Block polyether, block polyether ester, preparation method of block polyether and block polyether ester, cutting fluid and application of block polyether and block polyether ester
By introducing block polyether ester and wetting agent into the cutting liquid, a high lubrication, low bubbles and low surface tension cutting liquid formula was designed, which solved the problems of poor lubrication performance and high COD value of the existing cutting liquid, and achieved a more efficient cutting process and lower environmental impact.
Patent Information
- Application Number
- CN202411863212.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-17
- Publication Date
- 2025-03-21
AI Technical Summary
The existing cutting fluid has poor lubrication performance during the diamond wire cutting process, resulting in problems such as wire marks, silicon wafer thickness changes, dirt, etc., and the COD value is high, causing environmental pollution and increasing subsequent treatment costs.
Using block polyether and block polyether ester and their preparation method, by introducing block polyether ester instead of conventional polyether and combining wetting agents, a cutting liquid formula with high lubrication, low bubbles and low surface tension is designed to reduce the amount of lubricant and wetting agent, and achieve the goal of low COD value.
It improves the lubricating performance of the cutting fluid, reduces the changes in line marks, silicon wafer thickness and dirt problems, and reduces COD value, reducing environmental pollution and subsequent treatment costs.
Smart Images
Figure CN119661828A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a block polyether and a block polyether ester, a preparation method thereof, a cutting fluid and an application thereof. Background Art
[0002] At present, cutting fluid is usually used in the cutting process of diamond wire. However, the use of existing known cutting fluids for cutting will cause problems such as wire marks, silicon wafer thickness variation (TTV), dirt, etc. during the cutting process. This is because the thinner the silicon wafer, the more uneven the silicon powder generated by cutting is distributed, and it accumulates between the silicon wafers and cannot be removed in time, resulting in low cutting efficiency. In addition, the existing cutting fluids also have the problem of high chemical oxygen demand (COD), which will cause environmental pollution and increase the cost of subsequent treatment.
[0003] Therefore, it is urgent to develop a cutting fluid with the characteristics of high lubrication, low foaming and low surface tension, and reduce the amount of lubricant and wetting agent accordingly to achieve the effect of low COD value, thereby reducing environmental hazards and subsequent processing costs. Summary of the invention
[0004] In order to overcome the problem that the cutting fluid of the prior art has poor lubrication performance during the cutting process, thereby causing line marks, thickness variation of silicon wafers, dirt and other problems, and the existing cutting fluid also has the defect of high COD value; the present application provides block polyether and block polyether ester and their preparation methods, cutting fluid and application. In the cutting fluid formula, by introducing block polyether ester to replace conventional polyether and cooperating with a wetting agent, the lubrication performance of the formula can be effectively improved; and the cutting fluid has the characteristics of low foaming, fast defoaming rate and low surface tension, so the amount of lubricant and wetting agent can be reduced to achieve the goal of low COD value.
[0005] The present invention solves the above technical problems through the following technical solutions:
[0006] The present invention provides a block polyether, wherein the block polyether is a polymer as shown in Formula I:
[0007] Formula I
[0008] wherein a0 is an integer selected from 17 to 50, b0 is an integer selected from 40 to 110, and c0 is an integer selected from 17 to 50.
[0009] In some embodiments, a1 or a2 is an integer selected from 22 to 46, such as 22, 30, 40 or 46.
[0010] In some embodiments, the b1 or the b2 is 40, 55, 65 or 110.
[0011] In some embodiments, the c1 or the c2 is an integer selected from 22 to 46, for example, 22, 30, 40 or 46.
[0012] The present invention also provides a method for preparing the block polyether as described above, the preparation method comprising the following steps:
[0013] In a catalytic system under an inert atmosphere, a first ethylene oxide, a propylene oxide and a second ethylene oxide are introduced in sequence for reaction, the reaction temperature is 120-150° C., the reaction pressure is 0-0.4 MPa; the mass ratio of the first ethylene oxide, the propylene oxide and the second ethylene oxide is 1:(1.8-3.5):1.
[0014] In some embodiments, the catalyst of the catalytic system comprises propylene glycol and potassium hydroxide.
[0015] In some embodiments, the inert atmosphere comprises nitrogen.
[0016] In some embodiments, the feed rates of the first ethylene oxide and the second ethylene oxide are each independently 10-20 g / min, for example 10 g / min.
[0017] In some embodiments, the feed rate of propylene oxide is 5-10 g / min, for example, 10 g / min.
[0018] In one embodiment, the block polyether is prepared by the following preparation method: 50 g of propylene glycol and KOH catalyst are added to a reactor, replaced by N2, heated to 100-120°C, and ethylene oxide (EO), propylene oxide (PO) and ethylene oxide (EO) are introduced in sequence, and reacted at a temperature and pressure of 120-150°C and 0-0.4MPa, respectively; wherein, in the order of addition, the feeding time of EO is 1 h, and the reaction time is 30 min; the feeding time of PO is 2.5 h, and the reaction time is 1.5 h; the feeding time of EO is 1 h, and the reaction time is 1 h; the feeding rate of the two ethylene oxides is 10 g / min, and the feeding rate of propylene oxide is 10 g / min.
[0019] The present invention provides a block polyether ester, wherein the block polyether ester is a polymer as shown in Formula II or Formula III:
[0020] Formula II
[0021] Wherein, R1 is selected from C7~C 17 A hydrocarbon group, a1 is an integer selected from 17 to 50, b1 is an integer selected from 40 to 110, and c1 is an integer selected from 17 to 50;
[0022] Formula III
[0023] Wherein, R2 is selected from C7~C 17 The hydrocarbon group, R3 is selected from C7~C 17 a2 is an integer selected from 17 to 50, b2 is an integer selected from 40 to 110, and c2 is an integer selected from 17 to 50.
[0024] In the present invention, according to the above structure, the block polyether ester refers to "EO / PO / EO block polyether ester".
[0025] In some embodiments, the block polyether ester has a weight average molecular weight Mw of 4000-11000; preferably 4500-11000, such as 4500, 6000, 8000 or 10000.
[0026] In some embodiments, the molecular weight distribution index of the block polyether ester is 1.1-3.
[0027] In some embodiments, the R2 and the R3 are hydrocarbon groups with the same molecular structure.
[0028] In some embodiments, the R1 is selected from C 17 of hydrocarbon groups.
[0029] In some embodiments, a1 is an integer selected from 22 to 46, such as 22, 30, 40 or 46.
[0030] In some embodiments, the b1 or the b2 is 40, 55, 65 or 110.
[0031] In some embodiments, the c1 is an integer selected from 22 to 46, such as 22, 30, 40 or 46.
[0032] In one embodiment, the weight average molecular weight of the block polyether ester is 4500, and R1 is C 17 The hydrocarbon group has the molecular formula (CH)8(CH)2(CH2)7, a=22, b=40, c=22, and the molecular distribution index is 1.3.
[0033] In one embodiment, the weight average molecular weight of the block polyether ester is 6000; R1 is C 17 The hydrocarbon group has the molecular formula (CH)8(CH)2(CH2)7, a=30, b=55, c=30, and the molecular distribution index is 1.3.
[0034] In one embodiment, the weight average molecular weight of the block polyether ester is 8000; R1 is C 17The hydrocarbon group has the molecular formula (CH)8(CH)2(CH2)7, a=46, b=65, c=46, and the molecular distribution index is 1.3.
[0035] In one embodiment, the weight average molecular weight of the block polyether ester is 10000; R1 is C 17 The hydrocarbon group has the molecular formula (CH)8(CH)2(CH2)7, a=40, b=110, c=40, and the molecular distribution index is 1.3.
[0036] The present invention provides a method for preparing the above-mentioned block polyether ester, which comprises the following steps: subjecting the above-mentioned block polyether to an esterification reaction with an organic acid to obtain the block polyether ester.
[0037] In the present invention, EO / PO / EO block polyether is obtained by esterification reaction with organic acid; the specific synthesis path is as follows:
[0038]
[0039] The block polyether ester of formula II is a product obtained by a single-side esterification reaction, and the block polyether ester of formula III is a product obtained by a double-side esterification reaction.
[0040] In some embodiments, the organic acid is one or more of stearic acid, p-tert-butyl formic acid, and oleic acid.
[0041] In some embodiments, the molar ratio of the block polyether to the organic acid is (0.9-1.1):1;
[0042] In some embodiments, the temperature of the esterification reaction is 140-200°C.
[0043] In some embodiments, the pressure of the esterification reaction is -0.06~0.02 MPa, preferably -0.04~0.02 MPa.
[0044] In some embodiments, the esterification reaction time is 6 to 8 hours.
[0045] In some embodiments, the catalyst for the esterification reaction is p-toluenesulfonic acid.
[0046] In one embodiment, the block polyether ester preparation method is as follows: a certain amount of EO / PO / EO block polyether and organic acid are added as raw materials in a three-necked flask equipped with a thermometer, a vacuum condenser and a heating magnetic stirrer, and an esterification reaction is carried out for 6 hours at a temperature of 190° C., a catalyst of 0.5% p-toluenesulfonic acid, and a pressure of -0.04 MPa. After the reaction is completed and cooled to room temperature, the pH value of the product is measured, and the pH value of the product is adjusted to 6-7 with triethanolamine; wherein 0.5% p-toluenesulfonic acid refers to the mass percentage of p-toluenesulfonic acid in the solution.
[0047] Preferably, the molar ratio of the block polyether to the organic acid is 1:1; at this dosage ratio, the synthesized product consists of a unilaterally esterified block polyether ester (structure of Formula II) and a bilaterally esterified block polyether ester (structure of Formula III); wherein the unilaterally esterified block polyether ester is the main product, while the bilaterally esterified block polyether ester is the secondary product, and its content is less than 1%.
[0048] The present invention also provides a cutting fluid, which comprises the following components based on 100 parts by mass: 5-30 parts of a lubricant; 1-30 parts of a wetting agent; 1-10 parts of a solubilizer; and the balance is deionized water; wherein the lubricant comprises the block polyether ester described above; the wetting agent comprises an alcohol polyoxyalkylene ether; and the solubilizer comprises at least one of a polyol and a phenoxy alcohol.
[0049] In the present invention, through the reasonable design of the formula, the cutting fluid only contains lubricants and wetting agents, and the content is relatively low; in the existing cutting fluid formula, in addition to the necessary components such as lubricants and wetting agents, surfactants such as penetrants and defoamers are also added, which will lead to a high COD value; compared with the existing cutting fluid formula, the COD value in the cutting fluid of the present application is lower.
[0050] In the present invention, since the terminal ester group of the block polyether ester cannot form a hydrogen bond with water, it has the characteristics of both polyether and ester substances; the above-mentioned EO / PO / EO block polyether ester is combined with other components to have good lubrication performance, low foam, defoaming, solubilization, dispersion and other effects.
[0051] In the present invention, by adding a wetting agent into the cutting fluid and coordinating with other components, the effects of low foaming and wetting are achieved.
[0052] In the present invention, by adding specific types of solubilizers and wetting agents, the overall performance of the cutting fluid can be improved; if other types of solubilizers are added, the cutting fluid system will show poor performance.
[0053] In some embodiments, the alcohol polyoxyethylene ether is one or more of decynediol polyoxyethylene ether, dodecynediol polyoxyethylene ether, isomeric octanol polyoxyethylene ether, isomeric decanol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether and fatty alcohol polyoxyethylene polyoxypropylene ether.
[0054] In some embodiments, the polyol is one or more of propylene glycol, isohexylene glycol, and glycerol.
[0055] In some embodiments, the phenoxy alcohol is phenoxyethanol.
[0056] In some embodiments, the mass fraction of the lubricant is 10-15, such as 10, 11 or 12.
[0057] In some embodiments, the mass fraction of the wetting agent is 10-30, such as 22, 25 or 26.
[0058] In some embodiments, the wetting agent consists of decynediol polyoxyethylene ether, dodecynediol polyoxyethylene ether and isomeric decanol polyoxyethylene ether.
[0059] In some embodiments, the mass fraction of the solubilizer is 1-5, such as 1, 2 or 3.
[0060] In one embodiment, the cutting fluid comprises the following components: 12 parts of lubricant; 22 parts of wetting agent; 2 parts of solubilizer; 64 parts of deionized water; wherein the lubricant comprises a block polyether ester having the following structure:
[0061]
[0062] The weight average molecular weight of the block polyether ester is 4500, and R1 is C 17 The hydrocarbon group has a molecular formula of (CH)8(CH)2(CH2)7, a=22, b=40, c=22, and a molecular distribution index of 1.3; the wetting agent is composed of 5 parts of decynediol polyoxyethylene ether, 3 parts of dodecynediol polyoxyethylene ether and 14 parts of isomeric decanol polyoxyethylene ether; the solubilizer is phenoxyethanol.
[0063] In one embodiment, the cutting fluid comprises the following components: 11 parts of lubricant; 26 parts of wetting agent; 1 part of solubilizer; 62 parts of deionized water; wherein the lubricant comprises a block polyether ester having the following structure:
[0064]
[0065] The weight average molecular weight of the block polyether ester is 6000; R1 is C 17The hydrocarbon group has a molecular formula of (CH)8(CH)2(CH2)7, a=30, b=55, c=30, and a molecular distribution index of 1.3; the wetting agent is composed of 13 parts of decynediol polyoxyethylene ether, 2 parts of dodecynediol polyoxyethylene ether and 11 parts of isomeric decanol polyoxyethylene ether; the solubilizer is propylene glycol.
[0066] In one embodiment, the cutting fluid comprises the following components: 10 parts of lubricant; 25 parts of wetting agent; 3 parts of solubilizer; 62 parts of deionized water; wherein the lubricant comprises a block polyether ester having the following structure:
[0067]
[0068] The weight average molecular weight of the block polyether ester is 8000; R1 is C 17 The hydrocarbon group has a molecular formula of (CH)8(CH)2(CH2)7, a=46, b=65, c=46, and a molecular distribution index of 1.3; the wetting agent is composed of 10 parts of decynediol polyoxyethylene ether, 1 part of dodecynediol polyoxyethylene ether and 14 parts of isomeric decanol polyoxyethylene ether; the solubilizer is isohexanediol.
[0069] In one embodiment, the cutting fluid comprises the following components: 10 parts of lubricant; 25 parts of wetting agent; 2 parts of solubilizer; 63 parts of deionized water; wherein the lubricant comprises a block polyether ester having the following structure,
[0070]
[0071] The weight average molecular weight of the block polyether ester is 10000; R1 is C 17 The hydrocarbon group has a molecular formula of (CH)8(CH)2(CH2)7, a=40, b=110, c=40, and a molecular distribution index of 1.3; the wetting agent is composed of 13 parts of decynediol polyoxyethylene ether, 2 parts of dodecynediol polyoxyethylene ether and 10 parts of isomeric decanol polyoxyethylene ether; the solubilizer is glycerol.
[0072] The present invention also provides a use of the cutting fluid as described above in a diamond wire cutting process.
[0073] On the basis of being in accordance with the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.
[0074] The reagents and raw materials used in the present invention are commercially available.
[0075] The positive and progressive effects of the present invention are:
[0076] The components in the cutting fluid of the present invention cooperate with each other, the hydrophilicity is reduced, the lipophilicity is enhanced, the surface tension is reduced, and the lubrication performance of the formula is effectively improved; and it also has the advantages of low foaming, fast defoaming rate, low surface tension, etc. Therefore, the amount of wetting agent and lubricant can be reduced to achieve the goal of low COD value. BRIEF DESCRIPTION OF THE DRAWINGS
[0077] Figure 1 This is the infrared spectrum of the block polyether ester of Example 1 of the present application.
[0078] Figure 2 This is the gel chromatogram of the block polyether ester of Example 1 of the present application. DETAILED DESCRIPTION
[0079] The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions, or selected according to the product specifications.
[0080] Example 1
[0081] This embodiment provides a block polyether ester and a preparation method thereof;
[0082] The preparation method of the block polyether ester is as follows:
[0083] S1. Preparation of block polyether: 50 g of propylene glycol and KOH catalyst are added into a reactor, and replaced with N2, wherein the mass ratio of propylene glycol to KOH is 1000:1; the temperature is raised to 100-120°C, and ethylene oxide (EO), propylene oxide (PO) and ethylene oxide (EO) are introduced in sequence, and the reaction is carried out at a temperature and pressure of 140°C and 0.2 MPa, respectively; wherein, in the order of addition, the EO feeding time is 1 h (rate 10 g / min), the reaction time is 30 min, the PO feeding time is 2.5 h (rate 10 g / min), the reaction time is 1.5 h, the EO feeding time is 1 h (rate 10 g / min), and the reaction time is 1 h.
[0084] After a certain amount of epoxide has been passed through, the temperature is kept until there is no pressure change, the temperature is lowered to 100°C and then vacuumed, the temperature is lowered to 80°C and then neutralized and discharged to obtain a block polyether.
[0085] S2. Esterification of block polyether: In a three-necked flask equipped with a thermometer, a vacuum condenser and a heated magnetic stirrer; in a molar ratio of 1:1, the above-mentioned block polyether and oleic acid are used as raw materials, and the esterification reaction is carried out at a temperature of 190°C, a catalyst of 0.5% p-toluenesulfonic acid, and a pressure of -0.04 MPa for 6 hours. After the reaction is completed and cooled to room temperature, the pH value of the product is measured, and the pH value of the product is adjusted to 6-7 with triethanolamine; the above-mentioned block polyether ester is prepared; wherein 0.5% p-toluenesulfonic acid refers to the mass percentage of p-toluenesulfonic acid in the solution.
[0086] The block polyetherester is a polymer as shown below:
[0087]
[0088] Wherein R1 is selected from C 17 A hydrocarbon group, whose molecular formula is (CH)8(CH)2(CH2)7, a1 is 24, b1 is 46, and c1 is 24.
[0089] Nicolet iG50 FTIR spectrometer ATR7 was used to test the structure of block polyether ester. Figure 1 : is the infrared spectrum of the block polyether ester of this embodiment. Figure 1 As shown, at wave number 1731 cm -1 The characteristic peak of carbonyl group of carbon-oxygen double bond appeared near 2800-2900 cm -1 The infrared stretching vibration absorption peaks of methyl and methylene at 1380 cm -1 It is the infrared bending vibration absorption peak of methyl and methylene, 1094 cm -1 There is a strong CO single bond absorption peak nearby. It can be seen that the block polyether ester has an ester structure.
[0090] The block polyether ester was tested using a Waters 1515 gel permeation chromatograph (GPC) and a Waters 2414 refractive index detector; Figure 2 : is the gel chromatogram of the block polyether ester of the present embodiment. Figure 2 As shown, the molecular weight of the block polyether is about 4700. And the molecular weight distribution index of the block polyether ester is 1.3.
[0091] Example 2
[0092] This embodiment provides a cutting fluid, the formula of which is composed of the following parts by mass:
[0093] Lubricant: block polyether ester (weight average molecular weight 4500): 12 parts;
[0094] Wetting agent: decynediol polyoxyethylene ether: 5 parts; dodecynediol polyoxyethylene ether: 3 parts; isomeric octaol polyoxyethylene ether: 14 parts;
[0095] Solubilizer: phenoxyethanol: 2 parts;
[0096] Deionized water: 64 parts.
[0097] Wherein, the block polyether ester is a polymer as shown below:
[0098]
[0099] The block polyether ester is a unilaterally esterified block polyether ester, and the esterification reaction raw materials are block polyether and oleic acid, R1 is C 17 The hydrocarbon group has the molecular formula of (CH)8(CH)2(CH2)7, a=22, b=40, c=22, and the molecular distribution index is 1.3; EO feeding time is 1h (rate 10 g / min), reaction time is 30 min, PO feeding time is 2 h (rate 10 g / min), reaction time is 1.5h, EO feeding time is 1h (rate 10 g / min), reaction time is 1h.
[0100] The block polyether ester preparation method comprises the following steps: in a three-necked flask equipped with a thermometer, a vacuum condensation device and a heating magnetic stirrer, using the block polyether and oleic acid as raw materials at a molar ratio of 1.05:1, carrying out an esterification reaction for 6 hours at a temperature of 190°C, using 0.5% p-toluenesulfonic acid as a catalyst, and a pressure of -0.04 MPa, cooling the reaction to room temperature after the reaction is completed, measuring the pH value of the product, and adjusting the pH value of the product to 6-7 with triethanolamine; preparing the block polyether ester; wherein 0.5% p-toluenesulfonic acid refers to the mass percentage of p-toluenesulfonic acid in the solution.
[0101] Example 3
[0102] This embodiment provides a cutting fluid, the formula of which is composed of the following parts by mass:
[0103] Lubricant: block polyether ester (weight average molecular weight 6000): 11 parts;
[0104] Wetting agent: decynediol polyoxyethylene ether: 13 parts; dodecynediol polyoxyethylene ether: 2 parts; isomeric tridecanol polyoxyethylene ether: 11 parts;
[0105] Solubilizer: propylene glycol: 1 part;
[0106] Deionized water: 62 parts.
[0107] Wherein, the block polyether ester is a polymer as shown below:
[0108]
[0109] The block polyether ester is a unilaterally esterified block polyether ester, and the esterification reaction raw materials are block polyether and oleic acid, R1 is C 17 The hydrocarbon group has a molecular formula of (CH)8(CH)2(CH2)7, a=30, b=55, c=30, and a molecular distribution index of 1.3. EO feed time 1.5 h (rate 10 g / min), reaction time 45 min, PO feed time 3 h (rate 10 g / min), reaction time 2 h, EO feed time 1.5 h (rate 10 g / min), reaction time 1 h.
[0110] Example 4
[0111] The cutting fluid of this embodiment is formulated according to the following mass fractions:
[0112] Lubricant: block polyether ester (weight average molecular weight 8000): 10 parts;
[0113] Wetting agent: decynediol polyoxyethylene ether: 10 parts; dodecynediol polyoxyethylene ether: 1 part; isomeric decanol polyoxyethylene ether: 14 parts;
[0114] Solubilizer: isohexanediol: 3 parts
[0115] Deionized water: 62 parts.
[0116] Wherein, the block polyether ester is a polymer as shown below:
[0117]
[0118] The block polyether ester is a unilaterally esterified block polyether ester, and the esterification reaction raw materials are block polyether and oleic acid, R1 is C 17 The hydrocarbon group has a molecular formula of (CH)8(CH)2(CH2)7, a=46, b=65, c=46, and a molecular distribution index of 1.3. EO feed time 1h (rate 20 g / min), reaction 1h, PO feed time 3.5h (rate 10 g / min), reaction time 3h, EO feed time 1h (rate 20 g / min), reaction time 1.5h.
[0119] Example 5
[0120] The cutting fluid of this embodiment is formulated according to the following mass fractions:
[0121] Lubricant: block polyether ester (weight average molecular weight 10000): 10 parts;
[0122] Wetting agent: decynediol polyoxyethylene ether: 13 parts; dodecynediol polyoxyethylene ether: 2 parts; isomeric decanol polyoxyethylene ether: 10 parts;
[0123] Solubilizer: glycerol: 2 parts;
[0124] Deionized water: 63 parts.
[0125] Wherein, the block polyether ester is a polymer as shown below:
[0126]
[0127] The block polyether ester is a unilaterally esterified block polyether ester, and the esterification reaction raw materials are block polyether and oleic acid, R1 is C 17 The hydrocarbon group has a molecular formula of (CH)8(CH)2(CH2)7, a=40, b=110, c=40, and a molecular distribution index of 1.3. EO feed time 1 h (rate 20 g / min), reaction 1 h, PO feed time 6.5 h (rate 10 g / min), reaction time 4 h, EO feed time 1 h (rate 20 g / min), reaction time 1.5 h.
[0128] Effect Example 1
[0129] This effect example studies the cutting performance of the cutting fluids of Examples 2-5, including: average torque value, A-grade yield, A-line mark ratio, B-sheet line mark ratio, TTV and wire breakage rate. The specific test method is as follows:
[0130] The above-mentioned implementation cases 2-5 and commercially available competitive products 1-4 were diluted with deionized water at a ratio of 1:100-300, and the existing cutting process was used to cut solar-grade 210 mm single crystal silicon wafers under the same cutting parameter conditions (diamond wire diameter 40 μm, line speed 2240 m / min). The results are shown in Table 1, which shows the cutting effect of using the cutting fluid of Example 2-5.
[0131] In Table 1, the A-grade yield refers to the proportion of silicon wafers reaching Grade A; the A-line mark ratio refers to the proportion of silicon wafers with line marks; the B-wafer line mark refers to the proportion of silicon wafers with too many line marks that will be downgraded from Grade A to Grade B (wherein, the surface of Grade A is completely uncontaminated and the substrate has no defects, and Grade B has partial defects but does not affect the use); the torque value is tested using a tapping torque machine, and the lower the value, the better the lubrication performance; TTV refers to the overall deviation of the thickness change of the silicon wafer during the cutting process.
[0132] Table 1
[0133]
[0134] From the above data, it can be seen that at a concentration of 10%, the average torque values of Examples 2-5 are lower than those of commercially available competing products 1 to 3, indicating that the use of segmented polyether ester can effectively improve the lubrication performance of the formula; Examples 2-5 have obvious advantages over commercially available competing products 1 to 3 in terms of line mark percentage and TTV data, indicating that the cut silicon wafers are more uniform in thickness and have a lower wire breakage rate, indicating that Examples 2-5 have better lubrication performance than commercially available competing products 1 to 3.
[0135] It can be seen that the cutting fluid of the present application has reduced hydrophilicity, enhanced lipophilicity, reduced surface tension, good wettability, which is reflected by a low wire breakage rate; it also has good lubricity, which is reflected by a low torque value; good lubricity and good wettability result in low TTV.
[0136] In addition, the COD value of the cutting fluid of Examples 1-5 of the present application was tested, and the testing instruments included: HACH UV-Vis spectrophotometer DR6000, DRB200 COD digester; COD rapid digestion prefabricated tube range 100-1000 mg / L. The existing cutting fluid stock solution and the cutting fluid stock solution of the present application were diluted in the same proportion, falling within the above range, and then tested. The COD value of the existing cutting fluid is generally 900,000 mg / L-1.1 million mg / L; the COD value of the cutting fluid of the present application is 750,000 mg / L-850,000 mg / L.
[0137] Comparative Example 1
[0138] This comparative example discloses a cutting fluid, which is different from the cutting fluid of Example 2 in that: trans-block polyether 1740 is used as a lubricant, and the specific formula is composed of the following mass fractions:
[0139] Lubricant: trans-block polyether 1740: 12 parts; the manufacturer and model of the trans-block polyether 1740 are Wanhua Chemical and WANOL BE17R4 respectively;
[0140] Wetting agent: decynediol polyoxyethylene ether: 5 parts; dodecynediol polyoxyethylene ether: 3 parts; isomeric octaol polyoxyethylene ether: 14 parts;
[0141] Solubilizer: phenoxyethanol: 2 parts;
[0142] Deionized water: 64 parts.
[0143] Comparative Example 2
[0144] This comparative example discloses a cutting fluid, which differs from the cutting fluid of Example 2 in that: trans-block polyether 1720 is used as a lubricant, and the specific formula is composed of the following mass fractions:
[0145] Lubricant: trans-block polyether 1720: 12 parts; the manufacturer and model of the trans-block polyether 1740 are Wanhua Chemical and WANOL BE17R2 respectively;
[0146] Wetting agent: decynediol polyoxyethylene ether: 5 parts; dodecynediol polyoxyethylene ether: 3 parts; isomeric octaol polyoxyethylene ether: 14 parts;
[0147] Solubilizer: phenoxyethanol: 2 parts;
[0148] Deionized water: 64 parts.
[0149] Comparative Example 3
[0150] This comparative example discloses a cutting fluid, which differs from the cutting fluid of Example 2 in that isononanol polyether is used as a wetting agent, and the specific formula is composed of the following mass fractions:
[0151] Lubricant: block polyether ester (molecular weight 4500): 12 parts;
[0152] Wetting agent: isononyl alcohol polyether: 22 parts;
[0153] Solubilizer: phenoxyethanol: 2 parts;
[0154] Deionized water: 64 parts.
[0155] Wherein, the block polyether ester is a polymer as shown below:
[0156]
[0157] The block polyether ester is a unilaterally esterified block polyether ester, wherein the esterified reaction raw materials are block polyether and oleic acid, and R1 is selected from C 17 The hydrocarbon group has the molecular formula (CH)8(CH)2(CH2)7, a=22, b=40, c=22, and the molecular distribution index is 1.3.
[0158] Comparative Example 4
[0159] This comparative example discloses a cutting fluid, which differs from the cutting fluid of Example 2 in that isononanol polyether is used as a wetting agent, and the specific formula is composed of the following mass fractions:
[0160] Lubricant: block polyether ester (molecular weight 4500): 35 parts;
[0161] Wetting agent: decynediol polyoxyethylene ether: 5 parts; dodecynediol polyoxyethylene ether: 3 parts; isomeric octaol polyoxyethylene ether: 14 parts;
[0162] Solubilizer: phenoxyethanol: 2 parts;
[0163] Deionized water: 41 parts.
[0164] Wherein, the block polyether ester is a polymer as shown below:
[0165]
[0166] The block polyether ester is a unilaterally esterified block polyether ester, wherein the esterified reaction raw materials are block polyether and oleic acid, and R1 is selected from C 17 The hydrocarbon group has the molecular formula (CH)8(CH)2(CH2)7, a=22, b=40, c=22, and the molecular distribution index is 1.3.
[0167] Effect Example 2
[0168] This effect example studies other relevant performance parameters of the cutting fluids of Example 2 and Comparative Examples 1-4, including: surface tension, bubble height, and defoaming time. The specific test method is as follows:
[0169] Surface tension tester and method: KRUSS BP100 dynamic surface tension meter; weigh 0.8g cutting fluid and dilute it into 100g deionized water, record 6 bubbles / s data, the lower the surface tension, the better the wettability.
[0170] The tester and method for foaming time and height: HCR700 metalworking fluid anti-foaming tester is used. 1000ml of 0.8% concentration cutting fluid is poured into the instrument, the temperature is kept at 20℃, and the test is circulated for 10 minutes under 10V voltage conditions. The foaming height and defoaming time are recorded.
[0171] The results are shown in Table 2, which shows the surface tension, bubble height, and defoaming time of the cutting fluids of Example 2 and Comparative Examples 1-4.
[0172] Table 2
[0173]
[0174] Among them, surface tension can reflect the wetting performance. The lower the surface tension, the better the wetting performance. Foam height and defoaming time affect practical applications. Excessive foam can lead to situations such as foam overflowing the cylinder, and will increase the average torque value and wire breakage rate.
[0175] As shown in the table above, using Example 2 as a single-factor variable experiment, using commonly used lubricants trans-block polyethers 1740 and 1720 (Comparative Examples 1-2), the surface tension and foam properties are both deteriorated, which may have a negative impact in the actual application of the cutting fluid, such as cutting problems. Then the type of wetting agent is changed, and the commonly used isononanol polyether is used (Comparative Example 3). The isononanol polyether itself has poor wetting properties and poor compatibility with other components in the formula, which leads to an increase in the surface tension of the cutting fluid. If the amount of lubricant is increased (Comparative Example 4), the foam performance will deteriorate significantly. The cutting fluid formula of the present invention achieves the best effect. It can be seen that the performance of the cutting fluid of the present application is significantly better than that of the cutting fluid of the comparative example.
Claims
1. A block polyether, characterized in that: The block polyether is a polymer as shown in Formula I: Formula I wherein a0 is an integer selected from 17 to 50, b0 is an integer selected from 40 to 110, and c0 is an integer selected from 17 to 50.
2. The block polyether according to claim 1, characterized in that The block polyether satisfies one or more of the following conditions: ① a1 or a2 is an integer selected from 22 to 46, such as 22, 30, 40 or 46; ② b1 or b2 is 40, 55, 65 or 110; ③The c1 or the c2 is an integer selected from 22 to 46, for example 22, 30, 40 or 46.
3. A method for preparing a block polyether as claimed in claim 1, characterized in that: The preparation method comprises the following steps: In a catalytic system under an inert atmosphere, a first ethylene oxide, a propylene oxide and a second ethylene oxide are introduced in sequence for reaction, the reaction temperature is 120-150° C., the reaction pressure is 0-0.4 MPa; the mass ratio of the first ethylene oxide, the propylene oxide and the second ethylene oxide is 1: (1.8-3.5): 1; Preferably, the catalyst of the catalytic system comprises propylene glycol and potassium hydroxide; Preferably, the inert atmosphere comprises nitrogen; Preferably, the feed rates of the first ethylene oxide and the second ethylene oxide are independently 10-20 g / min; Preferably, the feed rate of propylene oxide is 5-10 g / min.
4. A block polyether ester, characterized in that: The block polyether ester is a polymer as shown in Formula II or Formula III: Formula II Wherein, R1 is selected from C7~C 17 A hydrocarbon group, a1 is an integer selected from 17 to 50, b1 is an integer selected from 40 to 110, and c1 is an integer selected from 17 to 50; Formula III Wherein, R2 is selected from C7~C 17 The hydrocarbon group, R3 is selected from C7~C 17 a2 is an integer selected from 17 to 50, b2 is an integer selected from 40 to 110, and c2 is an integer selected from 17 to 50.
5. The block polyetherester according to claim 4, characterized in that The block polyether ester meets one or more of the following conditions: ① The weight average molecular weight of the block polyether ester is 4000-11000; preferably 4500-11000, for example 4500, 6000, 8000 or 10000; ② The molecular weight distribution index of the block polyether ester is 1.1 to 3; ③ The R2 and R3 are hydrocarbon groups with the same molecular structure; ④ The R1 or R2 is selected from C 17 The hydrocarbon group; ⑤ a1 or a2 is an integer selected from 22 to 46, such as 22, 30, 40 or 46; ⑥ b1 or b2 is 40, 55, 65 or 110; ⑦ The c1 or c2 is an integer selected from 22 to 46, such as 22, 30, 40 or 46; Preferably, the weight average molecular weight of the block polyether ester is 4500, and R1 is C 17 The hydrocarbon group has the molecular formula (CH)8(CH)2(CH2)7, a=22, b=40, c=22, and the molecular distribution index is 1.3; Preferably, the weight average molecular weight of the block polyether ester is 6000; R1 is C 17 The hydrocarbon group has the molecular formula (CH)8(CH)2(CH2)7, a=30, b=55, c=30, and the molecular distribution index is 1.3; Preferably, the weight average molecular weight of the block polyether ester is 8000; R1 is C 17 The hydrocarbon group has the molecular formula (CH)8(CH)2(CH2)7, a=46, b=65, c=46, and the molecular distribution index is 1.3; Preferably, the weight average molecular weight of the block polyether ester is 10000; R1 is C 17 The hydrocarbon group has the molecular formula (CH)8(CH)2(CH2)7, a=40, b=110, c=40, and the molecular distribution index is 1.
3.
6. A method for preparing a block polyether ester as claimed in claim 4 or 5, characterized in that: The preparation method comprises the following steps: Esterifying the block polyether as claimed in claim 1 or 2 with an organic acid to obtain a block polyether ester; Preferably, the organic acid is one or more of stearic acid, p-tert-butyl formic acid and oleic acid; Preferably, the molar ratio of the block polyether to the organic acid is (0.9-1.1):1; Preferably, the temperature of the esterification reaction is 140-200°C; Preferably, the pressure of the esterification reaction is -0.06~0.02 MPa; Preferably, the esterification reaction time is 6 to 8 h; Preferably, the catalyst for the esterification reaction is p-toluenesulfonic acid.
7. A cutting fluid, characterized in that: The cutting fluid comprises the following components based on 100 parts by mass: 5-30 parts of lubricant; 1-30 parts of wetting agent; 1-10 parts of solubilizer; the balance is deionized water; Wherein, the lubricant comprises the block polyether ester as claimed in claim 3 or 4; The wetting agent includes alcohol polyoxyalkylene ether; The solubilizing agent includes at least one of a polyol and a phenoxy alcohol.
8. The cutting fluid according to claim 7, characterized in that The cutting fluid meets one or more of the following conditions: ① The alcohol polyoxyethylene ether is one or more of decynediol polyoxyethylene ether, dodecynediol polyoxyethylene ether, isomeric octyl alcohol polyoxyethylene ether, isomeric decanol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether and fatty alcohol polyoxyethylene polyoxypropylene ether; ② The polyol is one or more of propylene glycol, isohexylene glycol and glycerol; ③ The phenoxy alcohol is phenoxyethanol; ④ The mass fraction of the lubricant is 10-15, such as 10, 11 or 12; ⑤ The mass fraction of the wetting agent is 10-30, for example 22, 25 or 26; ⑥ The wetting agent is composed of decynediol polyoxyethylene ether, dodecynediol polyoxyethylene ether and isomeric decanol polyoxyethylene ether; ⑦ The mass fraction of the solubilizing agent is 1-5, such as 1, 2 or 3.
9. The cutting fluid according to claim 7, characterized in that The cutting fluid comprises the following components: 12 parts of lubricant; 22 parts of wetting agent; 2 parts of solubilizer; 64 parts of deionized water; Wherein, the lubricant comprises a block polyether ester having the following structure: The weight average molecular weight of the block polyether ester is 4500, and R1 is C 17 The hydrocarbon group has the molecular formula (CH)8(CH)2(CH2)7, a=22, b=40, c=22, and the molecular distribution index is 1.3; The wetting agent is composed of 5 parts of decynediol polyoxyethylene ether, 3 parts of dodecynediol polyoxyethylene ether and 14 parts of isomeric decanol polyoxyethylene ether; The solubilizing agent is phenoxyethanol; Alternatively, the cutting fluid comprises the following components: 11 parts of lubricant; 26 parts of wetting agent; 1 part of solubilizer; 62 parts of deionized water; Wherein, the lubricant comprises a block polyether ester having the following structure: The weight average molecular weight of the block polyether ester is 6000; R1 is C 17 The hydrocarbon group has the molecular formula (CH)8(CH)2(CH2)7, a=30, b=55, c=30, and the molecular distribution index is 1.3; The wetting agent is composed of 13 parts of decynediol polyoxyethylene ether, 2 parts of dodecynediol polyoxyethylene ether and 11 parts of isomeric decanol polyoxyethylene ether; The solubilizing agent is propylene glycol; Alternatively, the cutting fluid comprises the following components: 10 parts of lubricant; 25 parts of wetting agent; 3 parts of solubilizer; 62 parts of deionized water; Wherein, the lubricant comprises a block polyether ester having the following structure: The weight average molecular weight of the block polyether ester is 8000; R1 is C 17 The hydrocarbon group has the molecular formula (CH)8(CH)2(CH2)7, a=46, b=65, c=46, and the molecular distribution index is 1.3; The wetting agent is composed of 10 parts of decynediol polyoxyethylene ether, 1 part of dodecynediol polyoxyethylene ether and 14 parts of isomeric decanol polyoxyethylene ether; The solubilizing agent is isohexylene glycol; Alternatively, the cutting fluid comprises the following components: 10 parts of lubricant; 25 parts of wetting agent; 2 parts of solubilizer; 63 parts of deionized water; Wherein, the lubricant comprises a block polyether ester having the following structure: The weight average molecular weight of the block polyether ester is 10000; R1 is C 17 The hydrocarbon group has the molecular formula (CH)8(CH)2(CH2)7, a=40, b=110, c=40, and the molecular distribution index is 1.3; The wetting agent is composed of 13 parts of decynediol polyoxyethylene ether, 2 parts of dodecynediol polyoxyethylene ether and 10 parts of isomeric decanol polyoxyethylene ether; The solubilizing agent is glycerol.
10. Use of the cutting fluid according to any one of claims 6 to 9 in a diamond wire cutting process.