阅读说明：本技术 一种线切割用消泡剂及其制备方法 (Defoaming agent for linear cutting and preparation method thereof ) 是由 叶佳 于 2021-07-01 设计创作，主要内容包括：一种消泡剂,含有质量百分比含量为40～60％的炔二醇聚氧乙烯醚、质量百分比含量为5～30％的丙二醇嵌段聚醚、质量百分比含量为1～8％的疏水型白炭黑、及质量百分比含量为2～9％的脂肪醇聚氧乙烯醚。本发明还提供一种消泡剂的制备方法。本发明提供的消泡剂具有较佳的消抑泡性和相容性。(The defoaming agent comprises 40-60% by mass of acetylene glycol polyoxyethylene ether, 5-30% by mass of propylene glycol block polyether, 1-8% by mass of hydrophobic white carbon black and 2-9% by mass of fatty alcohol polyoxyethylene ether. The invention also provides a preparation method of the defoaming agent. The defoaming agent provided by the invention has better defoaming and foam inhibiting properties and compatibility.)

1. The defoaming agent is characterized by comprising 40-60% by mass of acetylene glycol polyoxyethylene ether, 5-30% by mass of propylene glycol block polyether, 1-8% by mass of hydrophobic white carbon black and 2-9% by mass of fatty alcohol polyoxyethylene ether.

2. The defoamer of claim 1, wherein the acetylenic diol polyoxyethylene ether has the formula:

wherein R is₁And R₂Is a straight-chain or branched alkyl radical, and m + n is an integer between 2 and 20.

3. The defoamer of claim 1, wherein said propylene glycol block polyether has the formula R₃(C₂H₄O)_x(C₃H₆O)_yR₄Wherein R is₃Is a straight chain or branched chain alkyl group having 1 to 30 carbon atoms, or a carbon atom numberA straight chain or branched chain unsaturated alkylene group of 1 to 10, R₄Is a straight chain or branched chain alkyl group with 11-10 carbon atoms, x is an integer between 1 and 50, and y is an integer between 1 and 50.

4. The defoamer of claim 1, wherein said fatty alcohol-polyoxyethylene ether has the formula R₅(C₂H₄O)_zH, wherein R₅Is a straight chain or branched chain alkyl with 6-20 carbon atoms, and z is an integer between 1 and 15.

5. The defoamer of claim 1, wherein the molecular weight of the acetylenic diol polyoxyethylene ether is 200 to 3000; and/or

The molecular weight of the propylene glycol block polyether is 2000-20000.

6. The preparation method of the defoaming agent is characterized by comprising the following steps:

providing acetylene glycol polyoxyethylene ether, propylene glycol block polyether, hydrophobic white carbon black and fatty alcohol polyoxyethylene ether; and

mixing the acetylene glycol polyoxyethylene ether, the propylene glycol block polyether, the hydrophobic white carbon black and the fatty alcohol-polyoxyethylene ether to obtain the defoaming agent, wherein the defoaming agent contains 40-60% of the acetylene glycol polyoxyethylene ether, 5-30% of the propylene glycol block polyether, 1-8% of the hydrophobic white carbon black and 2-9% of the fatty alcohol-polyoxyethylene ether.

7. The method for preparing an antifoaming agent according to claim 6, wherein the acetylenic diol polyoxyethylene ether has the structural formula:

wherein R is₁And R₂Is straight chain orBranched alkyl radicals, m + n being an integer between 2 and 20.

8. The method of claim 6, wherein the propylene glycol block polyether has the formula R₃(C₂H₄O)_x(C₃H₆O)_yR₄Wherein R is₃Is a linear or branched alkyl group having 1 to 30 carbon atoms or a linear or branched unsaturated alkenyl group having 1 to 10 carbon atoms, R₄Is a straight chain or branched chain alkyl group with 11-10 carbon atoms, x is an integer between 1 and 50, and y is an integer between 1 and 50.

9. The method for preparing an antifoaming agent according to claim 6, wherein the fatty alcohol-polyoxyethylene ether has the structural formula R₅(C₂H₄O)_zH, wherein R₅Is a straight chain or branched chain alkyl with 6-20 carbon atoms, and z is an integer between 1 and 15.

10. The method for preparing an antifoaming agent according to claim 6, wherein the molecular weight of the acetylenic diol polyoxyethylene ether is 200 to 3000; and/or

The molecular weight of the propylene glycol block polyether is 2000-20000.

Technical Field

The invention relates to the technical field of fine chemical preparations, in particular to a defoaming agent applied to silicon wafer cutting fluid or metal processing cutting fluid and a preparation method of the defoaming agent.

Background

The defoaming agent can be classified into a silicone type defoaming agent and a polyether type defoaming agent. The silicone defoaming agent has excellent defoaming and foam inhibiting properties, but has poor compatibility. Although the polyether defoamer has excellent compatibility, the defoaming property is poor.

Patents US4436647 and CN1593739A both disclose a silicone defoamer which, although having a better defoaming effect, has the disadvantage of poor compatibility. Patents CN107557120A and CN101638868 both disclose a polyether defoamer, which has the disadvantage of poor defoaming effect, although having good compatibility. Therefore, it is required to develop a defoaming agent excellent in both defoaming and foam suppressing properties and compatibility.

Disclosure of Invention

In view of the above, it is desirable to provide an antifoaming agent with good compatibility and defoaming property.

The defoaming agent comprises 40-60% by mass of acetylene glycol polyoxyethylene ether, 5-30% by mass of propylene glycol block polyether, 1-8% by mass of hydrophobic white carbon black and 2-9% by mass of fatty alcohol polyoxyethylene ether.

Further, the structural formula of the alkynediol polyoxyethylene ether is as follows:

wherein R is₁And R₂Is a straight-chain or branched alkyl radical, and m + n is an integer between 2 and 20.

Further, the structural formula of the propylene glycol block polyether is R₃(C₂H₄O)_x(C₃H₆O)_yR₄Wherein R is₃Is a linear or branched alkyl group having 1 to 30 carbon atoms or a linear or branched unsaturated alkenyl group having 1 to 10 carbon atoms, R₄Is a straight chain or branched chain alkyl group with 11-10 carbon atoms, x is an integer between 1 and 50, and y is an integer between 1 and 50.

Further, the structural formula of the fatty alcohol-polyoxyethylene ether is R₅(C₂H₄O)_zH, wherein R₅Is a straight chain or branched chain alkyl with 6-20 carbon atoms, and z is an integer between 1 and 15.

Further, the molecular weight of the alkynediol polyoxyethylene ether is 200-3000; and/or

The molecular weight of the propylene glycol block polyether is 2000-20000.

A preparation method of a defoaming agent comprises the following steps:

providing acetylene glycol polyoxyethylene ether, propylene glycol block polyether, hydrophobic white carbon black and fatty alcohol polyoxyethylene ether; and

mixing the acetylene glycol polyoxyethylene ether, the propylene glycol block polyether, the hydrophobic white carbon black and the fatty alcohol-polyoxyethylene ether to obtain the defoaming agent, wherein the defoaming agent contains 40-60% of the acetylene glycol polyoxyethylene ether, 5-30% of the propylene glycol block polyether, 1-8% of the hydrophobic white carbon black and 2-9% of the fatty alcohol-polyoxyethylene ether.

Further, the structural formula of the alkynediol polyoxyethylene ether is as follows:

wherein R is₁And R₂Is a straight-chain or branched alkyl radical, and m + n is an integer between 2 and 20.

Further, the structural formula of the propylene glycol block polyether is R₃(C₂H₄O)_x(C₃H₆O)_yR₄Wherein R is₃Is a linear or branched alkyl group having 1 to 30 carbon atoms or a linear or branched unsaturated alkenyl group having 1 to 10 carbon atoms, R₄Is a straight chain or branched chain alkyl group with 11-10 carbon atoms, x is an integer between 1 and 50, and y is an integer between 1 and 50.

Further, the structural formula of the fatty alcohol-polyoxyethylene ether is R₅(C₂H₄O)_zH, wherein R₅Is a straight chain or branched chain alkyl with 6-20 carbon atoms, and z is an integer between 1 and 15.

Further, the molecular weight of the alkynediol polyoxyethylene ether is 200-3000; and/or

The molecular weight of the propylene glycol block polyether is 2000-20000.

The defoaming agent provided by the invention contains 40-60% of acetylene glycol polyoxyethylene ether, 5-30% of propylene glycol block polyether, 1-8% of hydrophobic white carbon black and 2-9% of fatty alcohol polyoxyethylene ether. The hydrophobic white carbon black is used as a carrier, can adsorb bubbles and is beneficial to eliminating the bubbles. The acetylene glycol polyoxyethylene ether has better foam inhibition performance, the propylene glycol block polyether has better defoaming performance, and the fatty alcohol polyoxyethylene ether can increase the compatibility between the acetylene glycol polyoxyethylene ether and the propylene glycol block polyether, so that the defoaming agent not only has better foam inhibition performance, but also has better compatibility. The defoaming agent has better defoaming and foam inhibiting performance and compatibility, so that the defoaming agent also has better foam stabilizing performance.

Detailed Description

In order that the above objects, features and advantages of the present invention can be more clearly understood, the following detailed description of the present invention is given. In addition, the embodiments and features of the embodiments of the present application may be combined with each other without conflict. In the following description, numerous specific details are set forth to provide a thorough understanding of the present invention, and the described embodiments are merely a subset of the embodiments of the present invention, rather than a complete embodiment. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes all and any combination of one or more of the associated listed items.

In various embodiments of the present invention, for convenience in description and not in limitation, the term "coupled" as used in the specification and claims of the present application is not limited to physical or mechanical couplings, either direct or indirect. "upper", "lower", "left", "right", and the like are used merely to indicate relative positional relationships, and when the absolute position of the object being described is changed, the relative positional relationships are changed accordingly.

The embodiment of the invention provides a defoaming agent, which is applied to silicon wafer cutting fluid or metal processing cutting fluid.

The defoaming agent contains 40-60% by mass of acetylene glycol polyoxyethylene ether, 5-30% by mass of propylene glycol block polyether, 1-8% by mass of hydrophobic white carbon black and 2-9% by mass of fatty alcohol polyoxyethylene ether.

In at least one embodiment, the acetylenic diol polyoxyethylene ether has the formula:

wherein R is₁And R₂Is a straight-chain or branched alkyl group, m and n are the polymerization degree of ethylene oxide, and m + n is an integer of 2 to 20. The alkyne diol group of the alkyne diol polyoxyethylene ether can enable the defoaming agent to have better alkali resistance and lower surface tension.

In at least one embodiment, the molecular weight of the alkynediol polyoxyethylene ether is 200-3000, preferably 400-1000.

In at least one embodiment, m + n is preferably an integer between 2 and 8, more preferably an integer between 2 and 4.

In at least one embodiment, the propylene glycol block polyether has the structural formula R₃(C₂H₄O)_x(C₃H₆O)_yR₄Wherein R is₃Is a linear or branched alkyl group having 1 to 30 carbon atoms or a linear or branched unsaturated alkenyl group having 1 to 10 carbon atoms, R₄Is a straight chain or branched chain alkyl group with 11-10 carbon atoms, x is an integer between 1 and 50, and y is an integer between 1 and 50. C of the propylene glycol block polyether₂H₄O-and C₃H₆O-can make the defoaming agent have better foam inhibition.

In at least one embodiment, the molecular weight of the propylene glycol block polyether is 2000-20000, preferably 6000-12000.

In at least one embodiment, x is preferably an integer between 1 and 30.

In at least one embodiment, y is preferably an integer between 15 and 20.

In at least one embodiment, the fatty alcohol-polyoxyethylene ether has a structural formula R₅(C₂H₄O)_zH. Wherein R is₅Is a C6-20 linear chain or branched chain alkyl group, preferably a C10-12 linear chain or branched chain alkyl groupAnd z is an integer between 1 and 15. The fatty alcohol-polyoxyethylene ether is used as a solubilizer, so that the compatibility between the acetylenic diol polyoxyethylene ether and the propylene glycol block polyether can be improved.

In at least one embodiment, z is preferably an integer between 1 and 8.

In at least one embodiment, the specific surface area of the hydrophobic silica is more than 100 m/g. It is understood that the larger the specific surface area, the smaller the particle size of the hydrophobic silica, the higher the surface energy, and the stronger the adsorbability.

The defoaming agent provided by the invention contains 40-60% by mass of acetylene glycol polyoxyethylene ether, 5-30% by mass of propylene glycol block polyether and 2-9% by mass of fatty alcohol polyoxyethylene ether. The hydrophobic white carbon black is used as a carrier, can adsorb bubbles and is beneficial to eliminating the bubbles. The acetylene glycol polyoxyethylene ether has better foam inhibition performance, the propylene glycol block polyether has better defoaming performance, and the fatty alcohol polyoxyethylene ether can increase the compatibility between the acetylene glycol polyoxyethylene ether and the propylene glycol block polyether, so that the defoaming agent not only has better foam inhibition performance, but also has better compatibility. The defoaming agent has better defoaming and foam inhibiting performance and compatibility, so that the defoaming agent also has better foam stabilizing performance and has continuous strong foam inhibiting performance even in a strong alkaline environment. In addition, the compounding of the alkynediol polyoxyethylene ether, the propylene glycol block polyether, the hydrophobic white carbon black and the fatty alcohol polyoxyethylene ether can enable the defoaming agent to have lower static surface tension and dynamic surface tension, and the defoaming agent also has a wetting function while defoaming.

The embodiment of the invention also provides a preparation method of the defoaming agent. The preparation method of the defoaming agent comprises the following steps:

step S1: providing acetylene glycol polyoxyethylene ether, propylene glycol block polyether, hydrophobic white carbon black and fatty alcohol polyoxyethylene ether; and

step S2: mixing the acetylene glycol polyoxyethylene ether, the propylene glycol block polyether, the hydrophobic white carbon black and the fatty alcohol-polyoxyethylene ether to obtain the defoaming agent, wherein the defoaming agent contains 40-60% of the acetylene glycol polyoxyethylene ether, 5-30% of the propylene glycol block polyether, 1-8% of the hydrophobic white carbon black and 2-9% of the fatty alcohol-polyoxyethylene ether.

In at least one embodiment, the acetylenic diol polyoxyethylene ether has the formula:

wherein R is₁And R₂Is a straight-chain or branched alkyl group, m and n are the polymerization degree of ethylene oxide, and m + n is an integer of 2 to 20. The alkyne diol group of the alkyne diol polyoxyethylene ether can enable the defoaming agent to have better alkali resistance and lower surface tension.

In at least one embodiment, the molecular weight of the alkynediol polyoxyethylene ether is 200-3000, preferably 400-1000.

In at least one embodiment, m + n is preferably an integer between 2 and 8, more preferably an integer between 2 and 4.

In at least one embodiment, the propylene glycol block polyether has the structural formula R₃(C₂H₄O)_x(C₃H₆O)_yR₄Wherein R is₃Is a linear or branched alkyl group having 1 to 30 carbon atoms or a linear or branched unsaturated alkenyl group having 1 to 10 carbon atoms, R₄Is a straight chain or branched chain alkyl group with 11-10 carbon atoms, x is an integer between 1 and 50, and y is an integer between 1 and 50. C of the propylene glycol block polyether₂H₄O-and C₃H₆O-can make the defoaming agent have better foam inhibition.

In at least one embodiment, the molecular weight of the propylene glycol block polyether is 2000-20000, preferably 6000-12000.

In at least one embodiment, x is preferably an integer between 1 and 30.

In at least one embodiment, y is preferably an integer between 15 and 20.

In at least one embodiment, the fatty alcohol-polyoxyethylene ether has a structural formula R₅(C₂H₄O)_zH. Wherein R is₅Is a linear or branched alkyl group having 6 to 20 carbon atoms, preferably a linear or branched alkyl group having 10 to 12 carbon atoms, and z is an integer of 1 to 15. The fatty alcohol-polyoxyethylene ether is used as a solubilizer, so that the compatibility between the acetylenic diol polyoxyethylene ether and the propylene glycol block polyether can be improved.

In at least one embodiment, z is preferably an integer between 1 and 8.

In at least one embodiment, the specific surface area of the hydrophobic silica is more than 100 m/g. It is understood that the larger the specific surface area, the smaller the particle size of the hydrophobic silica, the higher the surface energy, and the stronger the adsorbability.

In the preparation method of the defoaming agent provided by the invention, the glycol polyoxyethylene ether, the propylene glycol block polyether, the hydrophobic white carbon black and the fatty alcohol-polyoxyethylene ether are mixed to obtain the defoaming agent. The defoaming agent contains 40-60% by mass of acetylene glycol polyoxyethylene ether, 5-30% by mass of propylene glycol block polyether, 1-8% by mass of hydrophobic white carbon black and 2-9% by mass of fatty alcohol polyoxyethylene ether. The hydrophobic white carbon black is used as a carrier, can adsorb bubbles and is beneficial to eliminating the bubbles. The acetylene glycol polyoxyethylene ether has better defoaming property, and the propylene glycol block polyether has better defoaming property. The fatty alcohol-polyoxyethylene ether can increase the compatibility between the acetylenic diol polyoxyethylene ether and the propylene glycol block polyether, so that the defoaming agent not only has better defoaming and foam inhibiting properties, but also has better compatibility. The defoaming agent has better defoaming and foam inhibiting performance and compatibility, so that the defoaming agent also has better foam stabilizing performance and has continuous strong foam inhibiting performance even in a strong alkaline environment. In addition, the compounding of the alkynediol polyoxyethylene ether, the propylene glycol block polyether, the hydrophobic white carbon black and the fatty alcohol polyoxyethylene ether can enable the defoaming agent to have lower static surface tension and dynamic surface tension, and the defoaming agent also has a wetting function while defoaming.

The step S2 includes the steps of:

step S21: mixing the acetylene glycol polyoxyethylene ether and the propylene glycol block polyether, and stirring for 30-60 min to obtain a mixture; and

step S22: and adding fatty alcohol-polyoxyethylene ether into the mixture under the stirring state to obtain the defoaming agent.

In the technical scheme of the invention, the acetylene glycol polyoxyethylene ether and the propylene glycol block polyether are mixed firstly, and then the fatty alcohol polyoxyethylene ether is added to fully mix all the components.

The present invention will be specifically described below with reference to specific examples.

Example one

Providing acetylene glycol polyoxyethylene ether, propylene glycol block polyether, hydrophobic white carbon black and fatty alcohol polyoxyethylene ether, wherein R of the acetylene glycol polyoxyethylene ether₁Is (CH)₃)₂CH₂CH₂-，R₂Is methyl, has a molecular weight of 226, and m + n is 2; r of the propylene glycol block polyether₃Is vinyl, R₄Is methyl, x is 10, y is 20, and the molecular weight is 1600; r of fatty alcohol-polyoxyethylene ether₅Is alkyl with 13 carbon atoms, n is 5, and the molecular weight is 1305; and

and mixing the acetylene glycol polyoxyethylene ether, the propylene glycol block polyether, the hydrophobic white carbon black and the fatty alcohol-polyoxyethylene ether to obtain the defoaming agent of the first embodiment, wherein the defoaming agent of the first embodiment comprises 60 mass percent of the acetylene glycol polyoxyethylene ether, 30 mass percent of the propylene glycol block polyether, 5 mass percent of the hydrophobic white carbon black and 5 mass percent of the fatty alcohol-polyoxyethylene ether.

Example two

Providing acetylene glycol polyoxyethylene ether, propylene glycol block polyether, hydrophobic white carbon black and fatty alcohol polyoxyethylene ether, wherein R of the acetylene glycol polyoxyethylene ether₁Is (CH)₃)₂CH₂CH₂CH₂-，R₂Is methyl, has a molecular weight of 400, and m + n is 3; r of the propylene glycol block polyether₃Is vinyl, R₄Is methyl, x is 10, y is 40, and the molecular weight is 2760; r of fatty alcohol-polyoxyethylene ether₅Is alkyl with 10 carbon atoms, n is 5, and the molecular weight is 1005; and

and mixing the acetylene glycol polyoxyethylene ether, the propylene glycol block polyether, the hydrophobic white carbon black and the fatty alcohol-polyoxyethylene ether to obtain the defoaming agent of the second embodiment, wherein the defoaming agent of the second embodiment comprises 60 mass percent of the acetylene glycol polyoxyethylene ether, 30 mass percent of the propylene glycol block polyether, 5 mass percent of the hydrophobic white carbon black and 5 mass percent of the fatty alcohol-polyoxyethylene ether.

EXAMPLE III

Providing acetylene glycol polyoxyethylene ether, propylene glycol block polyether, hydrophobic white carbon black and fatty alcohol polyoxyethylene ether, wherein R of the acetylene glycol polyoxyethylene ether₁Is (CH)₃)₂CH₂CH₂CH₂-，R₂Is methyl, has a molecular weight of 400, and m + n is 3; r of the propylene glycol block polyether₃Is vinyl, R₄Is methyl, x is 10, y is 40, and the molecular weight is 2760; r of fatty alcohol-polyoxyethylene ether₅Is alkyl with 10 carbon atoms, n is 5, and the molecular weight is 1005; and

and mixing the acetylene glycol polyoxyethylene ether, the propylene glycol block polyether, the hydrophobic white carbon black and the fatty alcohol-polyoxyethylene ether to obtain the defoaming agent of the third embodiment, wherein the defoaming agent of the third embodiment comprises 55 mass percent of the acetylene glycol polyoxyethylene ether, 30 mass percent of the propylene glycol block polyether, 7 mass percent of the hydrophobic white carbon black and 8 mass percent of the fatty alcohol-polyoxyethylene ether.

The surface tension of the defoaming agents of examples one to three, silicone-based defoaming agents and polyether-based defoaming agents purchased from the market were tested by the maximum bubble method. The test results are shown in Table 1.

Table 1 surface tension test results

	Surface tension (mN/m)
		Defoaming agent of example one	30.5
Defoaming agent of example two	32.2
		Example III antifoam agent	33.7
Silicone defoaming agent	41.4
		Polyether type defoaming agent	42.3

The lower the surface tension, the better the defoaming performance. The surface tension of the defoaming agents of examples one to three was smaller than that of commercially available silicone-based defoaming agents and polyether-based defoaming agents. This indicates that the defoaming agents of examples one to three have better defoaming properties.

The defoaming agents of examples one to three, silicone-based defoaming agents and polyether-based defoaming agents purchased from the market were tested for foam suppressing performance by a bubbling method. The test results are shown in Table 2.

TABLE 2 foam suppressing Performance test results

The lower the foam height, the better the foam suppressing performance, with the same bubbling time. The foam heights of the defoamers of examples one to three were all smaller than those of commercially available silicone-based defoamers and polyether defoamers at the same bubbling time. This indicates that the defoaming agents of examples one to three have better foam inhibition.

After the bubbling treatment was completed, the defoaming agents of examples one to three, silicone-based defoaming agents purchased from the market, and polyether-based defoaming agents were left to stand to test the foam stabilizing properties of the defoaming agents of examples one to three, silicone-based defoaming agents purchased from the market, and polyether-based defoaming agents. The test results are shown in Table 3.

TABLE 3 foam stabilizing Performance test results

When the standing time is the same, the lower the foam height is, the better the foam stabilizing performance is. The foam heights of the defoamers of examples one to three were all smaller than those of commercially available silicone-based defoamers and polyether defoamers when the standing time was the same. This indicates that the defoaming agents of examples one to three have better foam stability.

The surface tension of the defoaming agents of examples one to three, silicone-based defoaming agents commercially available, and polyether-based defoaming agents was tested under an alkaline environment (at least in one example, under an alkaline environment at a pH of 11) by the maximum bubble method. The test results are shown in Table 4.

Table 4 surface tension test results in alkaline environment

The lower the surface tension, the better the foam stabilizing properties. The surface tension of the defoaming agents of examples one to three was gradually smaller than those of commercially available silicone-based defoaming agents and polyether-based defoaming agents as time passed after the defoaming agents were treated in an alkaline environment. This indicates that the defoaming agents of examples one to three still have better foam stability in an alkaline environment.

Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention.