, 4g of specific surface area 60m²Per g of hydrophobic fumed silica, 7g of fatty acid zinc plusAnd (3) putting the mixture into a high-speed stirrer, starting stirring at the rotating speed of 1200rpm, dispersing for 1h at a high speed, slowly adding 39g of water, and continuously stirring for 1h to obtain the defoaming agent M7.

Example 8

(1) 46g of CH₃(CH₂)₉adding-COOH, 50g of dihexyltriamine and 3.8g of diethylenetriamine into a reaction kettle, starting a stirrer, heating to 190 ℃, uniformly stirring the reactants, adding 0.2g of p-toluenesulfonic acid, keeping the temperature for 3 hours, slowly heating to 240 ℃, performing amide dehydration reaction for 6 hours, and introducing inert gas in the reaction process to carry out produced water out to obtain an amide polymer A8;

(2) 57g of amide polymer A8, 10g of alkylbenzene and 4g of coconut oil, 6g of a specific surface area of 20m²Adding per gram of hydrophobic fumed silica, 4 grams of magnesium fatty acid and 4 grams of zinc fatty acid into a high-speed stirrer, starting stirring, rotating at 2000rpm, dispersing at high speed for 4 hours, slowly adding 15 grams of water, and continuously stirring for 3 hours to obtain the defoaming agent M8.

Example 9

(1) 50g of CH₃(CH₂)₆adding-COOH, 20g of dimethylaminopropylamine and 29.4g of tetraethylenepentamine into a reaction kettle, starting a stirrer, heating to 160 ℃, uniformly stirring the reactants, adding 0.3g of hydrochloric acid and 0.3g of p-toluenesulfonic acid, keeping the temperature for 2.8h, slowly heating to 180 ℃, performing amide dehydration reaction for 5h, and introducing inert gas to carry out the reaction to remove the generated water to obtain an amide polymer A9;

(2) 22g of amide polymer A9, 8g of coconut oil, 3g of a specific surface area of 150m²Adding the hydrophobic fumed silica, 2g of fatty acid aluminum and 3g of fatty acid calcium into a high-speed stirrer, starting stirring, rotating at 2800rpm, dispersing at high speed for 2h, then slowly adding 62g of water, and continuously stirring for 2h to obtain the defoaming agent M9.

Example 10

(1) 52g of CH₃(CH₂)₁₅adding-COOH and 47.5g of diethylenetriamine into a reaction kettle, starting a stirrer, raising the temperature to 140 ℃, uniformly stirring the reactants, adding 0.3g of sulfuric acid and 0.2g of nitric acid, preserving the heat for 2.5 hours, and thenSlowly heating to 160 ℃, carrying out amide dehydration reaction for 4h, and introducing inert gas in the reaction process to take out the generated water to obtain an amide polymer A10;

(2) 35g of amide polymer A10, 6g of olive oil, 6g of a specific surface area of 200m²Adding 4g of hydrophobic fumed silica and 4g of fatty acid calcium into a high-speed stirrer, starting stirring at the rotating speed of 1500rpm, dispersing at a high speed for 3.5h, slowly adding 49g of water, and continuously stirring for 0.5h to obtain the defoaming agent M10.

Example 11

(1) Adding 72g of CH₃(CH₂)₂₄adding-COOH and 27.6g of dimethylaminopropylamine into a reaction kettle, starting a stirrer, heating to 110 ℃, uniformly stirring reactants, adding 0.2g of phosphoric acid and 0.2g of hydrochloric acid, keeping the temperature for 1.5h, slowly heating to 180 ℃, carrying out amide dehydration reaction for 3h, and introducing inert gas in the reaction process to take out produced water to obtain an amide polymer A11;

(2) 50g of amide polymer A11, 2g of white oil and 6g of castor oil, 2g of a specific surface area of 100m²Adding 5g of hydrophobic fumed silica and 5g of fatty acid aluminum into a high-speed stirrer, starting stirring at the rotating speed of 600rpm, dispersing at a high speed for 3 hours, slowly adding 35g of water, and continuously stirring for 2.5 hours to obtain the defoaming agent M11.

Comparative example 1

(1) Adding 72g of CH₃(CH₂)₇adding-COOH and 30g of ethylenediamine into a reaction kettle, starting a stirrer, heating to 120 ℃, uniformly stirring reactants, adding 0.6g of phosphoric acid, keeping the temperature for 1.5h, slowly heating to 180 ℃, performing amide dehydration reaction for 3h, and introducing inert gas to carry out water removal in the reaction process to obtain an amide polymer A12;

(2) 50g of amide polymer A12, 8g of white oil, 2g of a specific surface area of 100m²Adding 5g of hydrophobic fumed silica and 5g of fatty acid aluminum into a high-speed stirrer, starting the high-speed stirrer, rotating at 600rpm, dispersing at high speed for 3h, slowly adding 35g of water, and continuously stirring for 2.5h to obtain the defoaming agent M12.

Comparative example 2

(1) 50g of CH₃(CH₂)₁₃adding-COOH and 50g of diethylamine into a reaction kettle, starting a stirrer, heating to 150 ℃, uniformly stirring reactants, adding 1g of sulfuric acid, keeping the temperature for 2.8 hours, slowly heating to 180 ℃, performing amide dehydration reaction for 5 hours, and introducing inert gas in the reaction process to take out generated water to obtain an amide polymer A13;

(2) 22g of amide polymer A9, 8g of coconut oil, 3g of a specific surface area of 150m²Adding 5g of hydrophobic fumed silica and 5g of fatty acid aluminum into a high-speed stirrer, starting the high-speed stirrer, rotating at 2800rpm, dispersing for 2h at high speed, slowly adding 62g of water, and continuously stirring for 2h to obtain the defoaming agent M13.

Comparative example 3

Defoamer M14 prepared according to example 1 of patent CN 201080043582.1.

Comparative example 4

Defoamer M15 prepared according to example 1 of patent cn201580015117. x.

Defoaming and foam suppressing performance test

Firstly, 600mL of black liquor is added into a circulating bubbler, the set temperature is 85 ℃, the flow is 6L/min, then a temperature control switch is turned on, a circulating pump is started after foaming liquor is heated to the set temperature, impact foaming is started, 0.2% of defoaming agent is added when foam rises to 300mL, and the change of the foam height along with the time is recorded. The better the performance of the defoamer, the lower the minimum scale reached by the foam; the better the foam suppressing performance of the defoamer, the longer the time the foam will reach again at 300 mL.

TABLE 1 defoaming and defoaming Performance test data