Classifications

• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
• • 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
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/02—Aliphatic polycarbonates
  • C08G64/0208—Aliphatic polycarbonates saturated
  • C08G64/0225—Aliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen
  • C08G64/0266—Aliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen containing silicon
• • 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
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/18—Block or graft polymers
  • C08G64/183—Block or graft polymers containing polyether sequences
• • 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
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/32—General preparatory processes using carbon dioxide
  • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
  • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
  • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
  • C08G65/2645—Metals or compounds thereof, e.g. salts
  • C08G65/2663—Metal cyanide catalysts, i.e. DMC's

Definitions

• the present invention relates to a curable composition suitable for sealants, adhesives, etc., containing a polymer having a reactive silicon group, and a cured product thereof.
• Polymers containing reactive silicon groups become flexible rubber-like cured products through the formation of siloxane bonds through hydrolysis and condensation reactions of the reactive silicon groups, so they are used in applications such as sealants and adhesives. Widely used.
• Patent Document 1 describes that a polyether polycarbonate polymer having a reactive silicon group has good strength and elongation of a cured product.
• Patent Document 2 also describes a silicone resin in which the reactive silicon group is a trialkoxysilyl group and the main chain has a polyoxyalkylene structure, and a silicone resin in which the reactive silicon group is a dialkoxysilyl group and the main chain is a polyoxyalkylene structure. It is described that a silicone-based resin composition containing a silicone-based resin is capable of bonding in an extremely short time.
• Patent Document 1 only describes a polymer having two reactive silicon groups as a polyether polycarbonate polymer having reactive silicon groups, and such polyether polycarbonate The polymer had a high viscosity and could not be said to have excellent handling properties. Further, the silicone resin composition described in Patent Document 2 has insufficient tensile properties and shear strength of the cured product depending on the test method, and there is room for improvement.
• the present invention has been made in view of these circumstances, and provides a curable composition containing a polymer having a reactive silicon group, which provides a cured product with excellent tensile properties and shear strength suitable as a sealing material.
• the present invention aims to provide a curable composition and a cured product thereof.
• the present invention provides a curable composition containing a polymer having reactive silicon groups, a polyfunctional polyether polycarbonate polymer having reactive silicon groups, and a polyfunctional oxyalkylene polymer having reactive silicon groups. This is based on the discovery that the cured product has good tensile properties and shear strength when used in combination.
• a reaction having three or more terminal groups in one molecule, and a unit based on carbon dioxide and a unit based on alkylene oxide, and at least a part of the terminal groups is represented by the following formula (1) a polyether polycarbonate polymer (A) which is a silicon group and has a number average molecular weight (Mn) of 2,000 to 50,000; An oxyalkylene polymer (B) having two or more terminal groups, at least a part of which is a reactive silicon group represented by the following formula (1), and having no carbon dioxide-based units.
• X is a halogen atom, a hydroxyl group, or a hydrolyzable group.
• R is a monovalent organic group having 1 to 20 carbon atoms and does not contain a hydrolyzable group.
• a is an integer from 1 to 3; when a is 1, two R's may be the same or different; when a is 2 or 3, multiple X's may be the same or different; May be different.
• the content of carbon dioxide-based units in the polyether polycarbonate polymer (A) is 10 to 30% by mass with respect to the total 100% by mass of carbon dioxide-based units and alkylene oxide-based units.
• [4] The curable composition according to any one of [1] to [3] above, wherein the polyether polycarbonate polymer (A) has a silylation rate of 70 to 100 mol%.
• a curable composition containing a polymer having a reactive silicon group it is possible to provide a curable composition that yields a cured product having excellent tensile properties and shear strength, and a cured product thereof.
• the curable composition of the present invention is useful, for example, as a sealant and an adhesive.
• the number average molecular weight (Mn) and the weight average molecular weight (Mw) are polystyrene equivalent molecular weights determined by gel permeation chromatography (GPC) based on a calibration curve created using a standard polystyrene sample.
• the terminal group in the polyether polycarbonate polymer includes not only the functional group at the end of the main chain of the polymer but also the functional group at the end of a branched chain equivalent to the main chain.
• the main chain in the oxyalkylene polymer includes initiator residues and repeating units (polyoxyalkylene chains) based on alkylene oxide monomers.
• the terminal group in the oxyalkylene polymer means an atomic group containing the oxygen atom closest to the molecular terminal among the oxygen atoms in the polyoxyalkylene chain.
• (Meth)acrylic is a general term for acrylic and methacrylic.
• the curable composition of the present invention has three or more terminal groups in one molecule, and also has a unit based on carbon dioxide and a unit based on alkylene oxide, and at least a part of the terminal groups has the following formula (1 ) and a polyether polycarbonate polymer (A) having a number average molecular weight (Mn) of 2,000 to 50,000, and having two or more terminal groups, It contains an oxyalkylene polymer (B) in which at least a portion of the terminal groups are reactive silicon groups represented by the following formula (1). -SiX a R 3-a (1)
• X is a halogen atom, a hydroxyl group, or a hydrolyzable group.
• R is a monovalent organic group having 1 to 20 carbon atoms and does not contain a hydrolyzable group.
• a is an integer from 1 to 3; when a is 1, two R's may be the same or different; when a is 2 or 3, multiple X's may be the same or different; May be different.
• a curable composition that uses a polyether polycarbonate polymer (A) and an oxyalkylene polymer (B) in combination as described above, a cured product having excellent tensile properties and shear strength can be obtained.
• the polyether polycarbonate polymer (A) has three or more terminal groups in one molecule, and also has units based on carbon dioxide and units based on alkylene oxide, and at least a part of the terminal groups has the following formula ( It is a reactive silicon group represented by 1) and has a number average molecular weight (Mn) of 2,000 to 50,000.
• the polyether polycarbonate polymer (A) may be used alone or in combination of two or more.
• alkylene oxide in the alkylene oxide-based unit examples include ethylene oxide, propylene oxide, butylene oxide, and tetramethylene oxide from the viewpoint of availability.
• One type of alkylene oxide may be used alone, or two or more types may be used in combination.
• the alkylene oxide-based units preferably include propylene oxide-based units.
• a unit based on carbon dioxide constitutes a carbonate group. Since the polyether polycarbonate polymer (A) has a carbonate group containing a unit based on carbon dioxide, the tensile properties and shear strength of the cured product of the curable composition are improved.
• the content of carbon dioxide-based units in the polyether polycarbonate polymer (A) is determined from the viewpoint of improving the tensile properties and shear strength of the cured product of the curable composition.
• the amount is preferably 10 to 30% by weight, more preferably 10 to 25% by weight, and still more preferably 10 to 20% by weight, based on the total of 100% by weight.
• the content of carbon dioxide-based units in the polyether polycarbonate polymer (A) can be determined by nuclear magnetic resonance (NMR) analysis, and specifically, by the method described in the Examples below. It will be done.
• the polyether polycarbonate polymer (A) has three or more terminal groups in one molecule, and at least a part of the terminal groups are reactive silicon groups represented by the above formula (1). If the polyether polycarbonate polymer (A) has less than three terminal groups in one molecule, the number of reactive silicon groups in the polyether polycarbonate polymer (A) will decrease, so the curable composition The tensile properties and shear strength of the cured product may decrease. From such a viewpoint, it is preferable that the polyether polycarbonate polymer (A) has four or more terminal groups in one molecule. Further, the polyether polycarbonate polymer (A) preferably has 10 or less terminal groups in one molecule, from the viewpoint of ease of handling when curing the curable composition and ease of coating. , more preferably 8 or less.
• Examples of the terminal groups that the polyether polycarbonate polymer (A) has three or more in one molecule include active hydrogen-containing groups and isocyanate groups in addition to the reactive silicon group represented by the above formula (1).
• Examples of the active hydrogen-containing group include a hydroxyl group, a carboxy group, an amino group, a monovalent functional group obtained by removing one hydrogen atom from a primary amine, a hydrazide group, and a mercapto group.
• the polyether polycarbonate polymer (A) may have reactive silicon groups other than those represented by formula (1), but the curable composition has good crosslinking reactivity and curability. From the viewpoint of improving the tensile properties and shear strength of the cured product of the composition, it is preferable that the reactive silicon group is only one represented by formula (1).
• the reactive silicon group represented by formula (1) is a crosslinking site of the polyether polycarbonate polymer (A), and can form a crosslinked structure by siloxane bonds.
• X is a halogen atom, a hydroxyl group, or a hydrolyzable group.
• the hydrolyzable group is a group that can form a silanol group (-Si-OH) by hydrolysis, and includes, for example, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, Examples include sulfanyl group and alkenyloxy group.
• the number of carbon atoms in the alkyl group or alkenyl group that may be contained in the hydrolyzable group is preferably 1 to 6, more preferably 1 to 3.
• X is preferably an alkoxy group, more preferably an alkoxy group having 1 to 3 carbon atoms, and even more preferably a methoxy group, an ethoxy group, or an isopropoxy group.
• methoxy groups or ethoxy groups are particularly preferred.
• R is a monovalent organic group having 1 to 20 carbon atoms and does not contain a hydrolyzable group.
• the organic group include a hydrocarbon group, a halohydrocarbon group, and a triorganosiloxy group, and the number of carbon atoms in the organic group is preferably 1 to 6, more preferably 1 to 3.
• R is preferably an alkyl group, a cycloalkyl group, an aryl group, a 1-chloroalkyl group, or a triorganosiloxy group, more preferably a straight or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, or a phenyl group.
• methyl group or ethyl group is preferable from the viewpoint of good curability of the polymer having a reactive silicon group and good stability of the curable composition, and good curing speed of the curable composition. From the viewpoint of 1-chloromethyl group is preferable, and from the viewpoint of easy availability, methyl group is preferable.
• a is an integer from 1 to 3.
• the two R's may be the same or different.
• the plurality of X's may be the same or different.
• a is preferably 2 or 3, more preferably 2.
• Examples of the reactive silicon group represented by formula (1) include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, and dimethoxymethyl group.
• Examples include silyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, diisopropoxymethylsilyl group, chloromethyldimethoxysilyl group, and chloromethyldiethoxysilyl group.
• trimethoxysilyl group triethoxysilyl group, dimethoxymethylsilyl group or diethoxymethylsilyl group, more preferably dimethoxymethylsilyl group or A trimethoxysilyl group, more preferably a dimethoxymethylsilyl group.
• the number of reactive silicon groups in the polyether polycarbonate polymer (A) is preferably more than 0.5 on average per end group, and 1 per end group.
• the number is 0.0 or less, more preferably 0.6 or more and 1.0 or less, even more preferably 0.7 or more and 1.0 or less.
• the average number of reactive silicon groups per terminal group can be calculated from H 1 -NMR or the charged equivalent weight (molar ratio) of the compound.
• Mn of the polyether polycarbonate polymer (A) is 2,000 to 50,000. If Mn is less than the above lower limit, the tensile properties and shear strength of the cured product of the curable composition may decrease, while if Mn exceeds the above upper limit, the curable composition will tend to have high viscosity. It may become difficult to handle during operations such as mixing. From this viewpoint, Mn of the polyether polycarbonate polymer (A) is preferably 5,000 to 30,000, more preferably 6,000 to 25,000.
• the molecular weight distribution of the polyether polycarbonate polymer (A), that is, Mw/Mn, is preferably 1.0 to 3.0, more preferably 1, from the viewpoint of making the curable composition low viscosity and easy to handle. .0 to 2.5, more preferably 1.0 to 2.0.
• Mn and Mw/Mn of the polyether polycarbonate polymer (A) can be controlled by the type of catalyst and polymerization conditions (temperature, stirring conditions, pressure, etc.).
• the above-mentioned Mn and Mw/Mn are applied to each of the two or more types.
• the polyether polycarbonate polymer (A) is, for example, a precursor polymer containing units based on carbon dioxide and units based on alkylene oxide, and having three or more terminal groups in one molecule into which reactive silicon groups can be introduced. It can be produced by a method of reacting (a) with a silylating agent.
• the method for producing the precursor polymer (a) is not particularly limited, and for example, an initiator having three or more terminal groups in one molecule is reacted with alkylene oxide and carbon dioxide in the presence of a catalyst, A method of obtaining the precursor polymer (a) by carrying out ring-opening addition polymerization is exemplified.
• a preferred method for producing the precursor polymer (a) is to perform ring-opening addition polymerization by reacting an initiator having three or more active hydrogen-containing groups in one molecule with an alkylene oxide and carbon dioxide in the presence of a catalyst.
• a method for obtaining the precursor polymer (a) can be mentioned. According to this method, the method has a polycarbonate chain consisting of units based on alkylene oxide and units based on carbon dioxide, and a polyoxyalkylene chain consisting of units based on alkylene oxide, and has active hydrogen as a terminal group in one molecule.
• a precursor polymer (a) having three or more containing groups is obtained.
• a precursor polymer (a) having three or more hydroxyl groups at the end can be obtained.
• a main chain structure in which units based on carbon dioxide and units based on alkylene oxide are randomly arranged can be easily formed.
• the polyether polycarbonate polymer (A) obtained from the precursor polymer (a) having such a randomly arranged main chain structure can contribute to improving the tensile properties and shear strength of the cured product of the curable composition. it is conceivable that.
• the initiator is preferably a polyol having three or more hydroxyl groups in one molecule.
• Specific examples of the initiator include glycerin, polyglycerin, trimethylolethane, trimethylolpropane, diglycerin, pentaerythritol, dipentaerythritol, tripentaerythritol, glucose, sorbitol, dextrose, fructose, sucrose, methylglucoside, and the above. Trivalent or higher polyhydric alcohols such as saccharides or derivatives thereof other than those described in .
• various optical isomers are also included.
• polyether polyols having a molecular weight of 50 to 8,000 in terms of hydroxyl value, which are obtained by reacting these with a small amount of alkylene oxide.
• Catalysts for ring-opening addition polymerization include, for example, multi-metal cyanide complex catalysts such as TBA-based multi-metal cyanide complex catalysts (hereinafter sometimes referred to as "DMC catalysts"); metal-salen complex catalysts such as cobalt-salen-based catalysts.
• DMC catalysts TBA-based multi-metal cyanide complex catalysts
• metal-salen complex catalysts such as cobalt-salen-based catalysts.
• Alkali catalysts such as sodium hydroxide, potassium hydroxide, and cesium hydroxide
• Ziegler-Natta catalysts consisting of organoaluminum compounds and transition metal compounds
• metal-coordination porphyrin catalysts as complexes obtained by reacting porphyrins
• phosphazene catalysts phosphazene catalysts
• imino groups Containing phosphazenium salts tris(pentafluorophenyl)borane; reduced Robson's type macrocyclic ligand catalyst
• DMC catalysts examples include zinc hexacyanocobaltate complexes whose ligand is t-butyl alcohol (hereinafter sometimes referred to as "TBA-DMC catalyst"), and ethylene glycol dimethyl ether (also referred to as "glyme”) whose ligand is t-butyl alcohol.
• TBA-DMC catalyst zinc hexacyanocobaltate complexes in which the ligand is diethylene glycol dimethyl ether (sometimes referred to as "diglyme”). These may be used alone or in combination of two or more.
• the TBA-DMC catalyst is preferred from the viewpoints of higher activity during polymerization, narrower Mw/Mn of the precursor polymer (a), and lower viscosity.
• metal salen complex catalysts examples include cobalt salen complexes, chromium salen complexes, and aluminum salen complexes described in Japanese Patent Publication No. 2012-500867, JP2015-129306A, and JP2015-28182A. These may be used alone or in combination of two or more.
• the catalyst may contain at least one selected from the group consisting of a DMC catalyst and a metal salen complex catalyst, from the viewpoint of easily adjusting the carbon dioxide introduction rate in the polyether polycarbonate polymer (A) to the preferred range in the present application. preferable. Further, the catalyst is preferably a DMC catalyst or a reduced Robson type macrocyclic ligand catalyst from the viewpoint of obtaining the precursor polymer (a) of the random polymer.
• the amount of catalyst added is not particularly limited as long as it is the amount necessary for carbon dioxide polymerization and alkylene oxide ring-opening polymerization, but it is preferably as small as possible, and 100% by mass of the obtained precursor polymer (a)
• the amount is preferably 0.001 to 10 parts by weight, more preferably 0.002 to 5 parts by weight, and even more preferably 0.05 to 3 parts by weight.
• alkylene oxide to be subjected to ring-opening addition polymerization examples include ethylene oxide, propylene oxide, butylene oxide, and tetramethylene oxide. Preferably, it contains propylene oxide.
• ring-opening addition polymerization is preferably carried out under a pressure of 0.1 to 15 MPa, more preferably carried out under a pressure of 0.2 to 10 MPa, and more preferably carried out under a pressure of 0.3 to 8 MPa. It is more preferable to do so.
• the polymerization temperature for ring-opening addition polymerization is not particularly limited, but is preferably 30 to 180°C, more preferably 70 to 160°C, and still more preferably 80 to 140°C.
• the polymerization temperature is 30° C. or higher, carbon dioxide polymerization and alkylene oxide ring-opening polymerization can be reliably started, and when it is 180° C. or lower, a decrease in the polymerization activity of the catalyst can be suppressed.
• the polymerization time for ring-opening addition polymerization is not particularly limited, but is preferably 2 to 18 hours, more preferably 2 to 16 hours. When the polymerization time is 2 hours or more, the reaction performance is excellent, and when it is 18 hours or less, it is economical.
• the amount of alkylene oxide charged is not particularly limited, but is preferably 40.0 to 99.0 parts by mass, more preferably 45.0 to 99.0 parts by mass, based on 100 parts by mass of the obtained precursor polymer (a). It is 98.0 parts by mass, more preferably 50.0 to 97.0 parts by mass.
• the amount of alkylene oxide charged is within the above range, the curable composition obtained has a low viscosity, the workability during coating work is improved, and the flexibility of the cured product tends to be better.
• the amount of carbon dioxide charged is not particularly limited, but is preferably 0.05 to 40 parts by mass, more preferably 0.10 to 35 parts by mass, based on 100 parts by mass of the obtained precursor polymer (a). parts, more preferably 1.15 to 30 parts by mass.
• the amount of carbon dioxide charged is within the above range, the tensile properties and shear strength of the cured product of the resulting curable composition are more likely to be improved.
• a known method can be used to react the precursor polymer (a) with the silylating agent.
• a method in which a precursor polymer (a) having an active hydrogen-containing group at the end is subjected to a urethanization reaction using a silylation agent having an isocyanate group; A method of introducing an isocyanate group into the active hydrogen-containing group of a), and then carrying out a urethanation reaction using a silylating agent having a functional group capable of reacting with the isocyanate group and a reactive silicon group represented by formula (1).
• Methodhod 2 Therefore, it is preferable that the polyether polycarbonate polymer (A) has a urethane bond. Moreover, it is preferable that the number of urethane bonds and the number of reactive silicon groups in one molecule of the polyether polycarbonate polymer (A) are the same.
• Examples of the silylating agent having an isocyanate group in Method 1 include isocyanate silane compounds described in JP-A No. 2011-178955. Specifically, 1-isocyanatemethyldimethoxymethylsilane, 1-isocyanatemethyldiethoxyethylsilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropylethyldiethoxysilane, 3-isocyanatepropylmethyldiethoxysilane, 3-isocyanatepropylmethyldiethoxysilane, Examples include isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, isocyanatemethyltrimethoxysilane, and isocyanatemethyltriethoxysilane.
• the silylating agents may be used alone or in combination of two or more. Among these, 1-isocyanatemethyldimethoxymethylsilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and isocyanatemethyltrimethoxysilane are preferred.
• the active hydrogen-containing group of the precursor polymer (a) that reacts with the silylation agent having an isocyanate group is also preferably a hydroxyl group derived from ethylene oxide from the viewpoint of good reactivity of the silylation reaction.
• the hydroxyl group of the precursor polymer (a) whose active hydrogen-containing group is a hydroxyl group is subjected to a urethanization reaction using a polyisocyanate compound to introduce an isocyanate group, and then the isocyanate group is introduced into the isocyanate group.
• a silylating agent having a reactive functional group and a reactive silicon group represented by formula (1) is reacted.
• three or more urethane bonds and a silylating agent residue reacted with an isocyanate group are introduced at the end of the precursor polymer (a).
• Examples of the polyisocyanate compound in method 2 include naphthalene-1,5-diisocyanate, polyphenylenepolymethylene polyisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate.
• Aromatic polyisocyanates such as xylylene diisocyanate and tetramethylxylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate and 2,4,4-trimethyl-hexamethylene diisocyanate; isophorone diisocyanate , 4,4'-methylenebis(cyclohexyl isocyanate); and urethane-modified products, biuret-modified products, allophanate-modified products, carbodiimide-modified products, and isocyanurate-modified products obtained from these.
• the polyisocyanate compounds may be used alone or in combination of two or more.
• tolylene diisocyanate is more preferred.
• the functional group capable of reacting with an isocyanate group of the silylating agent having a functional group capable of reacting with an isocyanate group and a reactive silicon group represented by formula (1) is, for example, a hydroxyl group, a carboxy group, a mercapto group.
• Examples include amino groups, amino groups, and amino groups in which one hydrogen atom is substituted with an alkyl group having 1 to 6 carbon atoms.
• groups having one or two active hydrogens are preferable, and hydroxyl groups, mercapto groups, amino groups, methylamino groups, ethylamino groups, and butylamino groups are preferable, and hydroxyl groups, amino groups, methylamino groups, and ethylamino groups are preferable. group, butylamino group is more preferable.
• the functional group capable of reacting with the isocyanate group is preferably bonded to the reactive silicon group represented by formula (1) via a divalent organic group having 1 to 20 carbon atoms.
• the organic group is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 10 carbon atoms, or 1 carbon atom substituted with an alkyl group having 1 to 4 carbon atoms.
• Aromatic hydrocarbon groups having ⁇ 10 carbon atoms, alicyclic hydrocarbon groups having 1 to 10 carbon atoms, and linear hydrocarbon groups having 1 to 12 carbon atoms are more preferable, and linear hydrocarbon groups having 1 to 8 carbon atoms.
• Hydrogen groups are more preferred, and linear hydrocarbon groups having 1 to 6 carbon atoms are particularly preferred.
• Method 1 the number of moles of reactive silicon groups introduced via a urethane bond per mole of hydroxyl groups in the precursor polymer (a), and in Method 2, the number of active hydrogen-containing groups in the precursor polymer (a).
• the number of moles of reactive silicon groups introduced via urethane bonds per mole is determined by the tensile properties and shear resistance due to appropriate crosslinking of the curable composition. From the viewpoint of improving strength, the content is preferably 70 to 100 mol%, more preferably 80 to 100 mol%.
• the silylation rate can be adjusted as appropriate depending on the amount of silylation agent used and the reaction conditions of the silylation reaction.
• the silylation rate can be measured by NMR analysis.
• a calculated value (theoretical value) based on the charged amount of the precursor polymer (a) and the silylation agent may be used as the value of the silylation rate.
• the amount of the silylating agent is 1 mol per mol of the group capable of introducing a reactive silicon group at the end of the precursor polymer (a), and the silylation rate is 100 mol%. In this case, there is one reactive silicon group per end group in the polyether polycarbonate polymer (A).
• the oxyalkylene polymer (B) has two or more terminal groups, at least a part of which is a reactive silicon group represented by formula (1), and does not have a unit based on carbon dioxide. It is a polymer. If the number of terminal groups per molecule of the oxyalkylene polymer (B) is less than 2, the tensile properties and shear strength of the cured product of the curable composition may decrease. From this point of view, the number of terminal groups per molecule of the oxyalkylene polymer (B) is preferably 2 to 6, more preferably 2 to 4.
• the reactive silicon group possessed by the oxyalkylene polymer (B) may be the same as or different from the reactive silicon group possessed by the polyether polycarbonate polymer (A).
• the oxyalkylene polymer (B) may be used alone or in combination of two or more.
• the oxyalkylene polymer (B) can be produced by a method in which a precursor polymer (b) having a terminal group into which a reactive silicon group can be introduced is reacted with a silylating agent.
• the terminal groups of the precursor polymer (b) are each independently preferably an unsaturated group or an active hydrogen-containing group.
• the active hydrogen-containing group is the same as the explanation given above for the polyether polycarbonate polymer (A).
• the precursor polymer (b) is preferably one obtained by addition polymerizing an alkylene oxide to an initiator having two or more active hydrogen-containing groups. That is, the oxyalkylene polymer (B) and the precursor polymer (b) contain units based on alkylene oxide. The oxyalkylene polymer (B) and the precursor polymer (b) do not have units based on carbon dioxide.
• the precursor polymer (b) is a precursor polymer (b'1) containing a polyoxyalkylene chain and having two or more active hydrogen-containing groups as terminal groups, or a precursor polymer (b'1) containing a polyoxyalkylene chain and having two or more active hydrogen-containing groups as terminal groups. A precursor polymer (b'2) having two or more saturated groups is preferred.
• the precursor polymer (b'1) can be produced by ring-opening addition polymerization of an alkylene oxide to an initiator having two or more active hydrogen-containing groups in the presence of a catalyst.
• the active hydrogen-containing group of the initiator is preferably a hydroxyl group.
• the initiator examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, polypropylene glycol having a molecular weight in terms of hydroxyl value of 50 to 8,000, Examples include glycerin, polyoxypropylene triol having a molecular weight of 50 to 8,000 in terms of hydroxyl value, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, 1,2,6-hexanetriol, diglycerin, and dipentaerythritol.
• the initiators may be used alone or in combination of two or more.
• alkylene oxide and catalyst used in the ring-opening addition polymerization examples include the alkylene oxide and catalyst described above in the explanation of the production of the precursor polymer (a).
• the alkylene oxide and catalyst used in the production of the precursor polymer (b'1) may be the same as or different from those used in the production of the precursor polymer (a).
• the precursor polymer (b'2) is produced by reacting a compound having a functional group and an unsaturated group capable of reacting with an active hydrogen-containing group with the precursor polymer (b'1) through an ester bond, a urethane bond, etc. It can be obtained by a method of introducing an unsaturated group.
• the terminal group of the precursor polymer (b'1) is a hydroxyl group
• the hydroxyl group is metal-oxidized to form an alcoholate, and then the hydroxyl group is converted into an alcoholate, and then converted to an unsaturated group-containing halogenated hydrocarbon such as allyl chloride, methallyl chloride, and propargyl bromide. It can be produced by a known reaction method.
• the hydroxyl group of the precursor polymer (b'1) is metal-oxidized to form an alcoholate, which is then reacted with an epoxy compound having an unsaturated group such as allyl glycidyl ether, and then reacted with an unsaturated group-containing halogenated hydrocarbon. It can also be manufactured by a known method.
• the method for obtaining an oxyalkylene polymer (B) by introducing a reactive silicon group into the terminal active hydrogen-containing group of the precursor polymer (b'1) is to introduce a reactive silicon group into the terminal active hydrogen-containing group of the precursor polymer (a).
• a method similar to that for introducing reactive silicon groups can be used.
• a method for obtaining the oxyalkylene polymer (B) by introducing a reactive silicon group into the terminal unsaturated group of the precursor polymer (b'2) for example, a precursor polymer having an unsaturated group at the terminal
• a method (method 3) in which (b'2) is reacted with a silylating agent that can undergo an addition reaction with an unsaturated group can be mentioned.
• the silylating agent capable of addition reaction to the unsaturated group includes, for example, a hydrosilane compound (for example, HSiX a R 3-a (X, R and a are the same as in formula (1)), Compounds having reactive silicon groups and mercapto groups are mentioned.
• a hydrosilane compound for example, HSiX a R 3-a (X, R and a are the same as in formula (1)
• Compounds having reactive silicon groups and mercapto groups are mentioned.
• the silylating agents may be used alone or in combination of two or more.
• trimethoxysilane, triethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane are preferred, and dimethoxymethylsilane or trimethoxysilane is more preferred since they have high reactivity and provide good curability.
• the oxyalkylene polymers (B) When the curable composition is cured, the oxyalkylene polymers (B) are crosslinked with each other, and a portion of the oxyalkylene polymer (B) reacts with the polyether polycarbonate polymer (A).
• the polyether polycarbonate polymer (A) has three or more terminal groups in one molecule, and at least a part of the terminal groups are reactive silicon groups, so the reactive silicon of the oxyalkylene polymer (B) When the number of groups is large, the proportion that can be uniformly cured with the polyether polycarbonate polymer (A) increases.
• the number of reactive silicon groups in the polyether polycarbonate polymer (A) is large and the number of reactive silicon groups in the oxyalkylene polymer (B) is small, the number of reactive silicon groups with the polyether polycarbonate polymer (A) will decrease. Differences occur, making it difficult for a uniform effect to develop within the system, resulting in a decrease in tensile properties and shear strength. Therefore, in order to improve the tensile properties and shear strength of the cured product of the curable composition and to prevent curing failure, it is necessary to It is important to balance the number of reactive silicon groups and the amount of the compound (B).
• the number of reactive silicon groups in the oxyalkylene polymer (B) increases, even if a large amount of the polyether polycarbonate polymer (A) is blended, the crosslinking reaction is less likely to be inhibited due to the quantitative ratio, and the polymer is less likely to become uncured. Therefore, the greater the number of reactive silicon groups in the oxyalkylene polymer (B), the better the curability of the curable composition. The tensile properties and shear strength of the cured product are further improved.
• the ratio of reactive silicon groups introduced to the unsaturated groups or active hydrogen-containing groups that are the terminal groups of the precursor polymer (b), that is, the silylation rate of the oxyalkylene polymer (B), is determined by the curable composition. From the viewpoint of good curability of the product, the content is preferably 50 to 100 mol%, more preferably 55 to 100 mol%, and even more preferably 60 to 100 mol%.
• the Mn of the oxyalkylene polymer (B) is preferably 10,000 to 50,000 from the viewpoint of improving the tensile properties and shear strength of the cured product of the curable composition, and making the curable composition easy to handle. , more preferably 12,000 to 40,000, still more preferably 14,000 to 30,000.
• Mw/Mn of the oxyalkylene polymer (B) is preferably 1.0 to 1 from the viewpoint of easy handling viscosity of the curable composition and improvement of tensile properties and shear strength of the cured product of the curable composition. .8, more preferably 1.0 to 1.7, even more preferably 1.0 to 1.5.
• the oxyalkylene polymer (B) has, for example, an unsaturated group, an active hydrogen-containing group, or an isocyanate group as a terminal group other than the reactive silicon group represented by formula (1). Examples and preferred embodiments of the unsaturated group and active hydrogen-containing group are as described above.
• the curable composition may contain components other than the polyether polycarbonate polymer (A) and the oxyalkylene polymer (B).
• Known additives may be used as other components depending on the use of the curable composition, such as curing catalysts, fillers, plasticizers, thixotropic agents, antioxidants, ultraviolet absorbers, Examples include light stabilizers, dehydrating agents, adhesion-imparting agents, amine compounds, oxygen-curable compounds, photo-curable compounds, epoxy compounds, acrylic compounds, and acrylic silicones. Each of these components may be used in combination of two or more.
• JP 2013/180203, WO 2014/192842, WO 2016/002907, JP 2014-88481, JP 2015-10162, JP 2015-105293, Known materials described in JP-A No. 2017-039728 and JP-A No. 2017-214541 can be used in appropriate combination.
• Other components may be blended within a range that does not impede the effects of the present invention.
• the total content of the polyether polycarbonate polymer (A) and the oxyalkylene polymer (B) in the curable composition is determined from the viewpoint of improving the tensile properties and shear strength of the cured product of the curable composition.
• the amount is preferably 10 to 60% by weight, more preferably 15 to 55% by weight, and even more preferably 20 to 50% by weight, based on 100% by weight of the substance.
• the curable composition preferably contains a curing catalyst to promote crosslinking through the formation of siloxane bonds based on reactive silicon groups.
• the content is a total of 100% of the polyether polycarbonate polymer (A) and the oxyalkylene polymer (B) from the viewpoint of obtaining a uniform cured product by promoting crosslinking appropriately.
• the amount is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, and even more preferably 0.5 to 2 parts by weight.
• the curable composition may be a one-component type in which all the ingredients are blended in advance, stored in a sealed container, and cured by moisture in the air after application.
• a two-component type may be used, in which the base composition containing (B) and the curing agent composition containing the curing catalyst are stored separately, and the curing agent composition and the base composition are mixed before use. From the viewpoint of ease of construction, a one-liquid type is preferable.
• the curable composition preferably does not contain water. It is preferable to dehydrate and dry the water-containing ingredients in advance, or to dehydrate them under reduced pressure or the like during mixing and kneading.
• the base composition is difficult to gel even if it contains a small amount of water, but from the viewpoint of good storage stability, it is preferable to dehydrate and dry the ingredients in advance. From the viewpoint of good storage stability, a dehydrating agent may be added to the one-component curable composition and the two-component base composition.
• the curable composition of the present invention can be cured at room temperature to obtain a cured product, and can be used for various purposes.
• sealants e.g., elastic sealants for construction, sealants for double-glazed glass, sealants for rust prevention and waterproofing of glass edges, sealants for the back of solar cells, sealants for buildings, ships
• electrical insulation materials insulating coating materials for electric wires and cables
• adhesives e.g., epoxy, epoxy, and potting materials.
• the area S1 of the signal ( ⁇ 1.34 ppm, 3H) attributed to the methyl group in the oxypropylene group whose both ends are bonded to the carbonate group, one end is bonded to the carbonate group and the other end is bonded to the oxypropylene group.
• Area S2 of the signal ( ⁇ 1.29ppm, 3H) attributed to the methyl group in the oxypropylene group, and the signal attributed to the methyl group in the oxypropylene group (formula weight 58) to which oxypropylene groups are bonded to both ends Based on the area S3 of ⁇ 1.14ppm, 3H) and the area S4 of the signal ( ⁇ 1.49ppm, 3H) attributed to the methyl group of the by-product propylene carbonate (formula weight 102), Proportion of CO2 -PO- CO2 chains (proportion of fully alternating copolymer), proportion of PO-PO- CO2 chains (proportion of random copolymer), proportion of PO-PO-PO chains (proportion of PPG) ), and the proportion of propylene carbonate were calculated.
• the formula weight of the oxypropylene group whose both ends are bonded to the carbonate group is 102
• the formula weight of the oxypropylene group whose one end is bonded to the carbonate group and the other end is bonded to the oxypropylene group is 102.
• the content of CO 2 units based on 100% by mass of the total of CO 2 units (formula weight 44) and units based on alkylene oxide in the polyol was calculated from the following formula.
• viscosity The viscosity of the precursor polymer (polyol) at 25° C. was measured using an E-type viscometer (VISCOMETER TV-22, manufactured by Toki Sangyo Co., Ltd.).
• Mn and Mw were measured by gel permeation chromatography (GPC) under the following measurement conditions (in terms of polystyrene), and the molecular weight distribution (Mw/Mn) was calculated from these values.
• silylation rate For Polymer B2, the ratio of the number of moles of reactive silicon groups added to 1 mole of allyl groups of the precursor polymer was determined by 1 H-NMR spectrum, and this was taken as the silylation rate.
• the silylation rates of polymers A1, A2, and B1 were defined as the ratio of the amount [mole] of 3-isocyanatepropylmethyldimethoxysilane charged to 1 mole of hydroxyl groups of the precursor polymer.
• ⁇ TBA-DMC catalyst Zinc hexacyanocobaltate complex with t-butyl alcohol as a ligand
• ⁇ U-860 Dioctyltin bis(isooctylthioglycolate); "Neostane (registered trademark) U-860", Nitto Kasei Manufactured by Shin-Etsu Chemical Co., Ltd.
• ⁇ KBM-803 3-Mercaptopropyltrimethoxysilane; "KBM-803", manufactured by Shin-Etsu Chemical Co., Ltd.
• the carbon dioxide pressure during synthesis was maintained at 1.5 MPa, 26.0 g of PO was added, and after confirming that heat was generated, the liquid temperature was lowered to 110 ° C., and further, 232 g of PO was added over 14 hours. .
• the liquid temperature was raised to 130°C and maintained under reduced pressure for 5 hours to remove propylene carbonate as a by-product.
• the reactants were taken out from the reactor and polyether polycarbonate polyol (precursor polymer a1; hydroxyl value 44.1 mgKOH/g, content of units based on carbon dioxide 12.3% by mass, viscosity at 25°C 6,000 mPa ⁇ s , 6 hydroxyl groups per molecule).
• the carbon dioxide pressure during synthesis was maintained at 1.5 MPa, 30.0 g of PO was added, and after confirming that heat was generated, the liquid temperature was lowered to 110 ° C., and then 270 g of PO was added over 16 hours. . After reacting at 110°C for 3 hours, the liquid temperature was raised to 130°C and maintained under reduced pressure for 5 hours to remove propylene carbonate as a by-product.
• the reactants were taken out from the reactor and polyether polycarbonate polyol (precursor polymer a2; hydroxyl value 28.9 mgKOH/g, content of units based on carbon dioxide 11.4% by mass, viscosity at 25°C 9,000 mPa ⁇ s , 3 hydroxyl groups per molecule).
• KBM-803 was added as a storage stabilizer to 100 parts by mass of precursor polymer a1
• a polyether polycarbonate polymer (polymer A1) in which a urethane bond and a dimethoxymethylsilyl group were introduced into the main chain was obtained.
• a curable composition for a sealant was manufactured using each polymer manufactured in the above synthesis example and various additives. The additives used are shown below.
• ⁇ Plasticizer DINP, diisononyl phthalate; "Vinicizer (registered trademark) 90", manufactured by Kao Corporation.
• ⁇ Filler-1 "White gloss CCR” (colloid calcium carbonate; product name of Shiraishi Calcium Co., Ltd.)
• ⁇ Filler-2 “Whiten (registered trademark) SB” (heavy calcium carbonate; manufactured by Shiroishi Calcium Co., Ltd.)
• Dehydrating agent “KBM-1003” (vinyltrimethoxysilane; Shin-Etsu Chemical Co., Ltd. product name)
• ⁇ Adhesive agent-1 “KBM-603” (3-(2-aminoethylamino)propyltrimethoxysilane; Shin-Etsu Chemical Co., Ltd.
• ⁇ Adhesive agent-2 “KBM-403” (3-glycidyloxypropyltrimethoxysilane; Shin-Etsu Chemical Co., Ltd. product name)
• ⁇ Stabilizer-1 “Irganox (registered trademark) 1010” (hindered phenol antioxidant; BASF product name)
• ⁇ Stabilizer-2 "HS Ester 765" (hindered amine ester; light stabilizer; manufactured by Toyokuni Oil Co., Ltd.)
• ⁇ Stabilizer-3 “Tinuvin (registered trademark) 326” (benzotriazole ultraviolet absorber; BASF product name)
• ⁇ Curing catalyst "Neostane (registered trademark) U-220H” (dibutyltin bis(acetylacetonate))
• Example 1 A mixture obtained by mixing 70 parts by mass of Polymer B2, 30 parts by mass of Polymer A1, 40 parts by mass of a plasticizer, and 3 parts by mass of a thixotropic agent and heating and swelling the mixture at 90°C, and Filler-1 75 Parts by mass and 75 parts by mass of Filler-2 were added and mixed by stirring using a planetary stirrer (manufactured by Kurabo Industries, Ltd.). The temperature of the obtained mixture was lowered to 25°C, and 3 parts by mass of dehydrating agent, 1 part by mass of tackifier-1, 1 part by mass of tackifier-2, 1 part by mass of stabilizer-1, and 1 part by mass of stabilizer-2 were added. , and 1 part by mass of stabilizer-3 were added and further stirred and mixed. Thereafter, 1 part by mass of a curing catalyst was added and mixed with stirring to produce a curable composition.
• a planetary stirrer manufactured by Kurabo Industries, Ltd.
• Example 1 a curable composition was produced in the same manner as in Example 1 except that the composition was changed to that shown in Table 3 below.
• the curable composition was filled into a mold with a thickness of 2 mm, and cured for 3 days in an atmosphere of a temperature of 23 °C and a relative humidity of 50%, and then for 4 days in an atmosphere of a temperature of 50 °C and a relative humidity of 65%. and cured.
• the obtained cured product was punched out to produce a dumbbell-shaped No. 3 test piece in accordance with JIS K 6251:2017.
• a tensile test was performed on each test piece using a Tensilon tester (temperature 23°C, tensile speed 500 mm/min), and the stress at 50% elongation (M50) [N/mm 2 ], maximum point cohesive force (Tmax) ) [N/mm 2 ] and maximum point elongation (Emax) [%] were measured.
• M50 50% elongation
• Tmax maximum point cohesive force
• Emax maximum point elongation

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