CN118290810B - Microporous foaming thermoplastic polyurethane substrate and preparation method and application thereof - Google Patents
Microporous foaming thermoplastic polyurethane substrate and preparation method and application thereof Download PDFInfo
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- CN118290810B CN118290810B CN202410721866.5A CN202410721866A CN118290810B CN 118290810 B CN118290810 B CN 118290810B CN 202410721866 A CN202410721866 A CN 202410721866A CN 118290810 B CN118290810 B CN 118290810B
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- polyurethane
- fluorine
- thermoplastic polyurethane
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- 238000005187 foaming Methods 0.000 title claims abstract description 71
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 50
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 50
- 239000000758 substrate Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229920002635 polyurethane Polymers 0.000 claims abstract description 71
- 239000004814 polyurethane Substances 0.000 claims abstract description 71
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000011737 fluorine Substances 0.000 claims abstract description 64
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 64
- 238000005498 polishing Methods 0.000 claims abstract description 42
- 239000004970 Chain extender Substances 0.000 claims abstract description 34
- 239000002105 nanoparticle Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 19
- 239000012530 fluid Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 40
- 238000003825 pressing Methods 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 23
- 229920005906 polyester polyol Polymers 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- -1 polytetrafluoroethylene Polymers 0.000 claims description 19
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 19
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 12
- 239000007822 coupling agent Substances 0.000 claims description 11
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 9
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 9
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229940014800 succinic anhydride Drugs 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 23
- 239000011148 porous material Substances 0.000 abstract description 14
- 230000002902 bimodal effect Effects 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920005830 Polyurethane Foam Polymers 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000011496 polyurethane foam Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/06—Polyurethanes from polyesters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a microporous foaming thermoplastic polyurethane substrate and a preparation method and application thereof, wherein the preparation method comprises the following steps: preparation of fluorine-containing chain extender, preparation of fluorine-containing modified polyurethane, preparation of modified nano particles and master batch, and preparation of polyurethane foaming precursor. The polyurethane foaming material with a special bimodal pore structure is successfully prepared by utilizing the solubility difference of the supercritical fluid in the thermoplastic polyurethane and the fluorine-containing modified polyurethane, and the difference of macropores and micropores can be regulated and controlled by the content of the fluorine-containing modified polyurethane and the foaming pressure. The thermoplastic polyurethane is added in two steps, and the microporous foamed thermoplastic polyurethane base material obtained by the preparation method has proper mechanical property and hardness under the assistance of modified nano particles, and the prepared polishing pad can overcome the problems of poor wear resistance and low removal rate.
Description
Technical Field
The invention relates to the technical field of polyurethane composite materials, in particular to a microporous foaming thermoplastic polyurethane substrate, and a preparation method and application thereof.
Background
Chemical-mechanical polishing (CMP) is an important process in the preparation of semiconductor materials, and polishing solutions and polishing pads are their main consumables. The polishing solution mainly comprises superfine nano particle grinding agents (such as SiO 2、Al2O3、CeO2 and the like), surfactants, stabilizers, oxidants and the like, and is introduced between a wafer and a polishing pad in a common CMP process, so that the polishing effect is achieved under the action of chemical and mechanical forces. Since the solid nanoparticles in the polishing liquid mainly provide the abrasive action, this requires a certain wear resistance of the polishing pad.
Polishing pads commonly used in CMP process technology are polyurethane polishing pads and polyurethane composite polishing pads. The polyurethane composite polishing pad is a polishing pad of composite polyurethane with non-woven fabrics, namely, the polyurethane is dissolved in an organic solvent, then a base material such as non-woven fabrics or woven fabrics formed by synthetic rubber or synthetic fibers is soaked in the polyurethane solution, and then wet coagulation or drying is carried out to prepare the polishing pad. The polyurethane composite polishing pad has the problems of large using amount of organic solvent, complex process, long time, uneven impregnation and the like. The polyurethane polishing pad is formed by pouring polyurethane foaming stock solution or is prepared by supercritical fluid foaming, the surface and the matrix of the polishing pad are provided with a large number of uniform pore structures, and the hardness of the material can be regulated and controlled by controlling the hardness of a base material and the size of the pores. Polishing pads made of harder materials exhibit high removal rates and have long service lives, but tend to cause numerous scratches on the polished surface during polishing. While polishing pads made of softer materials exhibit low substrate scratch advantages, but tend to exhibit lower removal rates and shorter useful lives. Thus, there is a need for a material for use in making polishing pads that combines wear resistance and good polishing efficiency.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and provides a microcellular foaming thermoplastic polyurethane substrate, and a preparation method and application thereof. The method is realized by adopting the following specific scheme.
The preparation method of the microcellular foaming thermoplastic polyurethane substrate comprises the following steps:
(1) Adding the dodecafluoroheptyl methacrylate and the ethylene glycol amine in an equimolar ratio into ethanol, stirring the mixture at room temperature to be 25-45 min until uniform, then stirring the mixture at 25-35 ℃ for 3-6 h, and purifying the obtained crude product by column chromatography to obtain the fluorine-containing chain extender.
(2) And (3) respectively placing the polyester polyol, the fluorine-containing chain extender prepared in the step (1) and Hexamethylene Diisocyanate (HDI) in a vacuum oven at 80-120 ℃ for drying for 1-5 h, after the water removal treatment is finished, uniformly mixing the fluorine-containing chain extender, the polyester polyol and the HDI according to a proportion at room temperature, pouring into a polytetrafluoroethylene mold, and curing to obtain the fluorine-containing modified polyurethane. Preferably, the fluorine-containing chain extender, the polyester polyol and the HDI are mixed uniformly in a molar ratio of 0.1-0.25:0.75-0.9:1. The curing temperature is 75-90 ℃ and the curing time is 24-36 h.
(3) Uniformly dispersing an aminosilane coupling agent and succinic anhydride in DMF (dimethyl formamide) in an equimolar ratio, stirring for 3-5 h, adding ultrasonically dispersed nano particles into the mixture, and continuously stirring for 4-6 h; and then washing by repeatedly using absolute ethyl alcohol and distilled water, and drying to obtain the modified nano particles. Preferably, the aminosilane coupling agent is at least one of KH550, a1110, a1120, KBM 602. The nano particles are at least one of mesoporous silica, nano montmorillonite, nano titanium dioxide, alumina and zirconia; the average particle size of the nano particles is 100-300 nm.
(4) Pouring the modified nano particles prepared in the step (3) into an organic solvent, adding thermoplastic polyurethane with a certain mass after ultrasonic dispersion is uniform, stirring to dissolve the thermoplastic polyurethane, pouring the obtained solution into a polytetrafluoroethylene mould, and volatilizing the organic solvent to obtain the modified nano particle master batch. The hardness of the thermoplastic polyurethane is preferably 55 to 85HD. The organic solvent is preferably at least one of tetrahydrofuran, acetone and ethanol.
(5) And (3) drying, melt blending and pressing the fluorine-containing modified polyurethane prepared in the step (2), the modified nanoparticle master batch prepared in the step (4) and the thermoplastic polyurethane to obtain a polyurethane foaming precursor. And (3) placing the polyurethane foaming precursor into a mould pressing foaming cavity, controlling the temperature in a mould of a mould pressing machine to be 125-140 ℃, controlling the pressure of supercritical fluid injected into the mould to be 8-12 MPa, keeping constant temperature and constant pressure to be 2-4 h, releasing pressure to normal pressure, and opening the mould to obtain the foaming substrate. The supercritical fluid is at least one of carbon dioxide and nitrogen.
The microporous foaming thermoplastic polyurethane substrate comprises the following components in parts by weight: 60-95 parts of thermoplastic polyurethane, 5-40 parts of fluorine-containing modified polyurethane and 3-10 parts of modified nano particles. The thermoplastic polyurethane is added in two steps in step (4) and step (5).
The microporous foamed thermoplastic polyurethane substrate prepared by the invention has a special bimodal pore structure, and can be made into a polishing pad after the substrate is subjected to the procedures of further peeling, grinding, grooving and the like.
The invention has the advantages that:
1. The fluorine-containing monomer is successfully grafted to the main chain of the polyurethane through the modification of the chain extender, so that the solubility of the polyurethane body to CO 2 or nitrogen is improved.
2. The carboxyl is successfully introduced to the surface of the nanoparticle by modifying the nanoparticle, and can form a hydrogen bond with the amino on polyurethane, so that the hardness and the wear resistance of the polyurethane body are further improved, and the hardness and the wear resistance of the matrix and the foaming substrate can be regulated and controlled by regulating the content of the carboxyl.
3. The solubility difference of CO 2 or nitrogen in two polyurethanes (thermoplastic polyurethane and fluorine-containing modified polyurethane) is utilized to successfully prepare the polyurethane foaming base material with a bimodal pore structure, and the difference of a large pore (the pore diameter is more than or equal to 20 mu m) and a small pore (the pore diameter is less than 20 mu m) can be regulated and controlled through the content of the fluorine-containing modified polyurethane and the foaming pressure.
4. The prepared foaming substrate has a special double-peak pore structure, and the macropores can play a role in storing polishing liquid in the polishing process, so that fresh polishing liquid is continuously supplied to the polishing surface, the polishing efficiency is improved, and the polishing effect is ensured. The hole wall of the small hole has higher number of 'micro-convex bodies', so that the removal rate of the polishing pad on the passivation layer of the wafer can be effectively improved. The large holes can also play a role in reducing the density of the polishing pad, and the small holes can also maintain the hardness and mechanical properties of the polishing pad.
Drawings
FIG. 1 is a cell structure (200 times enlarged) of the polyurethane foam substrate prepared in example 1, which has a distinct bimodal cell structure.
FIG. 2 is a cell structure (enlarged 200 times) of the polyurethane foam prepared in comparative example 1, the cell structure of which is a uniform cell structure.
Detailed Description
The following provides a detailed description of specific embodiments of the invention. The embodiment is implemented on the premise of the technical scheme of the invention, and detailed implementation modes and processes are given, but the protection scope of the invention is not limited to the following embodiment. Unless otherwise indicated, the materials used are all commercially available conventional articles. In the embodiment, the hardness of the thermoplastic polyurethane is 55-85HD, the nano particles are mesoporous silica, nano montmorillonite, nano titanium dioxide, alumina and zirconia, the average particle size of the nano particles is 100-300 nm, and the aminosilane coupling agent is KH550, A1110, A1120 and KBM602.
Example 1
Adding the dodecafluoroheptyl methacrylate and the ethylene glycol amine in an equimolar ratio into a round-bottom flask filled with ethanol, stirring at room temperature for 30 min, then heating to 30 ℃, stirring for 4h, and purifying the obtained crude product by column chromatography to obtain the fluorine-containing chain extender with higher purity.
And (3) placing the polyester polyol, the fluorine-containing chain extender and the HDI in a vacuum oven at 110 ℃ for drying for 3h, after the water removal treatment is finished, uniformly mixing the fluorine-containing chain extender, the polyester polyol and the HDI according to the mol ratio of 0.1:0.9:1 at room temperature, pouring the mixture into a polytetrafluoroethylene mould, and curing for 24: 24 h at 80 ℃ to obtain the fluorine-containing modified polyurethane.
Uniformly dispersing KH550 and succinic anhydride in DMF at an equal molar ratio, stirring for 3h, adding mesoporous silica subjected to ultrasonic dispersion, and stirring for 5: 5 h. And then washing by repeatedly using absolute ethyl alcohol and distilled water, and drying to obtain the modified mesoporous silica.
Pouring 10 parts of modified mesoporous silica into tetrahydrofuran, adding 10 parts of thermoplastic polyurethane after ultrasonic dispersion is uniform, stirring to dissolve the thermoplastic polyurethane, pouring the obtained solution into a polytetrafluoroethylene mould, and volatilizing an organic solvent to obtain the modified mesoporous silica master batch.
And (3) drying, melt blending and pressing the modified mesoporous silica master batch, 50 parts of thermoplastic polyurethane and 40 parts of fluorine-containing modified polyurethane to obtain a polyurethane foaming precursor. And (3) placing the polyurethane foaming precursor into a mould pressing foaming cavity, controlling the temperature in a mould of a mould pressing machine at 135 ℃, injecting supercritical CO 2 into the mould to 10 MPa, keeping constant temperature and constant pressure at 3 h, releasing pressure to normal pressure, and opening the mould to obtain the foaming substrate. The foaming base material is further peeled, ground, grooved and the like to prepare the polishing pad.
Example 2
Adding the dodecafluoroheptyl methacrylate and the ethylene glycol amine in an equimolar ratio into a round-bottom flask filled with ethanol, stirring at room temperature for 45 min, then heating to 35 ℃, stirring for 3h, and purifying the obtained crude product by column chromatography to obtain the fluorine-containing chain extender with higher purity.
And (3) placing the polyester polyol, the fluorine-containing chain extender and the HDI in a vacuum oven at 100 ℃ for drying 4 h, after the water removal treatment is finished, uniformly mixing the fluorine-containing chain extender, the polyester polyol and the HDI according to the mol ratio of 0.25:0.75:1 at room temperature, pouring the mixture into a polytetrafluoroethylene mould, and curing 24: 24 h at 90 ℃ to obtain the fluorine-containing modified polyurethane.
Equal molar ratios of a1110 and succinic anhydride were uniformly dispersed in DMF, silica ultrasonically dispersed was added thereto after stirring 3 h, and the suspension was continued to stir 5 h. And then washing by repeatedly using absolute ethyl alcohol and distilled water, and drying to obtain the modified silicon dioxide.
9 Parts of modified silicon dioxide is poured into tetrahydrofuran, 11 parts of thermoplastic polyurethane is added after the modified silicon dioxide is uniformly dispersed by ultrasonic, the thermoplastic polyurethane is stirred to be dissolved, and then the obtained solution is poured into a polytetrafluoroethylene mould to volatilize an organic solvent, so that modified silicon dioxide master batch is obtained.
And (3) drying, melt blending and pressing the modified silica master batch, 64 parts of thermoplastic polyurethane and 25 parts of fluorine-containing modified polyurethane to obtain a polyurethane foaming precursor. And (3) putting the polyurethane foaming precursor into a mould pressing foaming cavity, controlling the temperature in a mould of a mould pressing machine at 138 ℃, injecting supercritical CO 2 into the mould to be 11 MPa, keeping constant temperature and constant pressure to be 2.5 h, releasing pressure to normal pressure, and opening the mould to obtain the foaming substrate. The foaming base material is further peeled, ground, grooved and the like to prepare the polishing pad.
Example 3
Adding the dodecafluoroheptyl methacrylate and the ethylene glycol amine in an equimolar ratio into a round-bottom flask filled with ethanol, stirring at room temperature for 25 min, then heating to 25 ℃, stirring for 6 h, and purifying the obtained crude product by column chromatography to obtain the fluorine-containing chain extender with higher purity.
And (3) placing the polyester polyol, the fluorine-containing chain extender and the HDI in a vacuum oven at 80 ℃ for drying 5h, after the water removal treatment is finished, uniformly mixing the fluorine-containing chain extender, the polyester polyol and the HDI according to the mol ratio of 0.15:0.85:1 at room temperature, pouring the mixture into a polytetrafluoroethylene mould, and curing the mixture at 75 ℃ for 36: 36 h to obtain the fluorine-containing modified polyurethane.
Uniformly dispersing the A1120 and the succinic anhydride with equal molar ratio in DMF, stirring for 3h, adding the nanometer titanium dioxide subjected to ultrasonic dispersion into the mixture, and continuously stirring the suspension for 5: 5 h. And then washing by repeatedly using absolute ethyl alcohol and distilled water, and drying to obtain the modified nano titanium dioxide.
9.5 Parts of modified nano titanium dioxide is poured into acetone, 12 parts of thermoplastic polyurethane is added after the uniform ultrasonic dispersion, the thermoplastic polyurethane is stirred to be dissolved, the obtained solution is poured into a polytetrafluoroethylene mould to volatilize an organic solvent, and the modified nano titanium dioxide master batch is obtained.
And drying, melt blending and pressing the modified nano titanium dioxide master batch, 73 parts of thermoplastic polyurethane and 15 parts of fluorine-containing modified polyurethane to obtain a polyurethane foaming precursor. And (3) putting the polyurethane foaming precursor into a mould pressing foaming cavity, controlling the temperature in a mould of a mould pressing machine at 130 ℃, injecting supercritical CO 2 into the mould to be 12 MPa, keeping constant temperature and constant pressure at 2 h, releasing pressure to normal pressure, and opening the mould to obtain the foaming substrate. The foaming base material is further peeled, ground, grooved and the like to prepare the polishing pad.
Example 4
Adding the dodecafluoroheptyl methacrylate and the ethylene glycol amine in an equimolar ratio into a round-bottom flask filled with ethanol, stirring at room temperature for 35 min, then heating to 32 ℃, stirring for 3.5 h, and purifying the obtained crude product by column chromatography to obtain the fluorine-containing chain extender with higher purity.
And (3) placing the polyester polyol, the fluorine-containing chain extender and the HDI in a vacuum oven at 90 ℃ for drying 4.5 h, after the water removal treatment is finished, uniformly mixing the fluorine-containing chain extender, the polyester polyol and the HDI according to the mol ratio of 0.2:0.8:1 at room temperature, pouring the mixture into a polytetrafluoroethylene mould, and curing the mixture at 85 ℃ for 24: 24 h to obtain the fluorine-containing modified polyurethane.
KBM602 and succinic anhydride in equimolar ratio were uniformly dispersed in DMF, alumina after ultrasonic dispersion was added thereto after stirring 3 h, and the suspension was further stirred 5:5 h. And then washing by repeatedly using absolute ethyl alcohol and distilled water, and drying to obtain the modified alumina.
9 Parts of modified alumina silicon is poured into ethanol, 15 parts of thermoplastic polyurethane is added after ultrasonic dispersion is uniform, stirring is carried out to dissolve the modified alumina silicon, then the obtained solution is poured into a polytetrafluoroethylene mould to volatilize an organic solvent, and the modified alumina master batch is obtained.
And (3) drying, melt blending and pressing the modified alumina master batch, 80 parts of thermoplastic polyurethane and 5 parts of fluorine-containing modified polyurethane to obtain a polyurethane foaming precursor. And (3) putting the polyurethane foaming precursor into a mould pressing foaming cavity, controlling the temperature in a mould of a mould pressing machine at 140 ℃, injecting supercritical nitrogen into the mould at 11 MPa, keeping constant temperature and constant pressure at 2.5: 2.5 h, releasing pressure to normal pressure, and opening the mould to obtain the foaming substrate. The foaming base material is further peeled, ground, grooved and the like to prepare the polishing pad.
Example 5
Adding the dodecafluoroheptyl methacrylate and the ethylene glycol amine in an equimolar ratio into a round-bottom flask filled with ethanol, stirring at room temperature for 30min, then heating to 30 ℃, stirring for 4.5 h, and purifying the obtained crude product by column chromatography to obtain the fluorine-containing chain extender with higher purity.
And (3) placing the polyester polyol, the fluorine-containing chain extender and the HDI in a vacuum oven at 115 ℃ for drying for 3 h, after the water removal treatment is finished, uniformly mixing the fluorine-containing chain extender, the polyester polyol and the HDI according to the mol ratio of 0.25:0.75:1 at room temperature, pouring the mixture into a polytetrafluoroethylene mould, and curing for 34: 34 h at 75 ℃ to obtain the fluorine-containing modified polyurethane.
The aminosilane coupling agent and succinic anhydride were uniformly dispersed in DMF at an equimolar ratio, stirred 3 h, then the ultrasonically dispersed zirconia was added thereto, and the suspension was stirred for a further 5 h. And then washing by repeatedly using absolute ethyl alcohol and distilled water, and drying to obtain the modified zirconia. The aminosilane coupling agent in this example is a mixture of a1110 and KH550 in equimolar proportions.
7.5 Parts of modified zirconia is poured into acetone, 10 parts of thermoplastic polyurethane is added after ultrasonic dispersion is uniform, stirring is carried out to dissolve the thermoplastic polyurethane, then the obtained solution is poured into a polytetrafluoroethylene mould to volatilize an organic solvent, and the modified zirconia master batch is obtained.
And (3) drying, melt blending and pressing the modified zirconia master batch, 55 parts of thermoplastic polyurethane and 35 parts of fluorine-containing modified polyurethane to obtain a polyurethane foaming precursor. And (3) placing the polyurethane foaming precursor into a mould pressing foaming cavity, controlling the temperature in a mould of a mould pressing machine at 130 ℃, injecting supercritical nitrogen into the mould at 9 MPa, keeping constant temperature and constant pressure at 3.5 h, releasing pressure to normal pressure, and opening the mould to obtain the foaming substrate. The foaming base material is further peeled, ground, grooved and the like to prepare the polishing pad.
Example 6
Adding the dodecafluoroheptyl methacrylate and the ethylene glycol amine in an equimolar ratio into a round-bottom flask filled with ethanol, stirring at room temperature for 35 min, then heating to 28 ℃, stirring for 4.5 h, and purifying the obtained crude product by column chromatography to obtain the fluorine-containing chain extender with higher purity.
And (3) placing the polyester polyol, the fluorine-containing chain extender and the HDI in a vacuum oven at 100 ℃ for drying 4 h, after the water removal treatment is finished, uniformly mixing the fluorine-containing chain extender, the polyester polyol and the HDI according to the mol ratio of 0.12:0.88:1 at room temperature, pouring the mixture into a polytetrafluoroethylene mold, and curing the mixture at 80 ℃ for 32: 32 h to obtain the fluorine-containing modified polyurethane.
Uniformly dispersing an aminosilane coupling agent and succinic anhydride in DMF (dimethyl formamide) in an equimolar ratio, stirring 3 h, adding the ultrasonically dispersed nano titanium dioxide into the mixture, and continuously stirring the suspension for 5 h. And then washing by repeatedly using absolute ethyl alcohol and distilled water, and drying to obtain the modified nano titanium dioxide. The aminosilane coupling agent in this example is a mixture of A1110 and KBM602 in a molar ratio of 2:1.
Pouring 5 parts of modified nano titanium dioxide into tetrahydrofuran, adding 12 parts of thermoplastic polyurethane after ultrasonic dispersion is uniform, stirring to dissolve the thermoplastic polyurethane, pouring the obtained solution into a polytetrafluoroethylene die, and volatilizing an organic solvent to obtain modified nano titanium dioxide master batch.
And (3) drying, melt blending and pressing the modified nano titanium dioxide master batch, 50 parts of thermoplastic polyurethane and 38 parts of fluorine-containing modified polyurethane to obtain a polyurethane foaming precursor. And (3) putting the polyurethane foaming precursor into a mould pressing foaming cavity, controlling the temperature in a mould of a mould pressing machine at 125 ℃, injecting supercritical CO 2 into the mould to have the pressure of 10 MPa, keeping the constant temperature and the constant pressure of 2.5 h, releasing the pressure to normal pressure, and opening the mould to obtain the foaming substrate. The foaming base material is further peeled, ground, grooved and the like to prepare the polishing pad.
Example 7
Adding the dodecafluoroheptyl methacrylate and the ethylene glycol amine in an equimolar ratio into a round-bottom flask filled with ethanol, stirring at room temperature for 30min, then heating to 27 ℃, stirring for 5.5 h, and purifying the obtained crude product by column chromatography to obtain the fluorine-containing chain extender with higher purity.
And (3) placing the polyester polyol, the fluorine-containing chain extender and the HDI in a vacuum oven at 120 ℃ for drying 1h, after the water removal treatment is finished, uniformly mixing the fluorine-containing chain extender, the polyester polyol and the HDI according to the mol ratio of 0.1:0.9:1 at room temperature, pouring the mixture into a polytetrafluoroethylene mold, and curing 26: 26 h at 80 ℃ to obtain the fluorine-containing modified polyurethane.
Uniformly dispersing an aminosilane coupling agent and succinic anhydride in DMF (dimethyl formamide) in an equimolar ratio, stirring 3 h, adding nano montmorillonite subjected to ultrasonic dispersion into the mixture, and continuously stirring the suspension for 5 h. And then washing by repeatedly using absolute ethyl alcohol and distilled water, and drying to obtain the modified nano montmorillonite. The aminosilane coupling agent in this example is a 1:2 molar ratio of A1120 to KH550 mixture.
2.5 Parts of modified nano montmorillonite is poured into ethanol, 12 parts of thermoplastic polyurethane is added after ultrasonic dispersion is uniform, stirring is carried out to dissolve the modified nano montmorillonite, the obtained solution is poured into a polytetrafluoroethylene mould to volatilize an organic solvent, and the modified nano montmorillonite master batch is obtained.
And drying, melt blending and pressing the modified nano montmorillonite master batch, 52 parts of thermoplastic polyurethane and 36 parts of fluorine-containing modified polyurethane to obtain a polyurethane foaming precursor. And (3) putting the polyurethane foaming precursor into a mould pressing foaming cavity, controlling the temperature in a mould of a mould pressing machine at 135 ℃, injecting supercritical CO 2 into the mould to be 8 MPa, keeping constant temperature and constant pressure to be 4h, releasing pressure to normal pressure, and opening the mould to obtain the foaming substrate. The foaming base material is further peeled, ground, grooved and the like to prepare the polishing pad.
Comparative example 1
And (3) drying, melt blending and pressing 100 parts of thermoplastic polyurethane to obtain a polyurethane foaming precursor.
And (3) placing the polyurethane foaming precursor into a mould pressing foaming cavity, controlling the temperature in a mould of a mould pressing machine at 130 ℃, injecting supercritical CO 2 into the mould to be 12 MPa, keeping constant temperature and constant pressure to be 4h, releasing pressure to normal pressure, and opening the mould to obtain a foaming sample.
Comparative example 2
The preparation of the fluorine-containing chain extender is the same as in example 1 and will not be described in detail here.
And (3) placing the polyester polyol, the fluorine-containing chain extender and the HDI in a vacuum oven at 115 ℃ for drying 5h, after the water removal treatment is finished, uniformly mixing the fluorine-containing chain extender, the polyester polyol and the HDI according to the mol ratio of 0.15:0.85:1 at room temperature, pouring the mixture into a polytetrafluoroethylene mold, and curing the mixture at 80 ℃ for 24: 24 h to obtain the fluorine-containing modified polyurethane.
And (3) drying, melt blending and pressing 65 parts of thermoplastic polyurethane and 35 parts of fluorine-containing modified polyurethane to obtain a polyurethane foaming precursor. And (3) placing the polyurethane foaming precursor into a mould pressing foaming cavity, controlling the temperature in a mould of a mould pressing machine at 140 ℃, injecting supercritical CO 2 into the mould to be 11 MPa, keeping constant temperature and constant pressure at 3.5 and h, releasing pressure to normal pressure, and opening the mould to obtain a foaming sample.
Performance testing
TABLE 1 parts of materials used in examples 1-7 and comparative examples 1-2
| Thermoplastic polyurethane | Fluorine-containing modified polyurethane | Modified nanoparticles | |
| Example 1 | 60 | 40 | 10 |
| Example 2 | 75 | 25 | 9 |
| Example 3 | 85 | 15 | 9.5 |
| Example 4 | 95 | 5 | 9 |
| Example 5 | 65 | 35 | 7.5 |
| Example 6 | 62 | 38 | 5 |
| Example 7 | 64 | 36 | 2.5 |
| Comparative example 1 | 100 | / | / |
| Comparative example 2 | 65 | 35 | / |
The polyurethane foam materials prepared in examples 1 to 7 and comparative examples 1 to 2 were each tested for each property, and the test was repeated three times, and the test results are shown in table 2 below. Polyurethane foam was tested using the following method and conditions:
Density: obtained according to GB/T6343 test;
hardness: according to standard GB/T531.1 test;
Tensile strength: obtained according to the standard ASTM D3574-08 test.
Cell size: and shooting the section of the foaming material by a scanning electron microscope, and counting the diameters of 150 cells to obtain the average large/small pore diameter of the polyurethane foaming body. Large/small cell definition: the pore diameter is larger than or equal to 20 mu m, and the pore diameter is smaller than 20 mu m.
TABLE 2 parameters of polyurethane foam examples 1-7 and comparative examples 1-2
| Density g/cm 3 | Hardness Shore C | Tensile strength MPa | Average macropore diameter [ mu ] m | Average pore diameter μm | |
| Example 1 | 0.32 | 32 | 20.1 | 33.9 | 15.3 |
| Example 2 | 0.38 | 34 | 22.6 | 33.6 | 13.7 |
| Example 3 | 0.45 | 37 | 24.3 | 34.2 | 11.9 |
| Example 4 | 0.34 | 41 | 26.1 | 33.8 | 10.3 |
| Example 5 | 0.31 | 29 | 19.1 | 34.1 | 16.4 |
| Example 6 | 0.42 | 27 | 18.3 | 34.5 | 17.2 |
| Example 7 | 0.44 | 26 | 16.9 | 34.3 | 18.8 |
| Comparative example 1 | 0.45 | 22 | 15.2 | 39.3 | / |
| Comparative example 2 | 0.47 | 23 | 14.9 | 38.2 | 19.4 |
From examples 1-4, it is seen that the amount of fluorine-containing modified polyurethane affects the average diameter of small cells, and that the higher the amount, the higher the solubility of CO 2 in the blend, and the more CO 2 is available for cell growth, the smaller the difference in size of large/small cells.
From examples 1 and 5-7, it is clear that the content of modified nanoparticles affects the large/small cell size difference, the higher the content, the more pronounced the heterogeneous nucleation, the more pronounced the small cells are formed and the bimodal cell structure is. Meanwhile, the mechanical property and hardness of the foaming material can be improved through the denser small cells.
As is clear from examples 1 and comparative examples 1 to 2, the foam material containing no fluorine-containing modified polyurethane and modified nanoparticles has significantly large cell size/small cell size, resulting in a decrease in hardness and mechanical properties of the material, and an excessively large cell size during use adversely affects polishing effect.
The microporous foamed thermoplastic polyurethane substrate obtained by the preparation method has proper mechanical property and hardness, and the prepared polishing pad can overcome the problems of poor wear resistance and low removal rate.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (8)
1. A method for preparing a microcellular foamed thermoplastic polyurethane substrate, comprising the steps of:
(1) Adding dodecafluoroheptyl methacrylate and ethylene glycol amine in an equimolar ratio into ethanol, stirring uniformly at room temperature, then stirring at 25-35 ℃ for 3-6 h, and purifying the obtained crude product by column chromatography to obtain a fluorine-containing chain extender;
(2) Respectively vacuum drying polyester polyol, the fluorine-containing chain extender prepared in the step (1) and hexamethylene diisocyanate, uniformly mixing the fluorine-containing chain extender, the polyester polyol and the hexamethylene diisocyanate according to a proportion at room temperature, pouring into a polytetrafluoroethylene mold, and curing to obtain fluorine-containing modified polyurethane;
(3) Uniformly dispersing an aminosilane coupling agent and succinic anhydride in DMF (dimethyl formamide) in an equimolar ratio, stirring for 3-5 h, adding ultrasonically dispersed nano particles into the mixture, and continuously stirring for 4-6 h; then repeatedly washing with absolute ethyl alcohol and distilled water, and drying to obtain modified nano particles; the nano particles are at least one of mesoporous silica, nano montmorillonite, nano titanium dioxide, zirconia and alumina, and the average particle size of the nano particles is 100-300 nm;
(4) Pouring the modified nano particles prepared in the step (3) into an organic solvent, adding thermoplastic polyurethane with a certain mass after ultrasonic dispersion is uniform, stirring to dissolve the thermoplastic polyurethane, pouring the obtained solution into a polytetrafluoroethylene mould, and volatilizing the organic solvent to obtain modified nano particle master batch;
(5) Drying, melt blending and pressing the fluorine-containing modified polyurethane prepared in the step (2), the modified nanoparticle master batch prepared in the step (4) and the thermoplastic polyurethane to obtain a polyurethane foaming precursor; placing polyurethane foaming precursors into a mould pressing foaming cavity, controlling the temperature in a mould of a mould pressing machine to be 125-140 ℃, controlling the pressure of supercritical fluid injected into the mould to be 8-12 MPa, keeping constant temperature and constant pressure to be 2-4 h, then releasing pressure to normal pressure, and opening the mould to obtain a foaming substrate; the supercritical fluid is supercritical carbon dioxide or supercritical nitrogen;
The microporous foaming thermoplastic polyurethane substrate comprises the following components in parts by weight: 60-95 parts of thermoplastic polyurethane, 5-40 parts of fluorine-containing modified polyurethane and 3-10 parts of modified nano particles.
2. The method according to claim 1, wherein the fluorine-containing chain extender, the polyester polyol and the hexamethylene diisocyanate in the step (2) are uniformly mixed in a molar ratio of 0.1-0.25:0.75-0.9:1.
3. The method according to claim 1, wherein the curing temperature in step (2) is 75 to 90 ℃ and the curing time is 24 to 36 h.
4. The method according to claim 1, wherein the aminosilane coupling agent in the step (3) is at least one of KH550, a1110, a1120, KBM 602.
5. The method according to claim 1, wherein the thermoplastic polyurethane has a hardness of 55 to 85HD.
6. The method according to claim 1, wherein the organic solvent in the step (4) is at least one of tetrahydrofuran, acetone, and ethanol.
7. A microcellular foamed thermoplastic polyurethane substrate obtainable by the process according to any one of claims 1 to 6.
8. A polishing pad prepared by further processing the substrate of claim 7.
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| WO2011066060A1 (en) * | 2009-11-25 | 2011-06-03 | Dow Global Technologies Llc | Nanoporous polymeric foam having high porosity |
| WO2011082155A2 (en) * | 2009-12-30 | 2011-07-07 | 3M Innovative Properties Company | Polishing pads including phase-separated polymer blend and method of making and using the same |
| CN107446263B (en) * | 2017-08-09 | 2020-08-14 | 南通矽利康橡塑材料有限公司 | Foamed polymer with multimodal pore size distribution and preparation method thereof |
| EP3838972A1 (en) * | 2019-12-20 | 2021-06-23 | SHPP Global Technologies B.V. | Foamed polymer compositions including a nanostructured fluoropolymer |
| CN113999368B (en) * | 2021-11-05 | 2022-11-11 | 中国科学院过程工程研究所 | Polyurethane polishing pad and preparation method thereof |
| CN116872592B (en) * | 2023-01-10 | 2023-12-12 | 南通北风橡塑制品有限公司 | High-strength wear-resistant polyurethane composite board and processing technology thereof |
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