CN113717342A - Modified polyurethane and preparation method and application thereof - Google Patents
Modified polyurethane and preparation method and application thereof Download PDFInfo
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- CN113717342A CN113717342A CN202110853196.9A CN202110853196A CN113717342A CN 113717342 A CN113717342 A CN 113717342A CN 202110853196 A CN202110853196 A CN 202110853196A CN 113717342 A CN113717342 A CN 113717342A
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- 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
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- 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
- C08G18/4825—Polyethers containing two hydroxy groups
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- 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
- C08G18/6677—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 having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
- E01C13/00—Pavings or foundations specially adapted for playgrounds or sports grounds; Drainage, irrigation or heating of sports grounds
- E01C13/06—Pavings made in situ, e.g. for sand grounds, clay courts E01C13/003
- E01C13/065—Pavings made in situ, e.g. for sand grounds, clay courts E01C13/003 at least one in situ layer consisting of or including bitumen, rubber or plastics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention relates to a preparation method of modified polyurethane, which comprises the following steps: mixing 10 parts by mass of pentaerythritol triacrylate and 30-70 parts by mass of polydimethylmethylhydrosiloxane, heating to react under a catalytic condition, and separating a reaction product to prepare hydroxyl-containing organic silicone oil; heating and dehydrating 100 parts by mass of polyether glycol to prepare anhydrous polyether glycol; by mass, 30-60 parts of aromatic diisocyanate, 2-10 parts of trimethylolpropane and 20-65 parts of hydroxyl-containing organic silicone oil are sequentially added into the anhydrous polyether glycol to react to prepare the modified polyurethane, so that the strength and the aging resistance of the modified polyurethane can be improved, and the surface pulverization is reduced.
Description
Technical Field
The invention relates to the field of bonding materials, in particular to modified polyurethane and a preparation method and application thereof.
Background
Along with the continuous improvement of national economic level, people pay more and more attention to sports and health, sports floor materials have wide development space, common sports floor materials are prepared from organic silicon modified polyurethane materials, the organic silicon modified polyurethane is usually prepared by adopting a silane coupling agent grafting modification or nano-silica modification method, the organic silicon modified polyurethane has good aging resistance, and is green and environment-friendly, but the prepared organic silicon modified polyurethane sports floor materials have lower strength. And because the sports terrace material is often required to be constructed outdoors, the weather is changed frequently, and the sports terrace material is often exposed to the sun for a long time, the surface pulverization of the polyurethane coating is easily caused, the polyurethane coating is easy to delaminate, and the aging resistance is poor.
Disclosure of Invention
Based on the above, there is a need for a modified polyurethane having improved strength and aging resistance and reduced surface powdering, and a method for preparing the same.
The invention provides a preparation method of modified polyurethane, which comprises the following steps:
mixing 10 parts by mass of pentaerythritol triacrylate and 30-70 parts by mass of polydimethylmethylhydrosiloxane, heating to react under a catalytic condition, and separating a reaction product to prepare hydroxyl-containing organic silicone oil;
heating and dehydrating 100 parts by mass of polyether glycol to prepare anhydrous polyether glycol;
and sequentially adding 30-60 parts by mass of aromatic diisocyanate, 2-10 parts by mass of trimethylolpropane and 20-65 parts by mass of hydroxyl-containing organic silicone oil into the anhydrous polyether glycol, and reacting to prepare the modified polyurethane.
In one embodiment, the polyether diol is a polyoxypropylene diol; and/or the presence of a gas in the gas,
the aromatic diisocyanate is one or more of pure MDI, liquid MDI and TDI.
In one embodiment, the hydrogen content of the polydimethylmethylhydrogen siloxane is 0.5% -2%; and/or the presence of a gas in the gas,
the polyether glycol has a number average molecular weight of 1000g/mol to 4000 g/mol.
In one embodiment, in the process of preparing the hydroxyl group-containing silicone oil, the heating reaction comprises the following specific steps: reacting for 6-10 h at the temperature of 70-90 ℃; and/or the presence of a gas in the gas,
in the process of preparing the hydroxyl-containing organic silicone oil, the method for separating the reaction product is reduced pressure distillation, and the reduced pressure distillation comprises the following specific steps: heating the reaction system to 100-150 ℃, and distilling under reduced pressure for 30-180 min under the condition of negative pressure; and/or the presence of a gas in the gas,
in the process of preparing the anhydrous polyether glycol, the dehydration comprises the following specific steps: dehydrating for 2-4 h under the condition of negative pressure and the temperature of 100-150 ℃.
In one embodiment, in the process of preparing the modified polyurethane, after the aromatic diisocyanate is added into the anhydrous polyether glycol, the temperature is controlled to be 75-90 ℃, the reaction is carried out for 1-4 h, and then the trimethylolpropane is added after the temperature is reduced to 55-75 ℃; and/or the presence of a gas in the gas,
after the trimethylolpropane is added, reacting for 1-3 h, controlling the temperature to be 55-75 ℃, and then adding the hydroxyl-containing organic silicone oil; and/or the presence of a gas in the gas,
after the hydroxyl-containing organic silicon oil is added, the reaction is carried out for 1 to 3 hours, and the temperature is controlled to be 55 to 75 ℃.
The invention also provides modified polyurethane prepared by the preparation method of the modified polyurethane in any embodiment.
The invention also provides a preparation method of the modified polyurethane coating, which comprises the step of mixing 100 parts by mass of the modified polyurethane, 100-300 parts by mass of the filler and 30-80 parts by mass of the viscosity reducer to prepare the modified polyurethane coating.
In one embodiment, the filler is one or more of 400-1250 mesh talcum powder, heavy calcium carbonate, kaolin and titanium dioxide; and/or the presence of a gas in the gas,
the viscosity reducer is one or a mixture of more of chlorinated paraffin-52 and chlorinated palm oil.
The invention also provides a modified polyurethane coating prepared by the preparation method of the modified polyurethane coating in any embodiment.
The invention also provides a preparation method of the modified polyurethane sports terrace material, which comprises the steps of mixing 100 parts of the modified polyurethane coating with 0.1-1 part of water by mass part, and curing for 5-15 days.
The invention also provides a modified polyurethane sports floor material, which is prepared by the preparation method of the modified polyurethane sports floor material.
The invention also provides a modified polyurethane sports floor which is paved by the modified polyurethane sports floor material.
The hydroxyl-containing organic silicone oil with a specific multi-branched structure is prepared from pentaerythritol triacrylate and polydimethylsiloxane, and is grafted with the prepared branched isocyanate-terminated polyurethane prepolymer to form the modified polyurethane with the specific multi-branched structure, so that the tensile strength of the modified polyurethane can be effectively improved, the elongation at break, impact absorption and vertical deformation of the modified polyurethane are ensured, and meanwhile, the branched silicon-oxygen bonds migrate to the surface to protect the main chain of the polyurethane, so that the effect of improving the aging resistance is achieved.
Detailed Description
In order to facilitate understanding of the present invention, the modified polyurethane of the present invention, the preparation method and the application thereof will be more fully described below with reference to examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
An embodiment of the present invention provides a method for preparing modified polyurethane, including the following steps S110 to S130.
S110: mixing 10 parts by mass of pentaerythritol triacrylate and 30-70 parts by mass of polydimethylmethylhydrosiloxane, heating to react under a catalytic condition, and separating a reaction product to prepare the hydroxyl-containing organic silicone oil.
Further, by mass, 10 parts of pentaerythritol triacrylate and 40-60 parts of polydimethylmethylhydrosiloxane are mixed, heated to react under a catalytic condition, and a reaction product is separated to prepare the hydroxyl-containing silicone oil. Pentaerythritol triacrylate and polydimethylmethylhydrogensiloxane can be sufficiently added to form specific multi-branched siloxane structures.
Further, the content of hydrogen in the polydimethylmethylhydrogensiloxane is 0.5% -2%. Further, the content of hydrogen in the polydimethylmethylhydrogen siloxane is 0.8-1.2%.
In a specific example, in the preparation of the hydroxyl group-containing silicone oil, the catalytic condition is the addition of a catalyst, specifically, but not limited to, the addition of a platinum group catalyst, for example, a chloroplatinic acid catalyst may be added. Pentaerythritol triacrylate and polydimethylmethylhydrosiloxane can react quickly and be fully added under the catalytic condition. Optionally, the mass part of the chloroplatinic acid catalyst is 0.05-2 parts. Further, the mass part of the chloroplatinic acid catalyst is 0.1-1 part.
In a specific example, in the process of preparing the hydroxyl group-containing silicone oil, heating is beneficial to promote the addition reaction, and specifically, the temperature of the reaction system can be raised to 70-90 ℃ for 6-10 h. More specifically, the temperature of the reaction system can be raised to 70-80 ℃ for 6-8 h.
After the reaction is finished, the reaction product can be separated by means of reduced pressure distillation, for example, the reaction system can be heated to 100 ℃ to 150 ℃ and reduced pressure distillation is carried out for 30min to 180min under the condition of negative pressure. Further, the reaction system can be heated to 100-120 ℃ and distilled under reduced pressure for 30-120 min.
S120: the anhydrous polyether glycol is prepared by heating and dehydrating 100 parts by mass of polyether glycol.
Alternatively, the polyether diol may be a polyoxypropylene diol, wherein the polyether diol has a number average molecular weight of 1000g/mol to 4000 g/mol. Specifically, the number average molecular weight of the polyether glycol may be, but not limited to, 1000g/mol, 1500g/mol, 2000g/mol, 2500 g/mol, 3000g/mol, 3500g/mol, 4000 g/mol.
In one specific example, in the process of preparing the anhydrous polyether glycol, the specific steps of dehydration are: dehydrating for 2-4 h under the condition of negative pressure and the temperature of 100-150 ℃. Further, the dehydration comprises the following specific steps: dehydrating for 2-3 h under the condition of negative pressure and the temperature of 100-120 ℃. The polyether glycol is dehydrated, so that the generation of byproducts in the preparation process of the modified polyurethane coating can be reduced.
S130: according to the mass parts, 30-60 parts of aromatic diisocyanate, 2-10 parts of trimethylolpropane and 20-65 parts of hydroxyl-containing organic silicone oil are sequentially added into anhydrous polyether glycol to react, and the modified polyurethane is prepared.
Further, 40-55 parts by mass of aromatic diisocyanate, 3-8 parts by mass of trimethylolpropane and 30-60 parts by mass of hydroxyl-containing silicone oil are sequentially added to the anhydrous polyether glycol to react, and the modified polyurethane is prepared. Alternatively, the aromatic diisocyanate may be, but is not limited to, one or more of pure MDI, liquid MDI, and TDI.
In a specific example, in the process of preparing the modified polyurethane, after the aromatic diisocyanate is added into the anhydrous polyether glycol, the temperature is controlled to be 75-90 ℃, the reaction is carried out for 1-4 h, then the temperature is reduced to 55-75 ℃, and then the trimethylolpropane is added. Further, controlling the temperature to be 75-85 ℃, reacting for 2-3 h, cooling to 65-75 ℃, and adding trimethylolpropane. The anhydrous polyether glycol reacts with the aromatic diisocyanate to generate linear polyurethane, and then trihydroxymethyl propane is added to grow the polyurethane chain and enable the polyurethane chain to form a specific cross-linking structure.
In a specific example, after trimethylolpropane is added, the reaction is carried out for 1 to 3 hours, the temperature is controlled to be between 55 and 75 ℃, and then the organic silicone oil containing hydroxyl is added. Further, reacting for 1-2.5 h, and controlling the temperature to be 65-75 ℃.
In a specific example, after the hydroxyl-containing organic silicone oil is added, the reaction is carried out for 1 to 3 hours, and the temperature is controlled to be 55 to 75 ℃. Further reacting for 1-2 h, and controlling the temperature to be 65-75 ℃.
The modified polyurethane with the multi-branched structure and high crosslinking degree is formed by firstly preparing a mutually crosslinked branched isocyanate-terminated polyurethane prepolymer by anhydrous polyether diol and aromatic diisocyanate under the promotion of trimethylolpropane and then introducing a mode of grafting hydroxyl-containing organic silicone oil and the isocyanate-terminated polyurethane prepolymer.
The invention also provides a modified polyurethane prepared by the preparation method of any one of the specific examples.
The embodiment of the invention also provides a preparation method of the modified polyurethane coating, which comprises the step of mixing 100 parts of modified polyurethane, 100-300 parts of filler and 30-80 parts of viscosity reducer by mass part to prepare the modified polyurethane coating.
Further, 100 parts by mass of modified polyurethane, 100-200 parts by mass of filler and 30-50 parts by mass of viscosity reducer are mixed to prepare the modified polyurethane coating.
In a specific example, the filler may be, but is not limited to, one or more of 400-1250 mesh talc, heavy calcium carbonate, kaolin, and titanium dioxide. Further, the filler is dehydrated before use.
In a specific example, the viscosity reducer may be, but is not limited to, one or more of chlorinated paraffin-52 and chlorinated palm oil. Further, the viscosity reducer is dehydrated before use.
The invention also provides a modified polyurethane coating prepared by the preparation method of any one of the specific examples.
An embodiment of the invention also provides a preparation method of the modified polyurethane sports terrace material, wherein 100 parts by mass of the modified polyurethane coating is mixed with 0.1-1 part by mass of water and cured.
Further, 100 parts by mass of the modified polyurethane coating is mixed with 0.1 to 0.5 part by mass of water and cured.
In a specific example, the maturation time is between 5 days and 15 days. Further, the curing time is 7 to 10 days.
The invention also provides a modified polyurethane sports floor material, which is prepared by the preparation method of the modified polyurethane sports floor material in any specific example.
The invention further provides a modified polyurethane sports floor which is paved by the modified polyurethane sports floor material in any one of the specific examples.
The hydroxyl-containing organic silicone oil with a specific multi-branched structure is prepared from pentaerythritol triacrylate and polydimethylsiloxane, and is grafted with the prepared branched isocyanate-terminated polyurethane prepolymer to form the modified polyurethane with the specific multi-branched structure, so that the tensile strength of the modified polyurethane can be effectively improved, the elongation at break, impact absorption and vertical deformation of the modified polyurethane are ensured, and meanwhile, the branched silicon-oxygen bonds migrate to the surface to protect the main chain of the polyurethane, so that the effect of improving the aging resistance is achieved.
The following are specific examples, and in the following specific examples, all the raw materials may be commercially available unless otherwise specified. Among them, polydimethylmethylhydrogensiloxane and partially hydrogen-terminated polydimethylsiloxane are available from Ningbo Runzao high-new materials science and technology Co.
Example 1
(1) Preparing hydroxyl-containing organic silicone oil:
according to the mass parts, 10 parts of pentaerythritol triacrylate and 60 parts of polydimethylmethylhydrogensiloxane (with the hydrogen content of 0.95-1.05%) are respectively added into a reaction kettle under the condition of stirring, then 0.2 part of chloroplatinic acid is added, and the temperature is raised to 80 ℃ for reaction for 8 hours. After the reaction is finished, heating to 120 ℃, and distilling under reduced pressure of 0.095MPa for 30min to separate reaction products, thereby obtaining the hydroxyl-containing organic silicone oil.
(2) Preparing modified polyurethane:
adding 100 parts by mass of polyoxypropylene glycol (Mn is 2000g/mol) into a reaction kettle, heating to 100 ℃, dehydrating for 2h under the condition of negative pressure of 0.095MPa, adding 40 parts of 4,4' -diphenylmethane diisocyanate (pure MDI), reacting for 2h under the condition of 80 ℃, reducing to 70 ℃, adding 4 parts of trimethylolpropane, reacting for 1h, controlling the temperature to be 70 ℃, adding 60 parts of the hydroxyl-containing organic silicone oil prepared in the step (1), reacting for 2h, and controlling the temperature to be 70 ℃ to obtain the modified polyurethane.
(3) Preparing a modified polyurethane coating:
and (3) mixing 100 parts by mass of the modified polyurethane prepared in the step (2) with 200 parts by mass of dehydrated 400-mesh talcum powder and 50 parts by mass of dehydrated chlorinated paraffin-52, and uniformly stirring to obtain the modified polyurethane coating.
(4) Preparing a modified polyurethane sports terrace material:
mixing 100 parts by mass of the modified polyurethane coating prepared in the step (3) with 0.2 part by mass of water, and placing the mixture in a mold for curing at normal temperature for 7 days.
Example 2
(1) Preparing hydroxyl-containing organic silicone oil:
according to the mass parts, 10 parts of pentaerythritol triacrylate and 40 parts of polydimethylmethylhydrogensiloxane (with the hydrogen content of 0.95-1.05%) are respectively added into a reaction kettle under the condition of stirring, 0.2 part of chloroplatinic acid is added, and the temperature is raised to 70 ℃ for reaction for 7 hours. After the reaction is finished, heating to 120 ℃, and distilling under reduced pressure of 0.095MPa for 30min to separate reaction products, thereby obtaining the hydroxyl-containing organic silicone oil.
(2) Preparing modified polyurethane:
adding 100 parts by mass of polyoxypropylene glycol (Mn is 2000g/mol) into a reaction kettle, heating to 100 ℃, dehydrating for 2h under the condition of negative pressure of 0.095MPa, adding 55 parts of 4,4' -diphenylmethane diisocyanate (pure MDI), reacting for 2h under the condition of 85 ℃, reducing to 65 ℃, adding 5 parts of trimethylolpropane, reacting for 1h, controlling the temperature to 65 ℃, adding 45 parts of the hydroxyl-containing organic silicone oil prepared in the step (1), reacting for 2h, and controlling the temperature to 65 ℃ to obtain the modified polyurethane.
(3) Preparing a modified polyurethane coating:
and (3) mixing 100 parts by mass of the modified polyurethane prepared in the step (2) with 200 parts by mass of dehydrated 400-mesh talcum powder and 50 parts by mass of dehydrated chlorinated paraffin-52, and uniformly stirring to obtain the modified polyurethane coating.
(4) Preparing a modified polyurethane sports terrace material:
mixing 100 parts by mass of the modified polyurethane coating prepared in the step (3) with 0.2 part by mass of water, and placing the mixture in a mold for curing at normal temperature for 7 days.
Comparative example 1
(1) Preparing hydroxyl-containing organic silicone oil:
according to the mass parts, 10 parts of hydroxyethyl acrylate and 60 parts of polydimethylmethylhydrogensiloxane (with the hydrogen content of 0.95-1.05%) are respectively added into a reaction kettle under the condition of stirring, 0.2 part of chloroplatinic acid is added, and the temperature is raised to 80 ℃ for reaction for 8 hours. After the reaction is finished, heating to 120 ℃, and distilling under reduced pressure of 0.095MPa for 30min to separate reaction products, thereby obtaining the hydroxyl-containing organic silicone oil.
(2) Preparing modified polyurethane:
adding 100 parts by mass of polyoxypropylene glycol (Mn is 2000g/mol) into a reaction kettle, heating to 100 ℃, dehydrating for 2h under the condition of negative pressure of 0.095MPa, adding 40 parts of 4,4' -diphenylmethane diisocyanate (pure MDI), reacting for 2h under the condition of 80 ℃, reducing to 70 ℃, adding 4 parts of trimethylolpropane, reacting for 1h, controlling the temperature to be 70 ℃, adding 60 parts of the hydroxyl-containing organic silicone oil prepared in the step (1), reacting for 2h, and controlling the temperature to be 70 ℃ to obtain the modified polyurethane.
(3) Preparing a modified polyurethane coating:
and (3) mixing 100 parts by mass of the modified polyurethane prepared in the step (2) with 200 parts by mass of dehydrated 400-mesh talcum powder and 50 parts by mass of dehydrated chlorinated paraffin-52, and uniformly stirring to obtain the modified polyurethane coating.
(4) Preparing a modified polyurethane sports terrace material:
mixing 100 parts by mass of the modified polyurethane coating prepared in the step (3) with 0.2 part by mass of water, and placing the mixture in a mold for curing at normal temperature for 7 days.
Comparative example 2
(1) Preparing hydroxyl-containing organic silicone oil:
according to the mass parts, 10 parts of pentaerythritol triacrylate and 60 parts of partial hydrogen-terminated polydimethylsiloxane (with the hydrogen content of 0.95-1.05%) are respectively added into a reaction kettle under the condition of stirring, then 0.2 part of chloroplatinic acid is added, and the temperature is raised to 80 ℃ for reaction for 8 hours. After the reaction is finished, heating to 120 ℃, and distilling under reduced pressure of 0.095MPa for 30min to separate reaction products, thereby obtaining the hydroxyl-containing organic silicone oil.
(2) Preparing modified polyurethane:
adding 100 parts by mass of polyoxypropylene glycol (Mn is 2000g/mol) into a reaction kettle, heating to 100 ℃, dehydrating for 2h under the condition of negative pressure of 0.095MPa, adding 40 parts of 4,4' -diphenylmethane diisocyanate (pure MDI), reacting for 2h under the condition of 80 ℃, reducing to 70 ℃, adding 4 parts of trimethylolpropane, reacting for 1h, controlling the temperature to be 70 ℃, adding 60 parts of the hydroxyl-containing organic silicone oil prepared in the step (1), reacting for 2h, and controlling the temperature to be 70 ℃ to obtain the modified polyurethane.
(3) Preparing a modified polyurethane coating:
and (3) mixing 100 parts by mass of the modified polyurethane prepared in the step (2) with 200 parts by mass of dehydrated 400-mesh talcum powder and 50 parts by mass of dehydrated chlorinated paraffin-52, and uniformly stirring to obtain the modified polyurethane coating.
(4) Preparing a modified polyurethane sports terrace material:
mixing 100 parts by mass of the modified polyurethane coating prepared in the step (3) with 0.2 part by mass of water, and placing the mixture in a mold for curing at normal temperature for 7 days.
Comparative example 3
(1) Preparing hydroxyl-containing organic silicone oil:
according to the mass parts, 10 parts of pentaerythritol triacrylate and 60 parts of polydimethylmethylhydrogensiloxane (with the hydrogen content of 0.95-1.05%) are respectively added into a reaction kettle under the condition of stirring, then 0.2 part of chloroplatinic acid is added, and the temperature is raised to 80 ℃ for reaction for 8 hours. After the reaction is finished, heating to 120 ℃, and distilling under reduced pressure of 0.095MPa for 30min to separate reaction products, thereby obtaining the hydroxyl-containing organic silicone oil.
(2) Preparing modified polyurethane:
adding 100 parts by mass of polyoxypropylene glycol (Mn is 2000g/mol) into a reaction kettle, heating to 100 ℃, dehydrating for 2h under the condition of negative pressure of 0.095MPa, adding 40 parts of 4,4' -diphenylmethane diisocyanate (pure MDI), reacting for 2h under the condition of 80 ℃, reducing to 70 ℃, adding 60 parts of hydroxyl-containing organic silicone oil prepared in the step (1), reacting for 2h, and controlling the temperature to be 70 ℃ to obtain the modified polyurethane.
(3) Preparing a modified polyurethane coating:
and (3) mixing 100 parts by mass of the modified polyurethane prepared in the step (2) with 200 parts by mass of dehydrated 400-mesh talcum powder and 50 parts by mass of dehydrated chlorinated paraffin-52, and uniformly stirring to obtain the modified polyurethane coating.
(4) Preparing a modified polyurethane sports terrace material:
mixing 100 parts by mass of the modified polyurethane coating prepared in the step (3) with 0.2 part by mass of water, and placing the mixture in a mold for curing at normal temperature for 7 days.
Comparative example 4
(1) Preparing organic silicon oil mixture oil:
according to the mass parts, 10 parts of pentaerythritol triacrylate and 60 parts of polydimethylmethylhydrogensiloxane (with the hydrogen content of 0.95-1.05%) are respectively added into a reaction kettle under the stirring condition, the mixture is uniformly stirred, and the temperature is raised to 80 ℃ for reaction for 8 hours, so that the organic silicon oil mixture is obtained.
(2) Preparing modified polyurethane:
adding 100 parts by mass of polyoxypropylene glycol (Mn is 2000g/mol) into a reaction kettle, heating to 100 ℃, dehydrating for 2h under the condition of negative pressure of 0.095MPa, adding 40 parts of 4,4' -diphenylmethane diisocyanate (pure MDI), reacting for 2h under the condition of 80 ℃, reducing to 70 ℃, adding 4 parts of trimethylolpropane, reacting for 1h, controlling the temperature to be 70 ℃, adding 60 parts of the hydroxyl-containing organic silicone oil prepared in the step (1), reacting for 2h, and controlling the temperature to be 70 ℃ to obtain the modified polyurethane.
(3) Preparing a modified polyurethane coating:
and (3) mixing 100 parts by mass of the modified polyurethane prepared in the step (2) with 200 parts by mass of dehydrated 400-mesh talcum powder and 50 parts by mass of dehydrated chlorinated paraffin-52, and uniformly stirring to obtain the modified polyurethane coating.
(4) Preparing a modified polyurethane sports terrace material:
mixing 100 parts by mass of the modified polyurethane coating prepared in the step (3) with 0.2 part by mass of water, and placing the mixture in a mold for curing at normal temperature for 7 days.
The modified polyurethane sports flooring materials prepared in examples 1 to 2 and comparative examples 1 to 4 are subjected to mechanical property and aging resistance tests according to national standard GB36246-2018, and the test results are shown in the following table 1.
Table 1. modified polyurethane sports terrace material performance test results
As can be seen from table 1 above, the modified polyurethane sports flooring materials prepared in examples 1 to 2 have better tensile strength and elongation at break than those of comparative examples 1 to 4, and the aging resistance test result shows that the modified polyurethane sports flooring materials have no cracks, no pulverization, and more excellent aging resistance.
As can be seen from the performance test results of the embodiment 1 and the comparative example 1 and the embodiment 1 and the comparative example 2, compared with hydroxyethyl acrylate and poly (dimethyl methyl hydrogen siloxane) and partial hydrogen-terminated polydimethylsiloxane, the hydroxyl-containing organic silicone oil prepared by adopting the method is beneficial to preparing specific multi-branched modified polyurethane, and is further beneficial to improving the tensile strength, the elongation at break and the aging resistance of the modified polyurethane sports terrace material.
As can be seen from the performance test results of example 1 and comparative example 3, the addition of trimethylolpropane in the preparation process of the modified polyurethane can help to improve the tensile strength, elongation at break and aging resistance of the modified polyurethane sports terrace material.
As can be seen from the performance test results of example 1 and comparative example 4, the hydroxyl silicone oil is prepared first, and then the isocyanate-terminated polyurethane prepolymer is introduced, so that the performance of the prepared modified polyurethane sports floor material in terms of tensile strength, elongation at break and aging resistance is superior to that of the modified polyurethane sports floor material formed by directly reacting pentaerythritol triacrylate with MDI, and the polydimethylsiloxane is not compatible with the polyurethane system, thereby having adverse effects on various performances of the modified polyurethane sports floor material.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. A preparation method of modified polyurethane is characterized by comprising the following steps:
mixing 10 parts by mass of pentaerythritol triacrylate and 30-70 parts by mass of polydimethylmethylhydrosiloxane, heating to react under a catalytic condition, and separating a reaction product to prepare hydroxyl-containing organic silicone oil;
heating and dehydrating 100 parts by mass of polyether glycol to prepare anhydrous polyether glycol;
and sequentially adding 30-60 parts by mass of aromatic diisocyanate, 2-10 parts by mass of trimethylolpropane and 20-65 parts by mass of hydroxyl-containing organic silicone oil into the anhydrous polyether glycol, and reacting to prepare the modified polyurethane.
2. The method for producing a modified polyurethane according to claim 1, wherein the polyether diol is a polyoxypropylene diol; and/or the presence of a gas in the gas,
the aromatic diisocyanate is one or more of pure MDI, liquid MDI and TDI.
3. The preparation method of the modified polyurethane according to claim 1, wherein the hydrogen content of the polydimethylmethylhydrogensiloxane is 0.5% to 2%; and/or the presence of a gas in the gas,
the polyether glycol has a number average molecular weight of 1000g/mol to 4000 g/mol.
4. The method for preparing the modified polyurethane according to claim 1, wherein the heating reaction comprises the following specific steps in the process of preparing the hydroxyl group-containing silicone oil: reacting for 6-10 h at the temperature of 70-90 ℃; and/or the presence of a gas in the gas,
in the process of preparing the hydroxyl-containing organic silicone oil, the method for separating the reaction product is reduced pressure distillation, and the reduced pressure distillation comprises the following specific steps: heating the reaction system to 100-150 ℃, and distilling under reduced pressure for 30-180 min under the condition of negative pressure; and/or the presence of a gas in the gas,
in the process of preparing the anhydrous polyether glycol, the dehydration comprises the following specific steps: dehydrating for 2-4 h under the condition of negative pressure and the temperature of 100-150 ℃.
5. The method for preparing the modified polyurethane according to any one of claims 1 to 4, wherein in the process of preparing the modified polyurethane, after the aromatic diisocyanate is added to the anhydrous polyether glycol, the temperature is controlled to be 75-90 ℃, the reaction is carried out for 1-4 h, and then the trimethylolpropane is added after the temperature is reduced to 55-75 ℃; and/or the presence of a gas in the gas,
after the trimethylolpropane is added, reacting for 1-3 h, controlling the temperature to be 55-75 ℃, and then adding the hydroxyl-containing organic silicone oil; and/or the presence of a gas in the gas,
after the hydroxyl-containing organic silicon oil is added, the reaction is carried out for 1 to 3 hours, and the temperature is controlled to be 55 to 75 ℃.
6. A modified polyurethane, characterized by being prepared by the method for preparing a modified polyurethane according to any one of claims 1 to 5.
7. A preparation method of a modified polyurethane coating is characterized by mixing 100 parts by mass of the modified polyurethane of claim 6, 100-300 parts by mass of a filler and 30-80 parts by mass of a viscosity reducer to prepare the modified polyurethane coating.
8. The method for preparing the modified polyurethane paint as claimed in claim 7, wherein the filler is one or more of 400-1250 mesh talcum powder, heavy calcium carbonate, kaolin and titanium dioxide; and/or the presence of a gas in the gas,
the viscosity reducer is one or a mixture of more of chlorinated paraffin-52 and chlorinated palm oil.
9. A modified polyurethane coating, which is characterized by being prepared by the preparation method of the modified polyurethane coating of any one of claims 7 to 8.
10. A preparation method of the modified polyurethane sports terrace material is characterized in that 100 parts by mass of the modified polyurethane coating of claim 9 is mixed with 0.1-1 part by mass of water, and the mixture is cured for 5-15 days.
11. A modified polyurethane sports floor material, which is characterized by being prepared by the preparation method of the modified polyurethane sports floor material according to any one of claim 10.
12. A modified polyurethane sports terrace, characterized by that, it is paved by the modified polyurethane sports terrace material of claim 11.
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