Polyether polyol, polyether polyol functionality testing method, isocyanate prepolymer and polishing pad

Abstract

The invention relates to a polyether polyol functionality testing method, polyether polyol, an isocyanate prepolymer and a polishing pad, the polyether polyol is derivatized by adopting organic reaction, the molecular weight of the polyether polyol is measured by using gel permeation chromatography (GPC), the structure of the derivatized polyether polyol is measured by using a nuclear magnetic resonance spectrometer (NMR), and the functionality of the polyether polyol is measured by using the NMR. Calculating the functionality of the polyether polyol by using the integral proportion of the characteristic peak; in addition, polyether polyol as shown in the structural formula 1 is further synthesized, and when the values of x, y and z are adjusted to be within a certain range, the prepared isocyanate prepolymer shows a good polishing effect, and therefore the obtained polishing pad shows a good polishing effect. And # imgabs0 #.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer material analysis, and particularly relates to a method for testing the functionality of polyether polyols. Background Art

[0002] Polyether polyols are one of the important raw materials for the production of polyurethane and are used in elastomers, coatings, adhesives, soft foams, hard foams and other fields.

[0003] Polyether polyols are usually prepared by ring-opening polymerization of a revelation compound (initiator) having multiple active hydrogen atoms (multifunctionality) with one or more epoxy compounds (monomers) under the action of a catalyst. The polymerization reaction can use a variety of different catalysts and catalytic processes, such as alkaline catalysts such as KOH, phosphazene catalysts, bimetallic catalysts, etc., among which the polymerization process using an alkaline catalyst is the most commonly used polymerization process. Epoxides (monomers) generally refer to propylene oxide, ethylene oxide, butylene oxide or a mixture thereof. Multifunctional initiators such as polyols and amines, for example, diethylene glycol, glycerol, trimethylolpropane, diethanolamine, pentaerythritol, sorbitol, mannitol, etc.

[0004] For the polyether polyols sold on the market, there is often a certain difference between their nominal functionality and actual functionality. The main reason is that during the synthesis process of polyether polyols, there will be a series of side reactions. For example, propylene oxide undergoes a side reaction under alkaline catalysis to generate potassium propylene oxide, which will further polymerize and lead to a decrease in functionality. Impurities in the raw materials such as water, methanol, propylene glycol and other substances will also trigger polymerization reactions to generate low-functionality polyethers.

[0005] Polyurethane is the main component of polishing pads, a polishing consumable in the semiconductor field. The stability of its physical and chemical parameters has a significant impact on the polishing performance of the polishing pad. Polyether polyols, as one of the synthetic materials of polyurethane, also affect the physical and chemical parameters of polyurethane. The functionality of polyether polyols is one of the most common parameters, and its testing method has been widely studied. Among them: the American AIAA conference paper 78-122 reported the document "Functionality Determination in Hydroxyl-Terminated Prepolymers", which proposed a method for obtaining the number average functionality of terminal hydroxyl prepolymers using gel point test data; the British journal "British Polymer Journal" reported the document "The Molecular Characteristics of Hydroxyl-terminated Polybutadiene" in the first issue of 1985. The document proposed a method for determining the effective functionality of HTPB using a gel test, and proposed a method for determining the number average functionality using infrared spectroscopy (IR) combined with vapor pressure permeation test (VPO).

[0006] The existing testing methods for the functionality of polyether polyols in the prior art have large errors and require a large sample amount, which is not conducive to accurate measurement of data and is relatively complicated to operate. Therefore, a convenient and fast testing method for the functionality of polyether polyols with a small sample requirement is urgently needed. Summary of the invention

[0007] The present invention is based on the defects in the prior art. In a first aspect, the present invention provides a method for testing the functionality of a polyether polyol. The polyether polyol comprises a compound as shown in structural formula 1:

[0008]

[0009] Wherein, R represents any group, PO represents a structural fragment as shown in Structural Formula 2, EO represents a structural fragment as shown in Structural Formula 3, M PO represents the molecular weight of the fragment shown in structural formula 2, M EO represents the molecular weight of the fragment shown in structural formula 3, and * represents the bonding site:

[0010]

[0011] Determine the molecular weight M of the polyether polyol, perform an acetyl derivatization reaction on the hydroxyl groups at the chain ends of the polyether polyol, and then use a nuclear magnetic resonance (NMR) to determine the structure of the derivatized polyether polyol, wherein the structure of the derivatized polyether polyol includes three peaks a, b, and c in the NMR spectrum, the integral interval of the chemical shift of the a peak in the NMR spectrum is between 4.00ppm and 3.00ppm, the integral interval of the chemical shift of the b peak in the NMR spectrum is between 1.40ppm and 0.90ppm, and the integral interval of the chemical shift of the c peak in the NMR spectrum is between 2.08ppm and 1.96ppm, A represents the peak area of ​​the common peak a of PO and EO in NMR after the acetyl derivatization reaction of the polyether polyol, B represents the peak area of ​​the characteristic peak b of PO in NMR after the acetyl derivatization reaction of the polyether polyol, and C represents the peak area of ​​the characteristic peak c of acetyl in NMR after the acetyl derivatization reaction of the polyether polyol;

[0012] The single-chain molecular weight M1 of the polyether polyol and the functionality f of the polyether polyol are positive integers, which are calculated by rounding off, wherein M, M1 and f satisfy the following relationship:

[0013]

[0014] Further, the test method of the peak areas A, B, and C of the three peaks a, b, and c comprises the following steps: preparation of acetyl derivatization reaction reagents, acetyl derivatization reaction, sample separation, and nuclear magnetic resonance (NMR) testing;

[0015] The preparation of the acetyl derivatization reaction reagent comprises dissolving a certain amount of acetic anhydride and pyridine, wherein the molar ratio of acetic anhydride to pyridine is between 1:3 and 10, and standing for 1 hour to 24 hours to obtain a sample acetyl derivatization reaction reagent;

[0016] The acetyl derivatization reaction comprises taking a certain amount of polyether polyol and an excess of an acetyl derivatization reaction reagent, heating the acetyl derivatization reaction at 100° C. to 120° C. under nitrogen protection and stirring for 1 h to 5 h;

[0017] The sample separation comprises extracting and separating the polyether polyol after the acetyl derivatization reaction to obtain an organic phase, drying the organic phase, and rotary evaporating to obtain a nuclear magnetic resonance (NMR) test sample;

[0018] Wherein, the nuclear magnetic resonance (NMR) test includes dissolving the test sample in deuterated chloroform and then conducting the test;

[0019] Furthermore, the hydroxyl group at the end of the polyether polyol chain undergoes an acetyl derivatization reaction as shown in the chemical equation shown in the following equation 1:

[0020]

[0021] Further, the molecular weight M of the polyether polyol is determined using gel permeation chromatography (GPC), and the gel permeation chromatography test parameters are:

[0022] Chromatographic column: Agilent PLgel single pore size column, part number PL1110-6530, 7.5×300mm, with guard column, part number PL110-1520, 7.5×50mm;

[0023] Column temperature: 40°C;

[0024] Mobile phase: chromatography grade tetrahydrofuran;

[0025] Mobile phase flow rate: 0.7 ml / min;

[0026] Detector: differential detector;

[0027] Sample injection volume: 20 μL;

[0028] The second aspect of the present invention provides a polyether polyol, wherein the molecular weight of the polyether polyol is M, wherein M is between 1000 and 10000, and the polyether polyol comprises a compound as shown in structural formula 1:

[0029]

[0030] Wherein, R represents any group, PO represents a structural fragment as shown in Structural Formula 2, EO represents a structural fragment as shown in Structural Formula 3, and * represents a bonding site:

[0031]

[0032] The polyether polyol as shown in structural formula 1, wherein x, y, and z satisfy the following relationship, z is between 2 and 8, and x / y is between 1 and 100:

[0033]

[0034] The polyether polyol M PO represents the molecular weight of the fragment shown in structural formula 2, M EOrepresents the molecular weight of the fragment shown in structural formula 3, the structure of the polyether polyol after derivatization includes three peaks of a, b, and c in the NMR spectrum, the integral interval of the chemical shift of the a peak in the NMR spectrum is between 4.00ppm and 3.00ppm, the integral interval of the chemical shift of the b peak in the NMR spectrum is between 1.40ppm and 0.90ppm, and the integral interval of the chemical shift of the c peak in the NMR spectrum is between 2.08ppm and 1.96ppm, A represents the peak area of ​​the common peak a of PO and EO in NMR after the acetyl derivatization reaction of the polyether polyol, B represents the peak area of ​​the characteristic peak b of PO in NMR after the acetyl derivatization reaction of the polyether polyol, and C represents the peak area of ​​the characteristic peak c of acetyl in NMR after the acetyl derivatization reaction of the polyether polyol;

[0035] Preferably, in the structural formula 1, z is between 2 and 4, and x / y is between 1 and 10.

[0036] The third aspect of the present invention provides an isocyanate prepolymer obtained by reacting raw materials including multifunctional isocyanate and polyol, with NCO as the end-capping group, and the polyol includes the above-mentioned polyether polyol;

[0037] Furthermore, the polyfunctional isocyanate comprises an aromatic isocyanate and / or an aliphatic isocyanate, the aromatic isocyanate comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, and dimethyl diphenyl diisocyanate, preferably one or a combination of toluene diisocyanate and diphenylmethane diisocyanate; the aliphatic isocyanate comprises one or more of isophorone diisocyanate, 1,4-cyclohexane diisocyanate, and dicyclohexylmethane diisocyanate, preferably dicyclohexylmethane diisocyanate.

[0038] A fourth aspect of the present invention provides a polishing pad comprising a polishing layer, wherein the polishing layer comprises a polymeric substrate, and the polymeric substrate is obtained by curing the isocyanate prepolymer according to claim;

[0039] Furthermore, the polishing pad comprises a buffer layer, an adhesive layer and a back adhesive layer, the adhesive layer is used for bonding the polishing layer to the buffer layer, the back adhesive layer is used for bonding the polishing pad to the polishing machine, and the back adhesive layer also comprises release paper or release film.

[0040] Beneficial Effects

[0041] The method for detecting the functionality of polyether polyols involved in the present invention has the advantages of being more suitable for trace detection (samples below 50 mg), and is simple and easy to implement. In particular, it has a better effect on the functionality analysis of raw material polyether polyols in polyurethane materials, and can effectively improve the efficiency and accuracy of the analysis. At the same time, the present invention finds that when the structural parameters of the polyether polyol meet certain conditions, the isocyanate prepolymer prepared therefrom and then the polishing pad prepared therefrom exhibit excellent polishing performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0043] Figure 1 The peak positions and peak areas A, B, C of three peaks a, b, c of nuclear magnetic resonance (NMR) of the polyether polyol of the present invention after acetyl derivatization reaction;

[0044] Figure 2 It is the peak position of two peaks a' and b' of nuclear magnetic resonance (NMR) of polyether polyol before acetyl derivatization reaction;

[0045] Figure 3 It is a schematic diagram of the polishing device in the present invention;

[0046] 1- material to be polished, 2- polishing pad, 3- polishing machine, 4- bracket, 5- polishing liquid. DETAILED DESCRIPTION

[0047] The technical solution of the present invention will be described in detail below with reference to the accompanying drawings:

[0048] A method for testing the functionality of a polyether polyol, wherein the polyether polyol comprises a compound as shown in structural formula 1:

[0049]

[0050] Wherein, R represents any group, PO represents a structural fragment as shown in Structural Formula 2, EO represents a structural fragment as shown in Structural Formula 3, M PO represents the molecular weight of the structural fragment shown in structural formula 2, where MPO is 58, M EO It represents the molecular weight of the structural fragment shown in structural formula 3, where MEO is 44 and * represents the bonding site:

[0051]

[0052] Determine the molecular weight M of the polyether polyol, perform an acetyl derivatization reaction on the hydroxyl groups at the chain ends of the polyether polyol, and then use a nuclear magnetic resonance (NMR) to determine the structure of the derivatized polyether polyol, wherein the structure of the derivatized polyether polyol includes three peaks a, b, and c in the NMR spectrum, the integral interval of the chemical shift of the a peak in the NMR spectrum is between 4.00ppm and 3.00ppm, the integral interval of the chemical shift of the b peak in the NMR spectrum is between 1.40ppm and 0.90ppm, and the integral interval of the chemical shift of the c peak in the NMR spectrum is between 2.08ppm and 1.96ppm, A represents the peak area of ​​the common peak a of PO and EO in NMR after the acetyl derivatization reaction of the polyether polyol, B represents the peak area of ​​the characteristic peak b of PO in NMR after the acetyl derivatization reaction of the polyether polyol, and C represents the peak area of ​​the characteristic peak c of acetyl in NMR after the acetyl derivatization reaction of the polyether polyol;

[0053] In the embodiment of the present invention, as an example of the test method of the peak areas A, B, and C of the three peaks a, b, and c, the following method can be selected:

[0054] The specific optional steps include: preparation of acetyl derivatization reaction reagents, acetyl derivatization reaction, sample separation, and nuclear magnetic resonance (NMR) testing;

[0055] The preparation of the acetyl derivatization reaction reagent comprises dissolving a certain amount of acetic anhydride and pyridine, wherein the molar ratio of acetic anhydride to pyridine is between 1:3 and 10, and standing for 1 hour to 24 hours to obtain a sample acetyl derivatization reaction reagent;

[0056] The acetyl derivatization reaction comprises taking a certain amount of polyether polyol and an excess of an acetyl derivatization reaction reagent, and heating the acetyl derivatization reaction at 100° C. to 120° C. under nitrogen protection and stirring for 1 h to 5 h; wherein, there is no special limitation on the amount of the polyether polyol and the acetyl derivatization reaction reagent, as long as the amount of the acetyl derivatization reaction reagent is greater than the amount of the polyether polyol.

[0057] The sample separation comprises extracting and separating the polyether polyol after the acetyl derivatization reaction to obtain an organic phase, drying the organic phase, and rotary evaporating to obtain a nuclear magnetic resonance (NMR) test sample; wherein, the extraction can choose to use a common extractant in the art, as an example of the extractant, specifically one or more combinations of sodium bicarbonate aqueous solution, hydrochloric acid aqueous solution or saturated salt water can be selected, wherein the desiccant can choose to use a common desiccant in the art, as an example of the desiccant, specifically one of anhydrous sodium sulfate and anhydrous calcium chloride can be selected.

[0058] The nuclear magnetic resonance (NMR) test involves dissolving the test sample in deuterated chloroform and then testing it;

[0059] The acetyl derivatization reaction of the hydroxyl groups at the ends of the polyether polyol chains in the embodiments of the present invention is represented by the chemical equation shown below:

[0060]

[0061] In the embodiment of the present invention, after the polyether polyol is subjected to the acetyl derivatization reaction, the hydrogen atom peak positions thereof are divided into three regions, among which Figure 1 As shown, peak a includes two hydrogen atoms in a methylene group, one hydrogen atoms in a methine group, and four hydrogen atoms in two methylene groups in an EO group as shown in formula 3; peak b includes three hydrogen atoms in a methyl group in a PO group as shown in formula 2; and peak c includes three hydrogen atoms in a methyl group in an acetyl group as shown in formula 1 above.

[0062] Figure 2 is the NMR spectrum of polyether polyol without acetyl derivatization reaction. Figure 2 It can be seen that it only contains the a' peak, which includes two hydrogens in a methylene group in the PO fragment as shown in structural formula 2, one hydrogen in a methine group, and four hydrogens in two methylene groups in the EO fragment as shown in structural formula 3; the b' peak contains three hydrogens in the methyl group in the PO fragment as shown in structural formula 2, and does not contain the c peak.

[0063] Therefore, the present invention has found that the relationship between x and y, that is, the molar ratio of the PO segment to the EO segment, is calculated by comparing the peak area integral ratio of the a peak and the b peak, and the mass ratio of the PO segment to the EO segment is deduced by combining the molecular weights of the PO segment and the EO segment. Furthermore, the molecular weight M1 of the single chain in the polyether polyol molecule can be calculated by comparing the peak area integral ratio of the b peak and the c peak and the mass ratio of the PO segment to the EO segment, and then the functionality f of the polyether polyol is approximately calculated by combining the measured molecular weight M of the polyether polyol, wherein M, M1, and f satisfy the following relationship, wherein the value of the f value is a positive integer, and the rounding method can be selected for estimation:

[0064]

[0065] In the embodiment of the present invention, gel permeation chromatography (GPC) can be used to determine the molecular weight M of the polyether polyol. As the test parameters of the gel permeation chromatography, the test parameters can be selected as follows:

[0066] Chromatographic column: Agilent PLgel single pore size column, part number PL1110-6530, 7.5×300mm, with guard column, part number PL110-1520, 7.5×50mm;

[0067] Column temperature: 40°C;

[0068] Mobile phase: chromatography grade tetrahydrofuran (usually containing stabilizer);

[0069] Mobile phase flow rate: 0.7 ml / min;

[0070] Detector: differential detector;

[0071] Sample injection volume: 20 μL;

[0072] A polyether polyol is also provided in an embodiment of the present invention, wherein the molecular weight of the polyether polyol is M, wherein M is between 1000 and 10000, and the polyether polyol comprises a compound as shown in structural formula 1:

[0073]

[0074] Wherein, R represents any group, PO represents the structure shown in Structural Formula 2, EO represents the structure shown in Structural Formula 3, and * represents the bonding site:

[0075]

[0076] For example, the polyether polyol shown in structural formula 1, wherein x, y, and z satisfy the following relationship, z is between 2 and 8, and x / y is between 1 and 100; preferably, z is between 2 and 4, and x / y is between 1 and 10:

[0077]

[0078] In the polyether polyols of the present invention, M PO represents the molecular weight of the fragment shown in structural formula 2, M EOThe molecular weight of the fragment shown in structural formula 3 is represented. The structure of the polyether polyol after derivatization includes three peaks a, b and c in the NMR spectrum. The integral interval of the chemical shift of the a peak in the NMR spectrum is between 4.00ppm and 3.00ppm, the integral interval of the chemical shift of the b peak in the NMR spectrum is between 1.40ppm and 0.90ppm, and the integral interval of the chemical shift of the c peak in the NMR spectrum is between 2.08ppm and 1.96ppm. A represents the peak area of ​​the common peak a of PO and EO in NMR after the acetyl derivatization reaction of the polyether polyol, B represents the peak area of ​​the characteristic peak b of PO in NMR after the acetyl derivatization reaction of the polyether polyol, and C represents the peak area of ​​the characteristic peak c of acetyl in NMR after the acetyl derivatization reaction of the polyether polyol.

[0079] The ranges of the values ​​of x, y, and z in the embodiments of the present invention can be obtained by the above-mentioned test method for the functionality of polyether polyols.

[0080] In the embodiment of the present invention, the polyether polyol can be obtained by polymerization using small molecule polyols as initiators and propylene oxide and ethylene oxide as polymerization monomers. The specific polymerization method can be obtained using conventional methods in the art. The small molecule polyols include but are not limited to one or more combinations of propylene glycol, glycerol, pentaerythritol, xylitol, and sorbitol.

[0081] The embodiment of the present invention also provides an isocyanate prepolymer, which can be obtained by reacting raw materials of multifunctional isocyanate and polyol, with NCO as the end-capping group, and the polyol includes a polyether polyol.

[0082] As examples of polyfunctional isocyanates, specific examples include aromatic isocyanates and / or aliphatic isocyanates. The aromatic isocyanates include one or more of toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, and dimethyl diphenyl diisocyanate, preferably one or a combination of toluene diisocyanate or diphenylmethane diisocyanate; the aliphatic isocyanates include one or more of isophorone diisocyanate, 1,4-cyclohexane diisocyanate, and dicyclohexylmethane diisocyanate, preferably dicyclohexylmethane diisocyanate.

[0083] As examples of polyether polyols, conventional commercially available polyether polyols in the art or the above-mentioned polyether polyols in the present invention may be used, preferably the above-mentioned polyether polyols in the present invention.

[0084] The present invention also provides a polishing pad in an embodiment, comprising a polishing layer, wherein the polishing layer comprises a polymeric substrate, and the polymeric substrate can be obtained by curing the above-mentioned isocyanate prepolymer;

[0085] In the embodiment of the present invention, the polymer substrate further includes a curing agent and a hollow microsphere polymer. The curing agent is not particularly limited, and one or more combinations of amine curing agents or alcohol curing agents commonly used in the art can be selected. The hollow microsphere polymer is not particularly limited, and a conventional cystic structure with an outer wall of polyacrylonitrile and polyacrylonitrile copolymer in the art can be selected. Specifically, microspheres or microbeads can be purchased from any one of Akzo Nobel, Matsumoto Oil and Fat Pharmaceutical Co., Ltd. or Sekisui Chemical Co., Ltd.

[0086] In the embodiment of the present invention, the surface of the polishing layer also includes grooves, which can be selected from conventional grooves in the art. As examples of groove shapes, one or more combinations of concentric grooves, radial grooves, XY grid grooves, arc grooves, dot matrix perforated grooves, spiral grooves, and hexagonal grooves can be selected.

[0087] The polishing pad in the embodiment of the present invention comprises a buffer layer, an adhesive layer and a back adhesive layer. The adhesive layer is used for bonding the polishing layer to the buffer layer, and the back adhesive layer is used for bonding the polishing pad to the polishing machine. The back adhesive layer also comprises release paper or release film.

[0088] For example, using Figure 3 The polishing device shown in the figure is carried out, and the polishing device has a polishing machine table 3 supporting a polishing pad 2, a backing material for uniformly pressurizing a support 4 supporting a polished material 1 and a wafer, and a supply mechanism for a polishing liquid 5, wherein the polished material 1 is usually a semiconductor wafer. The polishing pad 2 is mounted on the polishing machine table 3, for example, by adhering a backing layer. The polishing machine table 3 and the support 4 are configured so that the polishing pad 2 and the polished material 1 supported by each are opposite to each other, and each has a rotation axis. In addition, a pressurizing mechanism for pressing the polished material 1 onto the polishing pad 2 is provided on one side of the support 4. When polishing, the polishing machine table 3 and the support 4 are rotated, and the polished material 1 is pressed onto the polishing pad 2, and polishing is performed while supplying slurry. There are no special restrictions on the flow rate of the slurry, the polishing load, the rotation speed of the polishing machine table, and the rotation speed of the wafer, and they can be adjusted appropriately.

[0089] Thus, the protruding parts of the surface of the polished material 1 are removed and polished to a flat state. Thereafter, semiconductor devices are manufactured by dicing, bonding, packaging, etc., and the semiconductor devices are used in arithmetic processing devices, storage devices, etc.

[0090] Example

[0091] The embodiments of the present invention will be described in detail below in conjunction with the examples, but those skilled in the art will appreciate that the following examples are only used to illustrate the present invention and should not be considered to limit the scope of the invention. If no specific conditions are specified in the examples, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0092] Example code indication:

[0093] Polyether polyol-1: Bluestar Dongda polyether polyol product "DL-4000D", with a nominal molecular weight of 4000 and a functionality of 2;

[0094] Polyether polyol-2: Bluestar Dongda polyether polyol product "MN-3050D", with a nominal molecular weight of 3000 and a functionality of 3;

[0095] TDI: toluene diisocyanate;

[0096] HMDI: dicyclohexylmethane diisocyanate.

[0097] Example 1

[0098] GPC Test:

[0099] Agilent PLgel single pore size column, part number PL1110-6530, 7.5 × 300 mm, with guard column, part number PL110-1520, 7.5 × 50 mm;

[0100] Column temperature: 40°C;

[0101] Mobile phase: chromatography grade tetrahydrofuran;

[0102] Mobile phase flow rate: 0.7 ml / min;

[0103] Detector: differential detector;

[0104] Test sample injection volume: 20μL;

[0105] The test sample is: polyether polyol-1.

[0106] The molecular weight of polyether polyol-1 measured by GPC is equal to 4000.

[0107] NMR test:

[0108] Preparation of acetic anhydride acylating agent: weigh 102.1g of acetic anhydride into a 1L brown bottle, add 395.5g of pyridine and shake thoroughly until it dissolves, and prepare a solution with a molar ratio of acetic anhydride to pyridine of 1:5. The solution should be left to stand overnight before use to avoid long-term exposure to the air to absorb moisture.

[0109] Put 50 mg of polyether polyol-1 into a 100 mL single-necked flask, add 5 mL of acetic anhydride acylating agent, connect a reflux condenser and a nitrogen protection device, and react in a (110±5)°C oil bath with magnetic stirring for 1 hour.

[0110] After the reaction, the reaction solution was cooled to room temperature, 50 mL of ethyl acetate was added, and the mixture was first extracted with a 1 mol / L sodium bicarbonate aqueous solution (40 mL*2), and the liquids were separated; the organic phase was then extracted with a 1 mol / L hydrochloric acid aqueous solution (40 mL*2), and the liquids were separated; the organic phase was finally extracted with saturated brine (40 mL*1), and the liquids were separated; the organic phase was dried over anhydrous sodium sulfate (5 g), and the organic phase was spin-dried to obtain ~60 mg of the product.

[0111] The product was measured by NMR using deuterated chloroform as solvent.

[0112] After the NMR test results, the peak areas A, B, and C of peaks a, b, and c are substituted into the calculation formula: where A = 100.00, B = 76.85, and C = 2.44:

[0113]

[0114] After calculation, it is obtained that M1=2139, M / M1=1.87, that is, f≈2, and the functionality of polyether polyol-1 is 2, which is consistent with the nominal data.

[0115] Example 2

[0116] Agilent PLgel single pore size column, part number PL1110-6530, 7.5 × 300 mm, with guard column, part number PL110-1520, 7.5 × 50 mm;

[0117] Column temperature: 40°C;

[0118] Mobile phase: chromatography grade tetrahydrofuran;

[0119] Mobile phase flow rate: 0.7 ml / min;

[0120] Detector: differential detector;

[0121] Test sample injection volume: 20μL;

[0122] The test sample is: polyether polyol-2.

[0123] The molecular weight of polyether polyol-2 measured by GPC is equal to 3000.

[0124] NMR test:

[0125] Preparation of acetic anhydride acylating agent: weigh 102.1g of acetic anhydride into a 1L brown bottle, add 395.5g of pyridine and shake thoroughly until it dissolves, and prepare a solution with a molar ratio of acetic anhydride to pyridine of 1:5. The solution should be left to stand overnight before use. Avoid long-term exposure to air to absorb moisture.

[0126] Take 30 mg of polyether polyol-2 and put it into a 100 mL single-necked flask, add 5 mL of acetic anhydride acylating agent, connect a reflux condenser and a nitrogen protection device, and react in a (110±5)℃ oil bath with magnetic stirring for 1 hour.

[0127] After the reaction, the reaction solution was cooled to room temperature, 50 mL of ethyl acetate was added, and the mixture was first extracted with a 1 mol / L sodium bicarbonate aqueous solution (40 mL*2), and the liquids were separated; the organic phase was then extracted with a 1 mol / L hydrochloric acid aqueous solution (40 mL*2), and the liquids were separated; the organic phase was finally extracted with saturated brine (40 mL*1), and the liquids were separated; the organic phase was dried over anhydrous sodium sulfate (5 g), and the organic phase was spin-dried to obtain ~60 mg of the product.

[0128] After the NMR test results, the peak areas A, B, and C of peaks a, b, and c are substituted into the calculation formula, where A = 100.00, B = 81.26, and C = 5.46:

[0129]

[0130] After calculation, it is obtained that M1=977, M / M1=3.07, that is, f=3, and the functionality of polyether polyol-2 is 3, which is consistent with the nominal data.

[0131] Synthesis example 1

[0132] 1 mol of sorbitol, 28.9 mol of propylene oxide, and 0.35 mol of ethylene oxide were reacted at 115° C. in the presence of 0.08 mol of potassium hydroxide catalyst to prepare polyether polyol-3 using sorbitol as the initiator. According to the same GPC test and NMR test as in Example 1, the molecular weight of polyether polyol-3 obtained was 3054 and the functionality was 8.

[0133] Among them, polyether polyol-3 has A=100.00, B=98.39, C=14.97, z=7.94, and x / y=81.47.

[0134] Synthesis example 2

[0135] 1 mol of pentaerythritol, 78.89 mol of propylene oxide, and 9.22 mol of ethylene oxide were reacted at 115° C. in the presence of 0.08 mol of potassium hydroxide catalyst to prepare polyether polyol-4 using pentaerythritol as the initiator. According to the same GPC test and NMR test as in Example 1, the molecular weight of polyether polyol-4 was 5541 and the functionality was 4.

[0136] Among them, polyether polyol-4 has A=98.41, B=85.15, C=3.77, z=3.89, and x / y=8.56.

[0137] Synthesis example 3

[0138] 1 mol of glycerol, 138.98 mol of propylene oxide, and 3.39 mol of ethylene oxide were reacted at 115° C. in the presence of 0.08 mol of potassium hydroxide catalyst to prepare polyether polyol-5 using glycerol as the initiator. According to the same GPC test and NMR test as in Example 1, the molecular weight of polyether polyol-5 obtained was 8954 and the functionality was 3.

[0139] Among them, polyether polyol-5 has A=99.94, B=96.79, C=1.99, z=3.12, and x / y=40.98.

[0140] Synthesis example 4

[0141] Polyether polyol-6 with propylene glycol as the initiator was prepared by reacting 1 mol of propylene glycol, 57.91 mol of propylene oxide and 39.40 mol of ethylene oxide at 115° C. in the presence of 0.08 mol of potassium hydroxide catalyst. According to the same GPC test and NMR test as in Example 1, the molecular weight of polyether polyol-6 was 6120 and the functionality was 2.

[0142] Among them, polyether polyol-6 has A=99.37, B=52.11, C=1.51, z=2.02, and x / y=1.47.

[0143] Comparative Synthesis Example 5

[0144] Polyether polyol-7 with glycerol as the initiator was prepared by reacting 1 mol of glycerol, 119.37 mol of propylene oxide, and 0.96 mol of ethylene oxide at 115° C. in the presence of 0.08 mol of potassium hydroxide catalyst. According to the same GPC test and NMR test as in Example 1, the molecular weight of polyether polyol-7 was 7568 and the functionality was 3.

[0145] Among them, polyether polyol-7 has A=99.98, B=98.92, C=2.38, z=3.12, and x / y=124.21.

[0146] Example 3

[0147] This embodiment provides a polishing pad, and the preparation method thereof is as follows:

[0148] Step 1: Take 32.52 parts by mass of TDI, 8 parts by mass of HMDI and 53.78 parts by mass of polyether polyol-3 to react to obtain an isocyanate-terminated prepolymer, heat it to 25-65°C, and degas it under vacuum (-0.095MPa) for 2 hours to remove the gas and small molecular compounds in the prepolymer; then add 8.99 parts by mass of hollow microsphere polymer 551DE40d42 with an average particle size of 40μm, stir to make the hollow microsphere polymer uniformly dispersed in the prepolymer, degas it again under vacuum (-0.095MPa) for 2 hours, and set aside.

[0149] Step 2: Heat 25.54 parts by mass of MOCA to 115° C. for standby use.

[0150] Step 3: Mix the prepolymer and curing agent under high-speed shearing, then cast into a round mold to form a casting block with a thickness of 12 cm, let it stand at room temperature for 10 minutes, and then place it in a 100°C oven for curing for 16 hours. After curing, let it cool down to room temperature in the oven automatically, and then cut into 80 mil thick sheets, a total of 60 sheets.

[0151] Step 4: The groove selection uses concentric grooves with a blank (ungrooved) area in the center. The groove parameters are: groove depth 30mil, groove width 20mil, groove spacing 120mil, and the center blank area diameter is 2 inches. After grooving, it becomes a polishing layer.

[0152] Step 5: Use double-sided tape for the intermediate glue and the back glue layer, use the intermediate glue to bond the above-mentioned polishing layer and the buffer layer, and bond the back glue layer on the other side of the buffer layer (the side not bonded with the polishing layer) to obtain the polishing pad P3, wherein the buffer layer uses a polyurethane impregnated non-woven fabric material (SUBA).

[0153] In Examples 4, 5, 6 and Comparative Example 1, except that polyether polyol-4, polyether polyol-5, polyether polyol-6 and polyether polyol-7 are used to replace polyether polyol-3, the other preparation methods are the same as those of Example 3.

[0154] Polishing performance evaluation of polishing pads

[0155] The polishing pads prepared in the examples and comparative examples were tested on a machine to evaluate the polishing performance. The test conditions were as follows:

[0156] The test machine is AMAT Refelxion (Modify 5Zone);

[0157] The polishing liquid was ANJI U3061A (slurry (g): DIW (g): 30% H2O2 (g) = 1: 10: 0.37), with a flow rate of 300 mL / min;

[0158] The dressing disk is Saesol Disk AJ27, 6lbf, in-situ 100%; Platen / Head Speed ​​= 97 / 91;

[0159] Zone Pressure: RR / Z1 / Z2 / Z3 / Z4 / Z5:5.90 / 5.10 / 2.40 / 2.15 / 2.10 / 2.20;

[0160] The wafer used is Pattern wafer: Semitech 754, Cu Blanket wafer PreThickness 10~12KA.

[0161] The change of removal rate during polishing was recorded, the data of 5 hrs was recorded, and the grinding rate non-uniformity (NU) of 5 hrs was recorded, using a four-probe film thickness meter (NAPSON Crestest / RG3000); the specific results are shown in Table 1.

[0162] Defect evaluation

[0163] The defects on the polished substrate after polishing are obtained using KLA-Tencor The SP2 defect inspection system was used to inspect the defect, and the size of the defect was 0.16 μm. The specific results are shown in Table 1.

[0164] Table 1

[0165]

[0166] It should be noted that, according to the explanation and elaboration of the above description, those skilled in the art to which the present invention belongs may also make changes and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some equivalent modifications and changes to the present invention should also be within the scope of protection of the claims of the present invention. In addition, although some specific terms are used in this specification, these terms are only for the convenience of description and do not constitute any limitation to the invention.

Claims

1. A method for testing the functionality of a polyether polyol, characterized in that: The polyether polyol comprises a compound as shown in structural formula 1: Wherein, R represents any group, PO represents a structural fragment as shown in Structural Formula 2, EO represents a structural fragment as shown in Structural Formula 3, M PO represents the molecular weight of the fragment shown in structural formula 2, M EO represents the molecular weight of the fragment shown in structural formula 3, and * represents the bonding site: Determine the molecular weight M of the polyether polyol, perform an acetyl derivatization reaction on the hydroxyl groups at the chain ends of the polyether polyol, and then use a nuclear magnetic resonance (NMR) to determine the structure of the derivatized polyether polyol, wherein the structure of the derivatized polyether polyol includes three peaks a, b, and c in the NMR spectrum, the integral interval of the chemical shift of the a peak in the NMR spectrum is between 4.00ppm and 3.00ppm, the integral interval of the chemical shift of the b peak in the NMR spectrum is between 1.40ppm and 0.90ppm, and the integral interval of the chemical shift of the c peak in the NMR spectrum is between 2.08ppm and 1.96ppm, A represents the peak area of ​​the common peak a of PO and EO in NMR after the acetyl derivatization reaction of the polyether polyol, B represents the peak area of ​​the characteristic peak b of PO in NMR after the acetyl derivatization reaction of the polyether polyol, and C represents the peak area of ​​the characteristic peak c of acetyl in NMR after the acetyl derivatization reaction of the polyether polyol; The single-chain molecular weight M1 of the polyether polyol and the functionality f of the polyether polyol are positive integers, which are calculated by rounding off, wherein M, M1 and f satisfy the following relationship:

2. The method for testing the functionality of a polyether polyol according to claim 1, wherein: The test method of the peak areas A, B and C of the three peaks a, b and c comprises the following steps: preparation of acetyl derivatization reaction reagent, acetyl derivatization reaction, sample separation and nuclear magnetic resonance (NMR) test; The preparation of the acetyl derivatization reaction reagent comprises dissolving a certain amount of acetic anhydride and pyridine, wherein the molar ratio of acetic anhydride to pyridine is between 1:3 and 10, and standing for 1 hour to 24 hours to obtain a sample acetyl derivatization reaction reagent; The acetyl derivatization reaction comprises taking a certain amount of polyether polyol and an excess of an acetyl derivatization reaction reagent, heating the acetyl derivatization reaction at 100° C. to 120° C. under nitrogen protection and stirring for 1 h to 5 h; The sample separation comprises extracting and separating the polyether polyol after the acetyl derivatization reaction to obtain an organic phase, and drying and rotary evaporating the organic phase to obtain a nuclear magnetic resonance (NMR) test sample; Wherein, the nuclear magnetic resonance (NMR) test includes dissolving the test sample in deuterated chloroform and then conducting the test.

3. The method for testing the functionality of polyether polyols according to claim 1, characterized in that: The hydroxyl group at the end of the polyether polyol chain undergoes an acetyl derivatization reaction as shown in the chemical equation shown in the following equation 1:

4. The method for testing the functionality of polyether polyols according to claim 1, characterized in that: The molecular weight M of the polyether polyol was determined using gel permeation chromatography (GPC), and the gel permeation chromatography test parameters were: Chromatographic column: Agilent PLgel single pore size column, part number PL1110-6530, 7.5×300mm, with guard column, part number PL110-1520, 7.5×50mm; Column temperature: 40°C; Mobile phase: chromatography grade tetrahydrofuran; Mobile phase flow rate: 0.7 ml / min; Detector: differential detector; Sample injection volume: 20 μL.

5. A polyether polyol, characterized in that The molecular weight of the polyether polyol is M, wherein M is between 1000 and 10000, and the polyether polyol comprises a compound as shown in structural formula 1: Wherein, R represents any group, PO represents a structural fragment as shown in Structural Formula 2, EO represents a structural fragment as shown in Structural Formula 3, and * represents a bonding site: The polyether polyol as shown in structural formula 1, wherein x, y, and z satisfy the following relationship, z is between 2 and 8, and x / y is between 1 and 100: The polyether polyol M PO represents the molecular weight of the fragment shown in structural formula 2, M EO The molecular weight of the fragment shown in structural formula 3 is represented. The structure of the polyether polyol after derivatization includes three peaks a, b and c in the NMR spectrum. The integral interval of the chemical shift of the a peak in the NMR spectrum is between 4.00ppm and 3.00ppm, the integral interval of the chemical shift of the b peak in the NMR spectrum is between 1.40ppm and 0.90ppm, and the integral interval of the chemical shift of the c peak in the NMR spectrum is between 2.08ppm and 1.96ppm. A represents the peak area of ​​the common peak a of PO and EO in NMR after the acetyl derivatization reaction of the polyether polyol, B represents the peak area of ​​the characteristic peak b of PO in NMR after the acetyl derivatization reaction of the polyether polyol, and C represents the peak area of ​​the characteristic peak c of acetyl in NMR after the acetyl derivatization reaction of the polyether polyol.

6. The polyether polyol according to claim 5, characterized in that In the structural formula 1, z is between 2 and 4, and x / y is between 1 and 10.

7. An isocyanate prepolymer, characterized in that: It is obtained by reacting raw materials including multifunctional isocyanate and polyol, with NCO as the end-capping group, and the polyol comprises the polyether polyol as described in claim 5 or 6.

8. The prepolymer according to claim 7, characterized in that The polyfunctional isocyanate comprises aromatic isocyanate and / or aliphatic isocyanate, wherein the aromatic isocyanate comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, and dimethyl diphenyl diisocyanate, preferably one or a combination of toluene diisocyanate and diphenylmethane diisocyanate; the aliphatic isocyanate comprises one or more of isophorone diisocyanate, 1,4-cyclohexane diisocyanate, and dicyclohexylmethane diisocyanate, preferably dicyclohexylmethane diisocyanate.

9. A polishing pad comprising a polishing layer, characterized in that: The polishing layer comprises a polymer substrate, and the polymer substrate is obtained by curing the isocyanate prepolymer according to any one of claims 7 or 8.

10. The polishing pad according to claim 9, characterized in that The polishing pad comprises a buffer layer, an adhesive layer and a back adhesive layer, wherein the adhesive layer is used for bonding the polishing layer to the buffer layer, the back adhesive layer is used for bonding the polishing pad to the polishing machine, and the back adhesive layer further comprises release paper or release film.

Images