CN113999368B - Polyurethane polishing pad and preparation method thereof - Google Patents
Polyurethane polishing pad and preparation method thereof Download PDFInfo
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- CN113999368B CN113999368B CN202111304242.6A CN202111304242A CN113999368B CN 113999368 B CN113999368 B CN 113999368B CN 202111304242 A CN202111304242 A CN 202111304242A CN 113999368 B CN113999368 B CN 113999368B
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/22—Expandable microspheres, e.g. Expancel®
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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Abstract
The invention relates to a polyurethane polishing pad and a preparation method thereof, wherein the preparation method comprises the following steps: step 1, reacting a mixture of aromatic isocyanate and aliphatic isocyanate with polyether polyol, a microsphere foaming agent and a chain extender to obtain foamed polyurethane; step 2, curing the foamed polyurethane through gradient temperature rise to obtain a polyurethane elastomer; and 3, slicing the polyurethane elastomer to obtain the polyurethane polishing pad. The method does not use catalysts and solvents, is environment-friendly and simple in process, and the formed polyurethane polishing pad has elasticity and hardness and is excellent in foaming effect.
Description
Technical Field
The invention relates to the technical field of polyurethane, in particular to a polyurethane polishing pad and a preparation method thereof.
Background
With the rapid development of the semiconductor industry, the requirement for the surface flatness of the semiconductor raw material wafer is higher and higher. Chemical Mechanical Polishing (CMP) is the only technology that can achieve global planarization, and a polishing pad is one of the essential core materials of the CMP process. The industrial application is most high polymer material polishing pads, and the main component of the polishing pads is foamed polyurethane.
CN111909353A discloses a method for preparing a polishing pad from low-viscosity polyurethane, which comprises preparing a curing agent component with the viscosity of 700-1600 mPa.s at 25 ℃ from polyether polyol, a catalyst, a chain extender and hollow filler or water; then prepolymer component with NCO content of 19-26wt% is prepared by polyol and diisocyanate under the protection of antioxidant, and viscosity is 100-600 mPa.s at 25 ℃. And (3) uniformly mixing the curing agent component and the prepolymer component at the temperature of 25-35 ℃, pouring the mixture into a mold, opening the mold, and vulcanizing to obtain the polishing pad product. The curing agent component and the prepolymer component disclosed by the method have the characteristics of low initial viscosity, no crystallization at normal temperature and the like, are easy to control viscosity and process, and can be mixed at normal temperature to prepare a polyurethane polishing pad product with Shore hardness of 45D-75D. The method disclosed therein uses water as the blowing agent, and there is a high possibility of uncontrollable foaming, resulting in uneven cells.
CN 102211319B discloses a method of manufacturing a polishing pad comprising forming a polishing layer from a polyurethane solution, wherein the polyurethane solution has a solids content of greater than about 90wt%, and drying the polyurethane solution at about 130 ℃ to about 170 ℃. The method disclosed by the method still uses a small amount of solvent, generates volatile organic compounds and is easy to cause pollution.
Currently, there are some difficulties in the performance or manufacturing process of the existing polyurethane polishing pad products. Firstly, the product needs to have elasticity and certain hardness; secondly, the viscosity of the polyurethane prepolymer is too high, so that the foaming agent cannot be uniformly dispersed, and the size and distribution of foam pores in the product are different; thirdly, the curing temperature-raising procedure is not clear, resulting in poor foaming effect. Fourthly, most production processes use catalysts and even solvents, which easily cause pollution to the environment.
In view of the above, it is important to develop a method for preparing a polyurethane polishing pad which does not use a catalyst and a solvent and has an excellent foaming effect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polyurethane polishing pad and a preparation method thereof, wherein the method does not use a catalyst and a solvent, is green and environment-friendly, has a simple process, and can form the polyurethane polishing pad with excellent elasticity, hardness and foaming effect.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a polyurethane polishing pad, the method comprising the steps of:
step 1, reacting a mixture of aromatic isocyanate and aliphatic isocyanate with polyether polyol, a microsphere foaming agent and a chain extender to obtain foamed polyurethane;
step 2, curing the foamed polyurethane through gradient temperature rise to obtain a polyurethane elastomer;
and 3, slicing the polyurethane elastomer to obtain the polyurethane polishing pad.
The preparation method of the polyurethane polishing pad is simple in process, does not use organic solvent and catalyst, takes the mixture of aromatic isocyanate and aliphatic isocyanate as raw materials, and regulates and controls the viscosity of the polymer. Meanwhile, the temperature is increased in a gradient manner, the uniformity of the temperature is guaranteed, the foam holes grow up slowly, and the polyurethane polishing pad with elasticity, hardness, high porosity and uniform foam hole distribution is prepared.
Preferably, in step 1, the foaming reaction specifically comprises:
heating a mixture of aromatic isocyanate and aliphatic isocyanate to 65-75 ℃ (such as 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃ and the like), and dropwise adding dehydrated polyether polyol into the mixture to obtain a first component;
and cooling the first component, uniformly mixing the first component with the microsphere foaming agent, mixing the first component with the chain extender, and defoaming to obtain the foamed polyurethane.
Preferably, the manner of dehydrating the polyether polyol comprises: the polyether polyol is dried at 110 to 120 deg.C (e.g., 112 deg.C, 114 deg.C, 116 deg.C, 118 deg.C, etc.).
Preferably, the drying time is 1-3h, such as 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h, 2.8h, and the like.
Preferably, in the step 1, the molar ratio of the polyether polyol, the mixture of the aromatic isocyanate and the aliphatic isocyanate to the chain extender is 1 (2-6) to (1-5), wherein 2-6 can be 3, 4, 5 and the like, and 1-5 can be 2, 3, 4 and the like.
Preferably, the polyether polyol comprises polytetrahydrofuran.
Preferably, the polyether polyol has a number average molecular weight of 600 to 3000g/mol, such as 1000g/mol, 1500g/mol, 2000g/mol, 2500g/mol, and the like.
Preferably, the chain extender is an alcohol chain extender.
Preferably, the mixture of the aromatic isocyanate and the aliphatic isocyanate has a mass percent of the aromatic isocyanate of more than or equal to 85wt% (e.g., 88%, 90%, 92%, 95%, etc.), and a mass percent of the aliphatic isocyanate of less than 15wt% (e.g., 15%, 12%, 10%, 5%, etc.).
In the present invention, the aromatic isocyanate is contained in the isocyanate mixture in an amount of 85% by mass or more because the strength and hardness of the polishing pad are maintained high. The specific area is too small, the mechanical property does not reach the standard, the service time of the polishing pad is too short, the consumption is large, and the cost is high.
Preferably, the aromatic isocyanate comprises any one of or a combination of at least two of diphenylmethane diisocyanate, naphthalene 1,5-diisocyanate, or toluene diisocyanate.
Preferably, the aliphatic isocyanate includes any one of meta-xylylene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate or a combination of at least two thereof.
Preferably, the mass percentage of the microsphere foaming agent is 0.1wt% to 1wt%, such as 0.2%, 0.4%, 0.6%, 0.8%, etc., based on 100wt% of the total mass of the polyether polyol, the mixture of aromatic isocyanate and aliphatic isocyanate, and the chain extender.
Preferably, the particle size of the microsphere foaming agent is 5-50 μm, such as 10 μm, 20 μm, 30 μm, 40 μm, and the like.
Preferably, the microsphere foaming agent is of a core-shell structure, the shell layer is an acrylic compound, and the core layer comprises C4-C8 alkane.
In the present invention, the C4 to C8 means the number of main chain carbon atoms, for example, C5, C6, C7, etc.
Preferably, in step 2, the gradient temperature rise specifically includes: preheating the foamed polyurethane to 40-60 deg.C (such as 42 deg.C, 45 deg.C, 48 deg.C, 50 deg.C, 52 deg.C, 55 deg.C, 58 deg.C, etc.), standing for 15-30min (such as 20min, 25min, 30min, etc.) at a temperature not equal to 60 deg.C, and performing the following steps:
heating to 60 deg.C within 0.5h (such as 0.5h, 0.3h, 0.2h, etc.), and maintaining for 0.5-1.5h (such as 0.6h, 0.7h, 0.8h, 1.0h, 1.2h, 1.4h, etc.);
heating to 80 deg.C within 0.5h (such as 0.5h, 0.3h, 0.2h, etc.), and maintaining for 1.5-2.5h (such as 1.6h, 1.8h, 2.0h, 2.2h, 2.4h, etc.);
heating to 90 deg.C within 2h (such as 2h, 1.5h, 1h, etc.), and maintaining for 0.5-1.5h (such as 0.6h, 0.7h, 0.8h, 1.0h, 1.2h, 1.4h, etc.);
heating to 100 deg.C within 2h (such as 2h, 1.5h, 1h, etc.), and maintaining for 3.5-4.5h (such as 3.6h, 3.8h, 4.0h, 4.2h, 4.4h, etc.);
the temperature is raised to 110 ℃ within 0.5h (e.g., 0.5h, 0.3h, 0.2h, etc.), and maintained for 5-7h, e.g., 5.5h, 6h, 6.5h, etc.
As a preferred technical scheme, the preparation method comprises the following steps:
step 1, heating a mixture of aromatic isocyanate with the mass percentage of more than or equal to 85% and aliphatic isocyanate with the mass percentage of less than 15% to 65-75 ℃, and dropwise adding dehydrated polyether polyol into the mixture to obtain a first component;
cooling the first component, uniformly mixing the first component with a microsphere foaming agent, mixing the first component with a chain extender, and defoaming to obtain the foamed polyurethane;
step 2, preheating the foamed polyurethane to 40-60 ℃, standing for 15-30min, heating to 60 ℃ within 0.5h, keeping for 0.5-1.5h, then heating to 80 ℃ within 0.5h, keeping for 1.5-2.5h, then heating to 90 ℃ within 2h, keeping for 0.5-1.5h, then heating to 100 ℃ within 2h, keeping for 3.5-4.5h, finally heating to 110 ℃ within 0.5h, keeping for 5-7h, and finishing curing to obtain a polyurethane elastomer;
and 3, slicing the polyurethane elastomer to obtain the polyurethane polishing pad.
In a second aspect, the present invention provides a polyurethane polishing pad prepared by the method of any one of claims 1-9.
Compared with the prior art, the invention has the following beneficial effects:
(1) The raw materials of the invention adopt aromatic and aliphatic isocyanate which are mixed according to a certain proportion, the viscosity of the polymer is adjusted, and the polishing pad with elasticity and hardness is obtained, the elasticity is more than 69 percent, and the hardness is more than 60D;
(2) The curing procedure adopts a gradient heating mode, so that the temperature uniformity is ensured, the foam holes can grow up slowly, the porosity of the obtained polyurethane polishing pad is high, the size of the foam holes is uniform and is distributed uniformly, the particle size of the foam holes is 14-20 mu m, and the porosity is more than 34%;
(3) The invention does not use organic solvent and catalyst, and is green and environment-friendly.
Drawings
FIG. 1 is a micro-topography of the polyurethane polishing pad described in example 1.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides a polyurethane polishing pad prepared by a method comprising the steps of:
(1) Placing a mixture (100.0 g) of diphenylmethane diisocyanate (MDI, 85.0 g) and m-xylylene diisocyanate (XDI, 15.0 g) in a round-bottom flask, heating to 70 ℃ in a water bath, heating and drying polytetrahydrofuran 1000 (104.5 g, available from Shanghai Aladdin Biotechnology Co., ltd., trade name P118599-500 mL) in a vacuum drying oven at 120 ℃ for 2h to remove water, slowly dropwise adding the mixture into the round-bottom flask, and mechanically stirring for 15min to obtain a first component;
(2) Removing the water bath, continuing stirring the first component, cooling the round-bottom flask to room temperature, adding a microsphere foaming agent (1.2 g) into the first component, increasing the rotating speed to 500rpm, fully and uniformly stirring, pouring the material into a defoaming mold, adding a chain extender 1,4-butanediol (28.3 g), and performing high-speed centrifugal defoaming to obtain a second component;
(3) And (3) allowing the second component material to flow into a polytetrafluoroethylene mold preheated to 50 ℃, and standing for 30min. Curing was carried out according to the following temperature gradient:
heating to 60 deg.C for 0.5h, and maintaining for 1h;
heating to 80 ℃ within 0.5h, and keeping for 2h;
heating to 90 ℃ within 2h, and keeping for 1h;
heating to 100 ℃ within 2h, and keeping for 4h;
heating to 110 ℃ at 0.5, and keeping for 6h;
cooling and then removing the mold to obtain a polyurethane elastomer;
(4) The polyurethane elastomer is sliced by a slicer to obtain the polyurethane polishing pad with high porosity and uniform foam pores.
Example 2
This example provides a polyurethane polishing pad prepared by a method comprising the steps of:
(1) Placing a mixture (100.0 g) of naphthalene 1,5-diisocyanate (NDI, 90.0 g) and hexamethylene diisocyanate (HDI, 10.0 g) in a round bottom flask, heating in a water bath to 70 ℃, heating and drying polytetrahydrofuran 1000 (243.7 g, available from Shanghai Aladdin Biotechnology Ltd., trade name P118599-500 mL) in a vacuum drying oven at 110 ℃ for 3h to remove water, slowly dropping into the round bottom flask, and mechanically stirring for 15min to obtain a first component;
(2) Removing the water bath, continuing stirring the first component, cooling the round-bottom flask to room temperature, adding a microsphere foaming agent (0.4 g) into the first component, increasing the rotating speed to 500rpm, fully and uniformly stirring, pouring the material into a defoaming mold, adding a chain extender 1,4-butanediol (22.0 g), and performing high-speed centrifugal defoaming to obtain a second component;
(3) And (3) allowing the second component material to flow into a polytetrafluoroethylene mold preheated to 40-60 ℃, and standing for 30min. Curing was carried out according to the following temperature gradient:
heating to 60 deg.C within 0.5h, and maintaining for 0.5h;
heating to 80 ℃ within 0.5h, and keeping for 1.5h;
heating to 90 ℃ within 2h, and keeping for 0.5h;
heating to 100 ℃ within 2h, and keeping for 3.5h;
heating to 110 ℃ at 0.5, and keeping for 5h;
cooling and then removing the mold to obtain a polyurethane elastomer;
(4) The polyurethane elastomer is sliced by a slicer to obtain the polyurethane polishing pad with high porosity and uniform foam pores.
Example 3
This example provides a polyurethane polishing pad prepared by a method comprising:
(1) Placing a mixture (100.0 g) of toluene diisocyanate (TDI, 95.0g and 95%) and isophorone diisocyanate (IPDI, 5.0g and 5%) in a round-bottom flask, heating in a water bath to 70 ℃, heating and drying polytetrahydrofuran 1000 (94.6 g, available from Shanghai Aladdin Biotechnology technology Co., ltd., under the brand of P118599-500 mL) in a vacuum drying oven at 115 ℃ for 1h to remove water, slowly dropwise adding the mixture into the round-bottom flask, and mechanically stirring for 15min to obtain a first component;
(2) Removing the water bath, continuing stirring the first component, cooling the round-bottomed flask to room temperature, adding a microsphere foaming agent (2.4 g) into the first component, increasing the rotating speed to 500rpm, fully and uniformly stirring, pouring the material into a defoaming mold, adding a chain extender 1,4-butanediol (42.7 g), and carrying out high-speed centrifugal defoaming to obtain a second component;
(3) And (3) allowing the second component material to flow into a polytetrafluoroethylene mold preheated to 40-60 ℃, and standing for 30min. Curing was carried out according to the following temperature gradient:
heating to 60 ℃ within 0.4h, and keeping for 1.5h;
heating to 80 ℃ within 0.4h, and keeping for 2.5h;
heating to 90 ℃ within 1.5h, and keeping for 1.5h;
heating to 100 ℃ within 1.5h, and keeping for 4.5h;
heating to 110 ℃ within 0.3h, and keeping for 7h;
cooling and then removing the mold to obtain a polyurethane elastomer;
(4) The polyurethane elastomer is sliced by a slicer to obtain the polyurethane polishing pad with high porosity and uniform foam pores.
Example 4
This example differs from example 1 in that the mass of MDI is 80.0g and the mass percentage in the isocyanate mixture is 80% by weight; the mass of XDI was 20.0g, and the weight percent in the isocyanate mixture was 20wt%, all the same as in example 1.
Examples 5 to 6
Examples 5-6 differ from example 1 in that the gradient ramp-up was carried out at 2h to 90 ℃ for 0.3h (example 5) and 2h (example 6), respectively, and the rest was the same as in example 1.
Example 7
The difference between this embodiment and embodiment 1 is that in the gradient temperature rise, some processes are different, specifically as follows:
the temperature was raised from 80 ℃ to 100 ℃ over 4 hours and held for 5 hours, all the other things being equal to example 1.
Comparative example 1
This comparative example differs from example 1 in that no gradient temperature ramp is used, and the preparation method comprises the following steps:
(1) Placing a mixture (100.0 g) of diphenylmethane diisocyanate (MDI) and m-Xylylene Diisocyanate (XDI) in a round-bottom flask, heating to 70 ℃ in a water bath, heating and drying polytetrahydrofuran 1000 (104.5 g) in a vacuum drying oven at 120 ℃ for 2h to remove water, slowly dropwise adding the polytetrahydrofuran into the round-bottom flask, and mechanically stirring for 15min to obtain a first component;
(2) Removing the water bath, continuing stirring the first component, cooling the round-bottom flask to room temperature, adding a microsphere foaming agent (1.2 g) into the first component, increasing the rotating speed to 500rpm, fully and uniformly stirring, pouring the material into a defoaming mold, adding a chain extender 1,4-butanediol (28.3 g), and performing high-speed centrifugal defoaming to obtain a second component;
(3) Allowing the second component material to flow into a polytetrafluoroethylene mold preheated to 40-60 ℃, standing for 30min, heating to 110 ℃ within 4.5h, and keeping for 14h;
cooling and then removing the mold to obtain a polyurethane elastomer;
(4) The polyurethane elastomer is sliced by a slicer to obtain the polyurethane polishing pad with high porosity and uniform foam pores.
Performance testing
Examples 1-7 and comparative example 1 were tested as follows:
(1) The appearance is as follows: the polishing pad was cut into 2cm × 2cm squares and observed with a Scanning Electron Microscope (SEM) under a certain magnification.
(2) Hardness: and (3) using a Shore durometer, vertically pressing the needle head on the surface of the sample at a constant speed with proper force, testing the surface of the sample at least three times each time, and taking the average value of the surface of the sample, namely the Shore hardness of the material.
(3) Elastic compressibility: and (3) putting the sample at the bottom of the resiliometer, enabling the steel ball to freely fall to the surface of the sample for three times and rebound, recording the rebound height, and taking the average value of the three rebound heights.
The test results are summarized in table 1 and fig. 1.
TABLE 1
| Hardness (Shao D) | Elastic compressibility/%) | Average pore diameter/. Mu.m | Porosity/% | |
| Example 1 | 63 | 72 | 20 | 40 |
| Example 2 | 62 | 75 | 20 | 39 |
| Example 3 | 65 | 72 | 20 | 40 |
| Example 4 | 63 | 71 | 19 | 36 |
| Example 5 | 60 | 70 | 15 | 36 |
| Example 6 | 62 | 71 | 16 | 37 |
| Example 7 | 61 | 69 | 14 | 34 |
| Comparative example 1 | 58 | 69 | 13 | 29 |
The data in Table 1 show that the polyurethane polishing pad formed by the method has the hardness of more than 60D, the elasticity of more than 69%, the cell diameter of 14-20 mu m and the porosity of more than 34%.
As can be seen from an analysis of comparative example 1 and example 1, comparative example 1 performed less well than example 1, demonstrating that the polyurethane polishing pad formed using a gradient temperature increase performed better.
FIG. 1 is a graph showing the apparent morphology of a polyurethane polishing pad formed by the method of the present invention, wherein it can be seen that the polishing pad formed by the method of the present invention has high porosity, uniform cell size and uniform distribution.
As can be seen from the analysis of example 4 and example 1, the performance of example 4 is inferior to that of example 1, and it is demonstrated that the polyurethane polishing pad formed by the isocyanate mixture containing more than 85% by mass of aromatic isocyanate and less than 15% by mass of aliphatic isocyanate has better performance.
As can be seen from the analysis of examples 5-7 and example 1, examples 5-7 are inferior to example 1, and example 7 is inferior to examples 5-6, which demonstrates that the performance of the polyurethane polishing pad is improved by the gradient temperature-raising method of the present invention.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (13)
1. A method of preparing a polyurethane polishing pad, comprising the steps of:
step 1, reacting a mixture of aromatic isocyanate and aliphatic isocyanate with polyether polyol, a microsphere foaming agent and a chain extender to obtain foamed polyurethane;
step 2, curing the foamed polyurethane through gradient temperature rise to obtain a polyurethane elastomer;
step 3, slicing the polyurethane elastomer to obtain a polyurethane polishing pad;
in the mixture of the aromatic isocyanate and the aliphatic isocyanate, the mass percentage of the aromatic isocyanate is more than or equal to 85 percent, and the mass percentage of the aliphatic isocyanate is less than 15 percent;
in step 2, the gradient temperature rise specifically comprises: preheating the foaming polyurethane to 40-60 ℃ which is not equal to 60 ℃, standing for 15-30min, and then performing the following steps:
heating to 60 ℃ in 0.5h, and keeping 0.5-1.5 h;
heating to 80 ℃ in 0.5h, and keeping 1.5-2.5 h;
heating to 90 ℃ in 2h, and keeping 0.5-1.5 h;
heating to 100 ℃ in 2h, and keeping 3.5-4.5 h;
the temperature is raised to 110 ℃ in 0.5h, and 5-7h is kept.
2. The preparation method according to claim 1, wherein in step 1, the reaction specifically comprises:
heating a mixture of aromatic isocyanate and aliphatic isocyanate to 65-75 ℃, and then dropwise adding dehydrated polyether polyol into the mixture to obtain a first component;
and cooling the first component, uniformly mixing the first component with the microsphere foaming agent, mixing the first component with the chain extender, and defoaming to obtain the foamed polyurethane.
3. The method of claim 2, wherein the polyether polyol is dehydrated by a method comprising: drying the polyether polyol at 110-120 ℃.
4. The method of claim 3, wherein the drying time is 1-3 h.
5. The method according to claim 1, wherein in the step 1, the molar ratio of the mixture of the polyether polyol, the aromatic isocyanate and the aliphatic isocyanate to the chain extender is 1 (2-6) to (1-5).
6. The method of claim 1, wherein the polyether polyol comprises polytetrahydrofuran.
7. The method of claim 1, wherein the polyether polyol has a number average molecular weight of 600 to 3000 g/mol.
8. The method of claim 1, wherein the chain extender is an alcohol chain extender.
9. The method of claim 1, wherein the aromatic isocyanate comprises any one of or a combination of at least two of diphenylmethane diisocyanate, naphthalene 1,5-diisocyanate, or toluene diisocyanate.
10. The method according to claim 1, wherein the aliphatic isocyanate comprises any one of or a combination of at least two of m-xylylene diisocyanate, hexamethylene diisocyanate, or isophorone diisocyanate.
11. The preparation method of claim 2, wherein the mass percentage of the microsphere foaming agent is 0.1-1 wt% based on 100wt% of the total mass of the polyether polyol, the mixture of the aromatic isocyanate and the aliphatic isocyanate and the chain extender.
12. The production method according to claim 11, wherein the particle size of the microsphere foaming agent is 5 to 50 μm.
13. A polyurethane polishing pad prepared by the method of any one of claims 1-12.
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