CN115284165A - Porous polyurethane polishing pad and preparation method thereof - Google Patents
Porous polyurethane polishing pad and preparation method thereof Download PDFInfo
- Publication number
- CN115284165A CN115284165A CN202210821977.4A CN202210821977A CN115284165A CN 115284165 A CN115284165 A CN 115284165A CN 202210821977 A CN202210821977 A CN 202210821977A CN 115284165 A CN115284165 A CN 115284165A
- Authority
- CN
- China
- Prior art keywords
- parts
- polishing pad
- stirring
- porous polyurethane
- polyurethane polishing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 53
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 53
- 239000004814 polyurethane Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 30
- 229920000570 polyether Polymers 0.000 claims abstract description 30
- 239000003381 stabilizer Substances 0.000 claims abstract description 27
- 239000006229 carbon black Substances 0.000 claims abstract description 25
- -1 siloxane chain Chemical group 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 229920002545 silicone oil Polymers 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000011148 porous material Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 13
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 12
- 150000003077 polyols Chemical class 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 11
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 11
- 150000001718 carbodiimides Chemical group 0.000 claims description 10
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 230000004927 fusion Effects 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005187 foaming Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 241001112258 Moca Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- B24B37/26—Lapping pads for working plane surfaces characterised by the shape of the lapping pad surface, e.g. grooved
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D11/00—Constructional features of flexible abrasive materials; Special features in the manufacture of such materials
- B24D11/001—Manufacture of flexible abrasive materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
-
- 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
- C08J2375/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The invention relates to a porous polyurethane polishing pad and a preparation method thereof, belonging to the technical field of polyurethane polishing pads, wherein the porous polyurethane polishing pad comprises the following raw materials: the air hole stabilizer is prepared by grafting polyether with a polycarbodiimide end group structure on the surface of straight-chain hydrogen-containing silicone oil, and because a siloxane chain segment and a polyether chain segment with a carbomide end group exist, the air hole stabilizer serves as an interface compatilizer of air holes and polyurethane gel, the aperture of the air holes can be adjusted by the hydrophobic siloxane chain segment with low surface tension, and the problem that the number of the air holes is reduced due to the mutual fusion of the air holes is solved; meanwhile, the carbon black is added in the polyurethane, and the carbon black can be physically crosslinked with a polyurethane matrix, so that the mechanical property and the wear resistance of the polyurethane are improved.
Description
Technical Field
The invention belongs to the technical field of polyurethane polishing pads, and particularly relates to a porous polyurethane polishing pad and a preparation method thereof.
Background
Chemical Mechanical Polishing (CMP) refers to a process in which a workpiece to be polished is moved relative to a polishing pad under a certain pressure and in the presence of a polishing slurry, and a smooth surface is formed on the surface of the workpiece to be polished by means of organic bonding between the grinding action of nanoparticles and the corrosive action of an oxidizing agent;
the polishing pad, which is one of the consumables in the chemical mechanical polishing process, can provide a certain mechanical load, and also serves to contain and transport the polishing solution (through the pores of the polishing pad). The polyurethane polishing pad has high hardness, and the processed finished product has good flatness, is acid-resistant and alkali-resistant, and is suitable for various polishing environments; the pore size and the uniformity of the foaming of the polyurethane polishing pad have great influence on the performance of the polishing pad, and the accumulation of abrasive particles is easily caused by too large pore size or uneven pore distribution, so that the surface of a workpiece is scratched, and the polishing performance is seriously influenced.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the present invention aims to provide a porous polyurethane polishing pad and a method for preparing the same.
The purpose of the invention can be realized by the following technical scheme:
a porous polyurethane polishing pad comprises the following raw materials in parts by weight: 70-110 parts of polyether polyol, 300-400 parts of carbodiimide modified 4,4 '-diphenylmethane diisocyanate (liquefied MDI), 20-30 parts of 1, 4-Butanediol (BDO), 20-30 parts of 3, 3-dichloro-4, 4' -diaminodiphenylmethane (MOCA), 15-18 parts of cerium oxide, 5-7 parts of carbon black, 2-5 parts of dibutyltin dilaurate, 2-5 parts of triethylamine, 8-10 parts of deionized water and 13-15 parts of a gas pore stabilizer;
the pore stabilizer is prepared by the following steps:
step A1: adding sodium hydroxide into a mixed solution of allyl alcohol, ethylene oxide and propylene oxide, heating to 100-120 ℃, stirring for reaction for 5 hours, cooling to room temperature, neutralizing with glacial acetic acid, and filtering to obtain allyl-terminated oxidized copolyether;
in the above reaction, allyl alcohol, ethylene oxide and propylene oxide are polymerized under the catalysis of sodium hydroxide to obtain allyl terminated oxide copolyether.
Step A2: adding polycarbodiimide alkene into allyl-terminated oxidation copolyether, heating to 70-80 ℃, adding stannous octoate, and stirring for reacting for 4 hours to obtain carbodiimide end group polyether;
in the reaction, under the catalytic action of stannous octoate, allyl-terminated oxidation copolyether and polycarbodiimide are subjected to addition reaction to prepare the polyether with the carbodiimide end group.
Step A3: adding chloroplatinic acid into the carbodiimide-terminated polyether, stirring and heating to 90-100 ℃ under the protection of nitrogen, adding straight-chain hydrogen-containing silicone oil, stirring and reacting for 2 hours, cooling and discharging to obtain the pore stabilizer.
In the reaction, under the catalytic action of chloroplatinic acid, polyether with a polycarbodiimide end group structure is grafted on the surface of linear chain hydrogen-containing silicone oil, the prepared pore stabilizer not only has a hydrophobic siloxane chain segment with low surface tension, but also has a hydrophilic polyether chain segment with a carbodiimide end group, two chemical reactions, namely a gel reaction and a foaming reaction, are existed in the preparation process of the polyurethane polishing material, the reaction of polyether polyol and liquefied MDI is the gel reaction, the foaming reaction is the reaction of deionized water and liquefied MDI, and the pore stabilizer has the siloxane chain segment and the polyether chain segment with the carbodiimide end group, so that the pore stabilizer serves as an interface compatilizer of pores and polyurethane gel, the size of pores can be adjusted by the hydrophobic siloxane chain segment with low surface tension, and the problem of reduction of the number of pores caused by mutual fusion of the pores is prevented.
Further, the polyether polyol is one of polyoxypropylene glycol (PPG), polytetramethylene ether glycol (PTMEG), and diethylene glycol (DEG).
Further, the polyether polyol has a number average molecular weight (Mn) of 400 to 2000, and too high a number average molecular weight of the polyether polyol may result in too low a hardness of the prepared polyurethane material, and too low a number average molecular weight may result in a loss of elasticity of the prepared polyurethane material.
Furthermore, the average particle size of the carbon black is 80-100nm, the addition of the carbon black increases the viscosity of the system while increasing the number of nucleation points, and the influence of the increase of the nucleation points and the increase of the viscosity on the foaming process of polyurethane are contradictory, so the particle size of the carbon black and the addition amount of the carbon black need to be controlled.
Further, in the step A1, the mass ratio of allyl alcohol, ethylene oxide, propylene oxide and sodium hydroxide is 5-10:30-45:58-70:0.35-0.5.
Further, in the step A2, the mass ratio of the allyl-terminated oxidation copolyether to the polycarbodiimide to the stannous octoate is 1: 0.05.
further, in the step A3, the mass ratio of the carbodiimide-terminated polyether, the chloroplatinic acid and the linear hydrogen-containing silicone oil is 4.5: 1.
further, the preparation method of the porous polyurethane polishing pad comprises the following steps:
step B1: placing polyether polyol at 100-120 ℃ for drying and dehydrating for 2-4h, introducing the polyether polyol into a reaction kettle, introducing nitrogen, stirring for 5min at 55-60 ℃ and at the rotating speed of 200-400r/min, slowly adding carbodiimide to modify 4,4' -diphenylmethane diisocyanate, heating to 80 ℃, stirring for reacting for 2h, and then defoaming in vacuum to obtain an intermediate 1;
in the above reaction, polyether polyol and liquefied MDI are polymerized by stepwise addition to produce polyurethane, and the polyurethane polishing pad is based on polyurethane.
And step B2: adding 1, 4-butanediol, 3-dichloro-4, 4' -diaminodiphenylmethane and the intermediate 1 into a reaction kettle, introducing nitrogen, stirring and reacting for 0.5-1h at the temperature of 80-85 ℃ and the rotating speed of 1000-1200r/min, then adding cerium oxide and carbon black into the reaction kettle, and continuing to stir and react for 0.5-1h to obtain an intermediate 2;
in the above reaction, BDO and MOCA act as an extension chain for the action of extending molecular chains and increasing molecular weight, contributing to the formation of linear macromolecules;
the cerium oxide can be used as polishing powder to improve the hardness and strength of the polishing material and also contribute to improving the grinding rate;
the carbon black can be physically crosslinked with a polyurethane matrix, a plurality of polyurethane molecular chains can be connected to a single carbon black, and physical crosslinking is generated among molecules, so that the mechanical property and the wear-resisting property of the polyurethane are improved.
And step B3: adding the intermediate 2, dibutyltin dilaurate, triethylamine, deionized water and a pore stabilizer into a reaction kettle, stirring and reacting for 10-15min at the temperature of 150-170 ℃ and the rotating speed of 800-1000r/min, and defoaming in vacuum after stirring until no bubble is generated to obtain an intermediate 3;
in the reaction, the balance relationship between the gelling reaction and the foaming reaction is adjusted by using dibutyltin dilaurate and triethylamine, wherein the dibutyltin dilaurate can promote the reaction of polyether polyol and liquefied MDI, assist in improving the molecular weight and viscosity of the polymer and promote gelling; the triethylamine can promote the reaction of the deionized water and the liquefied MDI, and the triethylamine and the liquefied MDI are matched and used to have a synergistic effect, so that the physical performance of the polyurethane polishing pad is ensured, and the number of air holes is increased to the maximum extent.
And step B4: preheating a mold to 70-80 ℃, then adding the intermediate 3 into the mold, standing for 2min at 80 ℃, curing for 16h at 100 ℃ after demolding, standing for 48-72h at room temperature to obtain a porous polyurethane elastomer, and cutting and grooving to obtain the porous polyurethane polishing pad.
The invention has the beneficial effects that:
firstly, the air hole stabilizer is prepared, the polyether with a polycarbodiimide end group structure is grafted on the surface of the straight-chain hydrogen-containing silicone oil, so that the compatibility of the air hole stabilizer and a polyester type raw material is improved, meanwhile, because a siloxane chain segment and a polyether chain segment with a carbodiimide end group exist, the air hole stabilizer serves as an interface compatilizer of air holes and polyurethane gel, the aperture of the air holes can be adjusted by the hydrophobic siloxane chain segment with low surface tension, and the problem of reduction of the number of the air holes caused by mutual fusion of the air holes is solved;
then, the carbon black is added in the invention, the carbon black can be physically crosslinked with a polyurethane matrix, a plurality of polyurethane molecular chains can be connected to a single carbon black, and complex physical crosslinking is generated among molecules, so that the mechanical property and the wear resistance of the polyurethane are improved.
Finally, the present invention utilizes carbon black to provide nucleation sites; the balance relation between the gel reaction and the foaming reaction is adjusted by mixing dibutyltin dilaurate and triethylamine, so that the quantity and efficiency of generated air holes are improved; controlling the pore diameter of the pores by the pore stabilizer; and then cerium oxide is added by adding a polishing agent. Through layer-by-layer matching, the hardness and the strength of the polyurethane polishing pad are ensured, the number and the uniformity of air holes are improved, and the polishing performance of the polyurethane polishing pad is effectively improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing a pore stabilizer:
step A1: adding 0.35g of sodium hydroxide into a mixed solution of 5g of allyl alcohol, 30g of ethylene oxide and 58g of propylene oxide, heating to 100 ℃, stirring for reaction for 5 hours, cooling to room temperature, neutralizing with glacial acetic acid, and filtering to obtain allyl-terminated oxidized copolyether;
step A2: adding 8g of polycarbodiimide into 40g of allyl-terminated oxide copolyether, heating to 70 ℃, adding 1g of stannous octoate, and stirring for reaction for 4 hours to obtain the carbodiimide-terminated polyether;
step A3: adding 0.5g of chloroplatinic acid into 45g of carbodiimide-terminated polyether, stirring and heating to 90 ℃ under the protection of nitrogen, adding 10g of straight-chain hydrogen-containing silicone oil, stirring and reacting for 2 hours, cooling and discharging to obtain the pore stabilizer.
Example 2
Preparing a pore stabilizer:
step A1: adding 0.5g of sodium hydroxide into a mixed solution of 10g of allyl alcohol, 45g of ethylene oxide and 70g of propylene oxide, heating to 120 ℃, stirring for reaction for 5 hours, cooling to room temperature, neutralizing by glacial acetic acid, and filtering to obtain allyl-terminated oxidized copolyether;
step A2: adding 10g of polycarbodiimide into 40g of allyl-terminated oxide copolyether, heating to 80 ℃, adding 1g of stannous octoate, and stirring for reaction for 4 hours to obtain the carbodiimide-terminated polyether;
step A3: adding 0.5g of chloroplatinic acid into 45g of carbodiimide-terminated polyether, stirring and heating to 100 ℃ under the protection of nitrogen, adding 10g of straight-chain hydrogen-containing silicone oil, stirring and reacting for 2 hours, cooling and discharging to obtain the pore stabilizer.
Example 3
Preparing a porous polyurethane polishing pad:
the feed comprises the following raw materials in parts by weight: 70 parts of polypropylene oxide glycol, 300 parts of carbodiimide-modified 4,4 '-diphenylmethane diisocyanate, 20 parts of 1, 4-butanediol, 20 parts of 3, 3-dichloro-4, 4' -diaminodiphenylmethane, 15 parts of cerium oxide, 5 parts of carbon black, 2 parts of dibutyltin dilaurate, 2 parts of triethylamine, 8 parts of deionized water and 13 parts of the pore stabilizer prepared in example 1, wherein the selected carbon black has an average particle size of 80nm;
the preparation method of the porous polyurethane polishing pad comprises the following steps:
step B1: placing polyoxypropylene glycol at 100 ℃ for drying and dehydrating for 2h, introducing the polyoxypropylene glycol into a reaction kettle, introducing nitrogen, stirring for 5min at 55 ℃ and 200r/min, slowly adding carbodiimide modified 4,4' -diphenylmethane diisocyanate, heating to 80 ℃, stirring for reacting for 2h, and defoaming in vacuum to obtain an intermediate 1;
and step B2: adding 1, 4-butanediol, 3-dichloro-4, 4' -diaminodiphenylmethane and the intermediate 1 into a reaction kettle, introducing nitrogen, stirring and reacting for 0.5h at the temperature of 80 ℃ and the rotating speed of 1000r/min, then adding cerium oxide and carbon black into the reaction kettle, and continuing to stir and react for 0.5h to obtain an intermediate 2;
and step B3: adding the intermediate 2, dibutyltin dilaurate, triethylamine, deionized water and a pore stabilizer into a reaction kettle, stirring and reacting for 10min at the temperature of 150 ℃ and the rotating speed of 800r/min, and defoaming in vacuum after stirring until no bubbles are generated to obtain an intermediate 3;
and step B4: preheating a mold to 70-80 ℃, then adding the intermediate 3 into the mold, standing for 2min at 80 ℃, curing for 16h at 100 ℃ after demolding, standing for 48h at room temperature to obtain the porous polyurethane elastomer, and cutting and grooving to obtain the porous polyurethane polishing pad.
Example 4
Preparing a porous polyurethane polishing pad:
the feed comprises the following raw materials in parts by weight: 110 parts of diethylene glycol, 400 parts of carbodiimide-modified 4,4 '-diphenylmethane diisocyanate, 30 parts of 1, 4-butanediol, 30 parts of 3, 3-dichloro-4, 4' -diaminodiphenylmethane, 18 parts of cerium oxide, 7 parts of carbon black, 5 parts of dibutyltin dilaurate, 5 parts of triethylamine, 10 parts of deionized water and 15 parts of the pore stabilizer prepared in example 2, wherein the average particle size of the selected carbon black is 100nm;
the preparation method of the porous polyurethane polishing pad comprises the following steps:
step B1: drying and dehydrating diethylene glycol at 120 ℃ for 4 hours, introducing the diethylene glycol into a reaction kettle, introducing nitrogen, stirring for 5 minutes at the temperature of 60 ℃ and the rotating speed of 400r/min, slowly adding carbodiimide to modify 4,4' -diphenylmethane diisocyanate, heating to 80 ℃, stirring for reacting for 2 hours, and then defoaming in vacuum to obtain an intermediate 1;
and step B2: adding 1, 4-butanediol, 3-dichloro-4, 4' -diaminodiphenylmethane and the intermediate 1 into a reaction kettle, introducing nitrogen, stirring and reacting for 1 hour at the temperature of 85 ℃ and the rotating speed of 1200r/min, then adding cerium oxide and carbon black into the reaction kettle, and continuing stirring and reacting for 1 hour to obtain an intermediate 2;
and step B3: adding the intermediate 2, dibutyltin dilaurate, triethylamine, deionized water and a pore stabilizer into a reaction kettle, stirring and reacting for 15min at the temperature of 170 ℃ and the rotating speed of 1000r/min, and defoaming in vacuum after stirring until no bubbles are generated to obtain an intermediate 3;
and step B4: preheating a mould to 80 ℃, then adding the intermediate 3 into the mould, standing for 2min at 80 ℃, curing for 16h at 100 ℃ after demoulding, standing for 72h at room temperature to obtain the porous polyurethane elastomer, and cutting and grooving to obtain the porous polyurethane polishing pad.
Comparative example 1
The pore stabilizer in example 3 was removed and the remaining raw materials and preparation process were kept unchanged.
Comparative example 2
The carbon black from example 4 was removed and the remaining raw materials and preparation were kept unchanged.
The porous polyurethane polishing pads prepared in examples 3 to 4 and comparative examples 1 to 2 were subjected to the following property tests, respectively:
hardness: measuring Shore hardness D, cutting the porous polyurethane polishing pad into samples of 2cm multiplied by 2cm (the thickness is about 2 mm), measuring the hardness of the samples by using a D-type Shore hardness tester, testing for three times or more and taking an average value to obtain the hardness of the samples;
average pore diameter: cutting the polishing pad into squares of 2cm × 2cm, observing by using a Scanning Electron Microscope (SEM) under the magnification of 100 times, measuring the pore diameter by using a ruler of the SEM, measuring a plurality of pore diameters, and averaging to obtain the average pore diameter of the sample;
tensile strength: using a universal testing machine to test the polishing pad at a speed of 500mm/min, and measuring the ultimate strength before fracture;
elongation percentage: the test was performed using the same measurement method as the tensile strength. The maximum deformation immediately before fracture was measured and the ratio of the maximum deformation to the initial length was expressed in percent.
The test results are shown in table 1:
TABLE 1
| Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| Hardness (ShoreD) | 59 | 61 | 58 | 52 |
| Average pore diameter (μm) | 34 | 35 | 52 | 39 |
| Tensile Strength (kgf/cm) | 21.7 | 22.8 | 21.9 | 20.1 |
| Elongation (%) | 147 | 156 | 148 | 131 |
The following conclusions can be drawn from the data in table 1:
1) The data for the average pore diameter for comparative example 3 and comparative example 1 can be found: after the pore stabilizer is added, the average pore diameter of the prepared porous polyurethane polishing pad is obviously reduced, and under the same condition, the number of pores is increased, which is beneficial to improving the polishing performance of the polishing pad;
2) Data on hardness, tensile strength and elongation for comparative example 4 and comparative example 2 can be obtained: the addition of carbon black significantly improves the physical properties of the porous polyurethane polishing pad.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only, and it will be appreciated by those skilled in the art that various modifications, additions and substitutions can be made to the embodiments described without departing from the scope of the invention as defined in the appended claims.
Claims (7)
1. A porous polyurethane polishing pad characterized by: the feed comprises the following raw materials in parts by weight: 70-110 parts of polyether polyol, 300-400 parts of carbodiimide modified 4,4 '-diphenylmethane diisocyanate, 20-30 parts of 1, 4-butanediol, 20-30 parts of 3, 3-dichloro-4, 4' -diaminodiphenylmethane, 15-18 parts of cerium oxide, 5-7 parts of carbon black, 2-5 parts of dibutyltin dilaurate, 2-5 parts of triethylamine, 8-10 parts of deionized water and 13-15 parts of a pore stabilizer;
the pore stabilizer is prepared by the following steps:
step A1: adding sodium hydroxide into a mixed solution of allyl alcohol, ethylene oxide and propylene oxide, heating to 100-120 ℃, stirring for reaction for 5 hours, cooling to room temperature, neutralizing with glacial acetic acid, and filtering to obtain allyl-terminated oxidized copolyether;
step A2: adding polycarbodiimide alkene into allyl-terminated oxidation copolyether, heating to 70-80 ℃, adding stannous octoate, and stirring for reacting for 4 hours to obtain carbodiimide end group polyether;
step A3: adding chloroplatinic acid into the carbodiimide-terminated polyether, stirring and heating to 90-100 ℃ under the protection of nitrogen, adding straight-chain hydrogen-containing silicone oil, stirring and reacting for 2 hours, cooling and discharging to obtain the pore stabilizer.
2. The porous polyurethane polishing pad of claim 1, wherein: the polyether polyol is one of polyoxypropylene glycol, polytetramethylene ether glycol and diethylene glycol.
3. The porous polyurethane polishing pad of claim 1, wherein: the average particle diameter of the carbon black is 80-100nm.
4. The porous polyurethane polishing pad of claim 1, wherein: in the step A1, the mass ratio of sodium hydroxide, allyl alcohol, ethylene oxide and propylene oxide is 0.35-0.5:5-10:30-45:58-70.
5. The porous polyurethane polishing pad of claim 1, wherein: in the step A2, the mass ratio of the allyl-terminated oxidized copolyether to the polycarbodiimide to the stannous octoate is 8-10:40:1.
6. the porous polyurethane polishing pad of claim 1, wherein: in the step A3, the mass ratio of the polyether with the carbodiimide end group, the chloroplatinic acid and the linear hydrogen-containing silicone oil is 45: 10.
7. the method of claim 1, wherein the step of preparing a porous polyurethane polishing pad comprises: the method comprises the following steps:
step B1: introducing the dehydrated polyether polyol into a reaction kettle, introducing nitrogen, stirring for 5min at the temperature of 55-60 ℃, slowly adding carbodiimide to modify 4,4' -diphenylmethane diisocyanate, heating to 80 ℃, stirring for reacting for 2h, and then defoaming in vacuum to obtain an intermediate 1;
and step B2: adding 1, 4-butanediol, 3-dichloro-4, 4' -diaminodiphenylmethane and the intermediate 1 into a reaction kettle, introducing nitrogen, stirring and reacting for 0.5-1h at the temperature of 80-85 ℃, then adding cerium oxide and carbon black, and continuing to stir and react for 0.5-1h to obtain an intermediate 2;
and step B3: adding the intermediate 2, dibutyltin dilaurate, triethylamine, deionized water and a pore stabilizer into a reaction kettle, stirring and reacting for 10-15min at the temperature of 150-170 ℃, and defoaming in vacuum after stirring until no bubble is generated to obtain an intermediate 3;
and step B4: preheating a mold to 70-80 ℃, then adding the intermediate 3 into the mold, standing for 2min at 80 ℃, curing for 16h at 100 ℃ after demolding, standing for 48-72h at room temperature to obtain a porous polyurethane elastomer, and cutting and grooving to obtain the porous polyurethane polishing pad.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210821977.4A CN115284165A (en) | 2022-07-12 | 2022-07-12 | Porous polyurethane polishing pad and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210821977.4A CN115284165A (en) | 2022-07-12 | 2022-07-12 | Porous polyurethane polishing pad and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115284165A true CN115284165A (en) | 2022-11-04 |
Family
ID=83822939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210821977.4A Pending CN115284165A (en) | 2022-07-12 | 2022-07-12 | Porous polyurethane polishing pad and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115284165A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115741509A (en) * | 2022-12-03 | 2023-03-07 | 三晃树脂（佛山）有限公司 | Waterborne polyurethane polishing material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1374331A (en) * | 2001-03-13 | 2002-10-16 | 小柳津善二郎 | Elastomer foamed grindstone material and its producing process |
| KR100963968B1 (en) * | 2010-03-25 | 2010-06-15 | (주) 피다텍 | Polishing pad and manufacturing method of the same |
| CN105171593A (en) * | 2015-08-11 | 2015-12-23 | 湖北鼎龙化学股份有限公司 | Weather-resisting chemico-mechanical polishing pad |
| CN107805306A (en) * | 2017-11-10 | 2018-03-16 | 苏州思德新材料科技有限公司 | A kind of organic foam stabilizer and preparation method and application |
| CN108349062A (en) * | 2015-10-27 | 2018-07-31 | 富士纺控股株式会社 | The manufacturing method of grinding-material and its manufacturing method and abrasive material |
| CN113195163A (en) * | 2018-12-18 | 2021-07-30 | 3M创新有限公司 | Abrasive article with particle coated abrasive particles |
| CN113956421A (en) * | 2021-11-16 | 2022-01-21 | 上海映智研磨材料有限公司 | Polyurethane polishing pad material and preparation method and application thereof |
-
2022
- 2022-07-12 CN CN202210821977.4A patent/CN115284165A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1374331A (en) * | 2001-03-13 | 2002-10-16 | 小柳津善二郎 | Elastomer foamed grindstone material and its producing process |
| KR100963968B1 (en) * | 2010-03-25 | 2010-06-15 | (주) 피다텍 | Polishing pad and manufacturing method of the same |
| CN105171593A (en) * | 2015-08-11 | 2015-12-23 | 湖北鼎龙化学股份有限公司 | Weather-resisting chemico-mechanical polishing pad |
| CN108349062A (en) * | 2015-10-27 | 2018-07-31 | 富士纺控股株式会社 | The manufacturing method of grinding-material and its manufacturing method and abrasive material |
| CN107805306A (en) * | 2017-11-10 | 2018-03-16 | 苏州思德新材料科技有限公司 | A kind of organic foam stabilizer and preparation method and application |
| CN113195163A (en) * | 2018-12-18 | 2021-07-30 | 3M创新有限公司 | Abrasive article with particle coated abrasive particles |
| CN113956421A (en) * | 2021-11-16 | 2022-01-21 | 上海映智研磨材料有限公司 | Polyurethane polishing pad material and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115741509A (en) * | 2022-12-03 | 2023-03-07 | 三晃树脂（佛山）有限公司 | Waterborne polyurethane polishing material and preparation method thereof |
| CN115741509B (en) * | 2022-12-03 | 2023-08-29 | 三晃树脂（佛山）有限公司 | Water-based polyurethane polishing material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4708251B2 (en) | Foamed polyurethane elastomer, method for producing the same and railroad pad | |
| JP4007426B2 (en) | Method for producing green tire comprising composite structure of modified PU elastic body tread and rubber tire body and method for producing the same | |
| US5698608A (en) | Microcellular polyurethane elastomer | |
| US11485819B2 (en) | Elastomer material modified by a hybrid hard segment material and preparation method thereof | |
| WO2021103376A1 (en) | Non-ionic waterborne polyurethane, preparation method therefor and application thereof | |
| CN115124693B (en) | Foaming polyurethane elastomer and preparation method and application thereof | |
| CN115284165A (en) | Porous polyurethane polishing pad and preparation method thereof | |
| KR20090082147A (en) | Composition for forming a polishing layer of a chemical mechanical polishing pad, chemical mechanical polishing pad, and chemical mechanical polishing method | |
| CN110563920A (en) | Conductive mixed isocyanate type polyurethane material and preparation method thereof | |
| CN114560989A (en) | Polishing pad based on low-free polyurethane prepolymer and preparation method thereof | |
| CN111019507B (en) | High-strength waterborne polyurethane/cellulose nano composite emulsion and preparation method thereof | |
| CN111423717B (en) | Floating body material for waterborne photovoltaic system and preparation method thereof | |
| CN115651524A (en) | High-strength self-cleaning polyurethane waterproof coating and preparation method thereof | |
| CN112194771A (en) | High-resilience casting type polyurethane elastomer | |
| JP2001525465A (en) | Polyurethane and polyurethane / urea thermoset and moisture cured elastomers with improved physical properties | |
| EP2774936A1 (en) | Improved elastomeric compositions | |
| JP3020022B2 (en) | Microcellular polyurethane elastomer and method for producing the same | |
| CN114369226B (en) | Lightweight polyurethane elastomer and manufacturing method and application thereof | |
| JPS5813620A (en) | Fine particle silica dispersed polyol and preparation of polyurethane using it | |
| CN112409562A (en) | Polyurethane resin special for soft basketball leather and preparation method thereof | |
| CN115678480A (en) | Polyurethane adhesive containing polydopamine modified alumina and preparation method thereof | |
| CN110437422B (en) | Preparation method and application of stable NDI prepolymer | |
| CN111072908B (en) | High-oxygen-resistance waterborne polyurethane/montmorillonite nano composite emulsion and preparation method thereof | |
| CN114045146A (en) | High-thermal-conductivity waterborne polyurethane composite material and preparation method thereof | |
| CN114437548A (en) | Moisture-heat dual-curing direct-writing 3D printing medium, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20221104 |