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
  • C08G65/32—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

Definitions

• the present invention relates to a polyoxyalkylene polymer having a hydrolyzable silyl group, a mixture thereof, and a curable composition containing the polymer or the mixture.
• Polymers with hydrolyzable silyl groups are known as moisture-reactive polymers, and are included in many industrial products such as adhesives, sealants, coating agents, paints, and pressure-sensitive adhesives, and are used in a wide range of fields. It's being used.
• Polyoxyalkylene-based polymers saturated hydrocarbon-based polymers, (meth)acrylic acid ester-based polymers and the like are known as the main chain skeleton of such polymers.
• a polyoxyalkylene polymer having a (for example, see Patent Document 1) has a relatively low viscosity at room temperature and is easy to handle, and the cured product obtained after the reaction exhibits good elasticity. Wide range.
• a polyoxyalkylene polymer having a hydrolyzable silyl group is required to exhibit good mechanical properties (for example, stress at elongation, stress at break, and resilience) after curing. Further, when the reactive diluent into which the above-mentioned hydrolyzable silyl group is introduced is blended with the polyoxyalkylene polymer having a hydrolyzable silyl group, a curable composition with low viscosity and easy handling is provided. can do. However, in the curable compositions hitherto reported, the mechanical properties after curing tended to deteriorate as the viscosity decreased.
• the first aspect of the present invention is a hydrolyzable silyl group-containing polyoxyalkylene polymer capable of forming a cured product exhibiting good mechanical properties, and a curable composition containing the same.
• a second aspect of the present invention is a mixture of a hydrolyzable silyl group-containing polyoxyalkylene polymer that can exhibit good mechanical properties after curing while having a low viscosity, and a curability containing the same
• the object is to provide a composition.
• a first aspect of the present invention is a polyoxyalkylene polymer having a hydrolyzable silyl group, wherein the hydrolyzable silyl group is represented by general formula (1): —SiR a X 3-a (1) (Wherein, R is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. X is the same or different and represents a hydroxyl group or a hydrolyzable group.
• the polyoxyalkylene polymer has a hydrolyzable silyl group or a molecular chain end containing a reactive group capable of introducing a hydrolyzable silyl group in one molecule and the average ratio of the number of the hydrolyzable silyl groups located at the molecular chain terminals to the number of the molecular chain terminals is 0.85 or more and 1.00 or less, and It relates to a polyoxyalkylene polymer, wherein the average ratio of the total number of hydrolyzable silyl groups to the number of molecular chain ends is 1.01 or more.
• the polyoxyalkylene polymer has a linear polymer backbone.
• the polyoxyalkylene polymer has a number average molecular weight of 9,000 or more.
• the polyoxyalkylene polymer has a structure represented by general formula (2) described later.
• the polyoxyalkylene polymer has two or more molecular chain ends in one molecule.
• a second aspect of the present invention is a mixture of polyoxyalkylene polymers (A) and (B) both having hydrolyzable silyl groups, wherein the polyoxyalkylene polymer (A) is Among the polyoxyalkylene-based polymers according to one aspect, the polyoxyalkylene-based polymer has two or more molecular chain ends in one molecule, and the polyoxyalkylene-based polymer (B) is hydrolyzable It has one molecular chain end containing a silyl group or a reactive group capable of introducing a hydrolyzable silyl group in one molecule, and the hydrolyzable silyl group possessed by the polyoxyalkylene polymer (B) is Represented by the general formula (1), the number average molecular weight of the polyoxyalkylene polymer (B) is smaller than the number average molecular weight of the polyoxyalkylene polymer (A), and the polyoxyalkylene polymer ( It relates to mixtures in which the mixing ratio of A):(B
• a in the general formula (1) represents 1.
• the polyoxyalkylene polymer (B) has a number average molecular weight of 10,000 or less.
• the polyoxyalkylene polymer (B) is the polyoxyalkylene polymer according to the first aspect.
• a second aspect of the present invention relates to a curable composition containing the polyoxyalkylene polymer according to the first aspect or the mixture, and also to a cured product of the curable composition. .
• a first aspect of the present invention provides a hydrolyzable silyl group-containing polyoxyalkylene polymer capable of forming a cured product exhibiting good mechanical properties, and a curable composition containing the same. be able to.
• a mixture of a hydrolyzable silyl group-containing polyoxyalkylene polymer that can exhibit good mechanical properties after curing while having a low viscosity, and a mixture containing the same A curable composition can be provided.
• the polyoxyalkylene-based polymer according to the present embodiment has a polyoxyalkylene polymer skeleton and a molecular chain terminal bonded to the polymer skeleton.
• the polymer backbone and the molecular chain end may be directly bonded, but are preferably indirectly bonded via an intermediate structure.
• the intermediate structure include a structure derived from an epoxy compound (G1) described later (that is, a structure in parentheses having n structures in formula (2) described later).
• the polymer backbone refers to a polymer main chain composed of oxyalkylene repeating units.
• the polymer backbone may be linear or branched.
• a linear polymer skeleton is preferable because the cured product of the curable composition has high elongation, and a branched polymer skeleton is preferable because the cured product of the curable composition has high strength.
• a linear polymer backbone can be formed by using an initiator having one or two hydroxyl groups per molecule in the polymerization process to form the polymer backbone, and a branched polymer The backbone can be formed by using initiators with 3 or more hydroxyl groups in one molecule.
• the polymer skeleton is a polymer skeleton composed only of a plurality of oxyalkylene repeating units linked to each other, or is derived from the initiator used during polymerization in addition to the plurality of oxyalkylene repeating units. It preferably contains a structure and is a polymer skeleton composed only of these.
• the oxyalkylene repeating unit refers to a repeating unit constituting a polyether, for example, an oxyalkylene unit having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.
• the polymer skeleton of polyoxyalkylene is not particularly limited, but examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxy A butylene copolymer etc. are mentioned. Polyoxypropylene is preferred. As the polymer skeleton, only one type may be used, or two or more types may be used in combination.
• molecular chain end refers to a site located at the end of a polyoxyalkylene polymer.
• the molecular chain end does not include a molecular chain end containing a hydrolyzable silyl group, a molecular chain end containing a reactive group capable of introducing a hydrolyzable silyl group, or a hydrolyzable silyl group and the reactive group. It is classified as a molecular chain end.
• the reactive group into which a hydrolyzable silyl group can be introduced refers to a reactive group that can be converted into a hydrolyzable silyl group through one-step or two-step or more reactions. Specific examples of the reactive group include, but are not limited to, hydroxyl groups and carbon-carbon unsaturated bonds (carbon-carbon double bonds or carbon-carbon triple bonds).
• the polyoxyalkylene polymer according to the present embodiment has one or more molecular chain ends containing a hydrolyzable silyl group or a reactive group capable of introducing a hydrolyzable silyl group in one molecule.
• a polyoxyalkylene polymer having two or more molecular chain ends is referred to as a multi-reactive terminal polymer (a)
• a polyoxyalkylene polymer having one molecular chain end is referred to as a single reaction. It is called a terminal polymer (b).
• the polymer with multiple reactive ends (a) has a linear polymer skeleton, there are two molecular chain ends, and both of the two molecular chain ends are hydrolyzable silyl groups, or It contains a reactive group capable of introducing a hydrolyzable silyl group.
• a polymer molecule having two molecular chain ends each containing a hydrolyzable silyl group (ii) one molecular chain end containing a hydrolyzable silyl group and a hydrolyzable silyl
• a polymer molecule having one molecular chain end containing a reactive group capable of introducing a group and (iii) a polymer molecule having two molecular chain ends each containing a reactive group capable of introducing a hydrolyzable silyl group. corresponds to the multi-reactive terminal polymer (a).
• Such a multi-reactive terminal polymer (a) can be obtained, for example, by one-step or two-step polymerization of introducing a hydrolyzable silyl group after polymerizing an epoxy compound in the presence of an initiator having two hydroxyl groups in one molecule. It can be produced by performing reactions in stages or more. If the introduction rate of the hydrolyzable silyl groups in the introduction reaction is 100%, then all of the molecular chain terminals in the polymer (a) will contain hydrolyzable silyl groups.
• the polymer (a) when the introduction rate is less than 100%, has a molecular chain end containing a hydrolyzable silyl group and a molecular chain end containing a reactive group capable of introducing a hydrolyzable silyl group. will coexist.
• the polymer having multiple reactive ends (a) has a branched polymer skeleton, there are three or more molecular chain ends, and at least two of them (preferably, all end of the molecular chain) contains a hydrolyzable silyl group or a reactive group capable of introducing a hydrolyzable silyl group.
• a multi-reactive terminal polymer (a) can be produced, for example, in one step or by introducing a hydrolyzable silyl group after polymerizing an epoxy compound in the presence of an initiator having 3 or more hydroxyl groups in one molecule. It can be produced by performing reactions in two or more stages.
• the multi-reactive terminal polymer (a) is preferably a polymer having a linear polymer backbone.
• a polymer having a branched polymer backbone may be used, or a polymer having a linear polymer backbone and a branched polymer A polymer having a combined skeleton may be used in combination.
• the single reactive end polymer (b) refers to a polymer having only one molecular chain end containing a hydrolyzable silyl group or a reactive group capable of introducing a hydrolyzable silyl group in one molecule. That is, when the single-reactive terminal polymer (b) has a linear polymer skeleton, (iv) one molecular chain terminal containing a hydrolyzable silyl group, a hydrolyzable silyl group and the reactive group (v) a molecular chain containing a reactive group capable of introducing a hydrolyzable silyl group A polymer molecule containing one terminal and one non-reactive molecular chain terminal corresponds to the single reactive terminal polymer (b).
• Such a homoreactive terminal polymer (b) is obtained by, for example, one step of introducing a hydrolyzable silyl group after polymerizing an epoxy compound in the presence of an initiator having only one hydroxyl group in one molecule, or It can be produced by performing reactions in two or more stages.
• the resulting polyoxyalkylene polymer contains a structure derived from the initiator at one molecular chain end.
• the resulting polyoxyalkylene polymer contains a butyl group at one molecular chain end. Structures derived from such initiators result in non-reactive chain ends that contain neither hydrolyzable silyl groups nor the aforementioned reactive groups.
• the polyoxyalkylene polymer according to the present embodiment is a polymer with a high introduction rate of hydrolyzable silyl groups to the ends of the molecular chains.
• the average ratio of the number of hydrolyzable silyl groups located at the molecular chain ends of the polyoxyalkylene polymer to the number of molecular chain ends of the polyoxyalkylene polymer (hereinafter referred to as "to the molecular chain end (also referred to as "the number of hydrolyzable silyl groups introduced”) is preferably 0.85 or more and 1.00 or less.
• Polyoxyalkylene polymers having a large number of hydrolyzable silyl groups introduced to the ends of the molecular chains have characteristics related to the total number of hydrolyzable silyl groups introduced, which will be described later. It can show mechanical properties.
• the number of hydrolyzable silyl groups to be introduced to the molecular chain end is the molecular chain end containing the hydrolyzable silyl group, which can be calculated by NMR measurement of the polyoxyalkylene polymer, and the hydrolyzable silyl group. It can be calculated from the ratio of the molecular chain ends containing the hydrolyzable silyl group to the total molecular chain ends containing the reactive groups that can be introduced.
• the number of hydrolyzable silyl groups introduced to the molecular chain terminal is calculated by [the number of hydrolyzable silyl groups located at the molecular chain terminal of the polyoxyalkylene polymer/the number of molecular chain terminals of the polyoxyalkylene polymer (However, the number of non-reactive molecular chain ends is excluded)], and the total number of molecular chain ends of the polyoxyalkylene polymer (however, the number of non-reactive molecular chain ends is It can also be rephrased as the average ratio of the number of molecular chain ends containing a hydrolyzable silyl group of the polyoxyalkylene polymer to the polyoxyalkylene polymer.
• the number of molecular chain ends of the polyoxyalkylene polymer is 2 when the polymer backbone is entirely linear, and is 3 or more when the polymer backbone is entirely branched. It can also average between 2 and 3 if the polymer backbone is a mixture of linear and branched.
• the term "hydrolyzable silyl group located at the molecular chain end of the polyoxyalkylene polymer” is a concept excluding the hydrolyzable silyl group contained in the intermediate structure described above.
• the number of hydrolyzable silyl groups introduced to the molecular chain end in the polyoxyalkylene polymer is 0.85 or more, but since the mixture according to the present embodiment can exhibit better mechanical properties after curing, the number of 0 0.88 or more is preferable, 0.90 or more is more preferable, 0.93 or more is still more preferable, and 0.95 or more is particularly preferable.
• the number of introduction is 1.00 or less, it is preferably 0.99 or less, more preferably 0.98 or less, because production is easy.
• the number of hydrolyzable silyl groups introduced to the molecular chain ends in the single reactive terminal polymer (b) is the number of hydrolyzable silyl groups or hydrolyzed silyl groups without considering the number of non-reactive molecular chain ends. It is the average ratio of the number of hydrolyzable silyl groups located at the molecular chain terminus to the number of molecular chain termini containing a reactive group capable of introducing a silyl group.
• the polyoxyalkylene polymer according to the present embodiment also has a hydrolyzable silyl group at a site other than the molecular chain terminal (specifically, an intermediate structure), and the polyoxyalkylene polymer has It is also a polymer with a high total number of hydrolyzable silyl groups.
• the average ratio of the total number of hydrolyzable silyl groups possessed by the polyoxyalkylene polymer to the number of molecular chain ends of the polyoxyalkylene polymer (hereinafter referred to as "total introduction of hydrolyzable silyl groups number”) is 1.01 or more.
• the polyoxyalkylene polymer having a large total number of hydrolyzable silyl groups introduced in this way also has the above-described characteristics related to the number of hydrolyzable silyl groups introduced to the ends of the molecular chains, so that after curing, it has a good It can show mechanical properties.
• the total number of introduced hydrolyzable silyl groups is calculated by the NMR measurement of the polyoxyalkylene polymer, and the molecular chain end containing the hydrolyzable silyl group and the reaction capable of introducing the hydrolyzable silyl group. It can be calculated from the ratio of the total of the hydrolyzable silyl groups to the total of the molecular chain ends containing groups.
• the total number of hydrolyzable silyl groups introduced is [total number of hydrolyzable silyl groups possessed by the polyoxyalkylene polymer/number of molecular chain ends of the polyoxyalkylene polymer (however, non-reactive molecules excluding the number of chain ends)], and the total number of molecular chain ends of the polyoxyalkylene polymer (excluding the number of non-reactive molecular chain ends), the polyoxyalkylene It can also be rephrased as the average ratio of the total number of hydrolyzable silyl groups possessed by the polymer.
• the total number of hydrolyzable silyl groups introduced in the polyoxyalkylene polymer according to the present embodiment is 1.01 or more, since the polyoxyalkylene polymer can exhibit better mechanical properties after curing, 1.20 or more is preferable, 1.30 or more is more preferable, 1.50 or more is still more preferable, and 1.60 or more is particularly preferable.
• the upper limit of the total number of introductions is not particularly limited, but is preferably 5.00 or less, more preferably 4.00 or less, even more preferably 3.00 or less, and particularly preferably 2.00 or less.
• the total number of hydrolyzable silyl groups introduced in the single reactive terminal polymer (b) is the number of hydrolyzable silyl groups or hydrolyzable silyl groups without considering the number of non-reactive molecular chain terminals. It is the average ratio of the total number of hydrolyzable silyl groups to the number of molecular chain ends containing reactive groups that can be introduced.
• the hydrolyzable silyl group possessed by the polyoxyalkylene polymer according to this embodiment is represented by the following general formula (1). —SiR a X 3-a (1)
• R is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
• the number of carbon atoms is preferably 1 to 10, more preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.
• the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogen groups such as chloro, alkoxy groups such as methoxy, and amino groups such as N,N-diethylamino. .
• R is, for example, unsubstituted alkyl such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-hexyl group, 2-ethylhexyl group, n-dodecyl group, etc.
• substituted alkyl group such as chloromethyl group, methoxymethyl group and N,N-diethylaminomethyl group
• unsaturated hydrocarbon group such as vinyl group, isopropenyl group and allyl group
• cycloalkyl group such as cyclohexyl group
• phenyl group aryl groups such as , toluyl group and 1-naphthyl group
• aralkyl groups such as benzyl group.
• Preferred are substituted or unsubstituted alkyl groups more preferred are methyl groups, ethyl groups, chloromethyl groups and methoxymethyl groups, still more preferred are methyl groups and methoxymethyl groups, and particularly preferred are methyl groups.
• R only one type of group may be used, or two or more types of groups may be used in combination.
• X is the same or different and represents a hydroxyl group or a hydrolyzable group.
• Examples of X include hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group and alkenyloxy group.
• the above alkoxy group and the like may have a substituent.
• An alkoxy group is preferred because it is moderately hydrolyzable and easy to handle, methoxy, ethoxy, n-propoxy and isopropoxy are more preferred, methoxy and ethoxy are still more preferred, and methoxy is particularly preferred.
• As X only one type of group may be used, or two or more types of groups may be used in combination.
• a in the general formula (1) is 0, 1 or 2.
• the value of a in the general formula (1) is preferably 1 because the mechanical properties of the resulting cured product are improved.
• hydrolyzable silyl groups represented by general formula (1) include trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, methyldimethoxysilyl group, methyl diethoxysilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylamino methyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group and the like.
• a methyldimethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, and (N,N-diethylaminomethyl)dimethoxysilyl group are preferred.
• trimethoxysilyl group, (chloromethyl)dimethoxysilyl group, and (methoxymethyl)dimethoxysilyl group are more preferable.
• a methyldimethoxysilyl group and a methyldiethoxysilyl group are more preferable.
• a methyldimethoxysilyl group is more preferable because it is easy to produce.
• the molecular chain end containing a hydrolyzable silyl group is indirectly bonded to the polymer skeleton via an intermediate structure containing a hydrolyzable silyl group, as described above. preferably.
• the molecular chain end containing a hydrolyzable silyl group and the intermediate structure containing a hydrolyzable silyl group possessed by the polyoxyalkylene polymer can be represented by, for example, the following general formula (2).
• the site represented by —R 1 —CH(R 2 )—CH 2 —SiR a X 3-a corresponds to the end of the molecular chain containing the hydrolyzable silyl group, and there are n
• the structure in parenthesis corresponds to the intermediate structure.
• the “hydrolyzable silyl group located at the end of the molecular chain” refers to the hydrolyzable silyl group contained in the site represented by —R 1 —CH(R 2 )—CH 2 —SiR a X 3-a .
• hydrolyzable silyl group contained in the intermediate structure is not located at the molecular chain terminal and does not correspond to the hydrolyzable silyl group located at the molecular chain terminal.
• the hydrolyzable silyl group located at the molecular chain terminal and the hydrolyzable silyl group contained in the intermediate structure may be the same or different.
• R 1 represents a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms.
• R 2 represents hydrogen or an alkyl group having 1 to 6 carbon atoms.
• R 3 represents a direct bond or a divalent linking group having 1 to 6 carbon atoms.
• R 4 represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.
• n is an integer from 1 to 10;
• the oxygen at the left end represents the oxygen in the oxyalkylene unit located at the end of the polymer backbone composed of a plurality of oxyalkylene units linked together.
• R, X and a are the same as described above for general formula (1) above.
• R 1 is preferably a hydrocarbon group having 1 to 3 carbon atoms, more preferably a hydrocarbon group having 1 to 2 carbon atoms.
• the hydrocarbon group is preferably an alkylene group, and a methylene group, ethylene group, propylene group, or butylene group can be used. Methylene groups are particularly preferred.
• R 2 is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.
• the alkyl group include hydrogen, methyl group, ethyl group, propyl group, butyl group and the like.
• R 2 is preferably an alkyl group having 1 to 4 carbon atoms, such as 1 to 3 carbon atoms, because it improves the number of hydrolyzable silyl groups introduced to the ends of the molecular chain and easily achieves 0.85 or more. is more preferred, a methyl group and an ethyl group are more preferred, and a methyl group is particularly preferred.
• R 2 hydrogen and an alkyl group having 1 to 4 carbon atoms may coexist.
• R 3 may be a divalent organic group having 1 to 6 carbon atoms.
• the organic group is preferably a hydrocarbon group or a hydrocarbon group containing an oxygen atom.
• the number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, even more preferably 1 to 2.
• -CH 2 OCH 2 -, -CH 2 O- and -CH 2 - are preferred, and -CH 2 OCH 2 - is more preferred.
• R 4 is preferably hydrogen or a hydrocarbon group having 1 to 5 carbon atoms, more preferably hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and even more preferably hydrogen or a hydrocarbon group having 1 to 2 carbon atoms. . Hydrogen and methyl groups are particularly preferred, and hydrogen is most preferred.
• the number average molecular weight of the polyoxyalkylene polymer according to the present embodiment is not particularly limited, but the number average molecular weight of the polyreactive terminal polymer (a) should be 9,000 or more in terms of polystyrene equivalent molecular weight in GPC. is preferred. Thereby, the mechanical properties of the obtained cured product can be improved. It is more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 25,000 or more. Although the upper limit of the number average molecular weight of the polymer with multiple reactive terminals (a) is not particularly limited, it is preferably 40,000 or less, more preferably 35,000 or less, and even more preferably 30,000 or less.
• the number average molecular weight can be determined in terms of polystyrene by GPC measurement.
• the number average molecular weight of the homoreactive terminal polymer (b) conforms to the number average molecular weight of the polyoxyalkylene polymer (B) described later.
• the molecular weight distribution (Mw/Mn) of the polyoxyalkylene polymer according to the present embodiment is not particularly limited, it is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, still more preferably 1.5 or less, and particularly preferably 1.4 or less. Moreover, from the viewpoint of improving various mechanical properties such as improving the durability and elongation of the cured product, it is preferably 1.2 or less.
• the molecular weight distribution (Mw/Mn) can be calculated from the number-average molecular weight and the weight-average molecular weight obtained in terms of polystyrene by GPC measurement.
• the polyreactive terminal polymer (a) or the singly reactive terminal polymer (b) can be synthesized separately, and the polyreactive terminal polymer (b) can be synthesized in one system.
• the terminal polymer (a) and the monoreactive terminal polymer (b) can be synthesized simultaneously.
• the polyoxyalkylene polymer according to the first aspect uses the reactivity of hydroxyl groups to introduce a carbon-carbon unsaturated bond into the hydroxyl-terminated polyoxyalkylene polymer (E), and then the carbon- It can be produced by reacting a hydrolyzable silyl group-containing compound having reactivity with a carbon unsaturated bond to introduce a hydrolyzable silyl group.
• a hydrolyzable silyl group-containing compound having reactivity with a carbon unsaturated bond to introduce a hydrolyzable silyl group.
• the polymer backbone of the polyoxyalkylene-based polymer can be formed by polymerizing an epoxy compound with an initiator having a hydroxyl group by a conventionally known method, whereby a hydroxyl-terminated polyoxyalkylene-based polymer (E) can be obtained. is obtained.
• a hydroxyl-terminated polyoxyalkylene-based polymer (E) can be obtained.
• Mw/Mn small molecular weight distribution
• a polymerization method using a double metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex is used. is preferred.
• the initiator having a hydroxyl group is not particularly limited, examples of the initiator having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1 ,4-butanediol, 1,6-hexanediol, low molecular weight polyoxypropylene diol, low molecular weight polyoxypropylene triol, glycerin, trimethylolpropane, triethylolethane, sorbitol, pentaerythritol and the like.
• monohydric alcohols can be used, for example, methanol, ethanol, 2-propanol, n-butanol, iso-butanol, 2-butanol, t-butanol, 2-ethyl hexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, oleyl alcohol and the like.
• low-molecular-weight polyoxypropylene monoalkyl ethers and the like are also included.
• the initiator having a hydroxyl group a mixture of an initiator having two or more hydroxyl groups in one molecule and an initiator having one hydroxyl group in one molecule is used, and an epoxy compound is produced in the presence of the mixture.
• a hydroxyl group-terminated polyoxyalkylene polymer (E) can be obtained as a mixture of two types of polymers.
• the resulting hydroxyl-terminated polyoxyalkylene polymer (E) is a polyoxyalkylene polymer having hydroxyl groups at both ends.
• a mixture of an alkylene polymer and a polyoxyalkylene polymer having a hydroxyl group at one end is obtained. Thereafter, by carrying out the step of introducing a carbon-carbon unsaturated bond and the step of introducing a hydrolyzable silyl group, which will be described later, in one system, the polyreactive terminal polymer (a) and the single reactive terminal polymer It becomes possible to synthesize mixtures of coalescence (b).
• the multi-reactive terminal polymer (a) can be synthesized, and if only an initiator having one hydroxyl group is used, for example, a homoreactive terminal polymer (b) can be synthesized.
• epoxy compound is not particularly limited, examples thereof include alkylene oxides such as ethylene oxide and propylene oxide. Propylene oxide is preferred.
• reaction with alkali metal salt In introducing a carbon-carbon unsaturated bond to the hydroxyl group-terminated polyoxyalkylene polymer (E), first, an alkali metal salt is allowed to act on the hydroxyl group-terminated polyoxyalkylene polymer (E) to obtain a terminal hydroxyl group. is preferably converted to a metaloxy group.
• a double metal cyanide complex catalyst can also be used instead of the alkali metal salt.
• the metaloxy group-terminated polyoxyalkylene-based polymer (F) is thus formed.
• the alkali metal salt is not particularly limited, examples thereof include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, cesium alkoxide and the like.
• Sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred from the viewpoint of ease of handling and solubility, and sodium methoxide and sodium tert. -butoxide is more preferred. From the standpoint of availability, sodium methoxide is particularly preferred, and from the standpoint of reactivity, sodium tert-butoxide is particularly preferred.
• the alkali metal salt may be dissolved in a solvent before being subjected to the reaction.
• the amount of the alkali metal salt to be used is not particularly limited. 7 or more is more preferable, and 0.8 or more is even more preferable.
• the molar ratio is preferably 1.2 or less, more preferably 1.1 or less.
• the alkali metal salt is used to convert the hydroxyl groups of the hydroxyl-terminated polyoxyalkylene polymer (E) into metaloxy groups. It is preferable to previously remove substances having hydroxyl groups other than the alkylene polymer from the reaction system. For removal, known methods may be used, such as heat evaporation, vacuum devolatilization, spray vaporization, thin film evaporation, azeotropic devolatilization, and the like.
• the temperature at which the alkali metal salt is allowed to act can be appropriately set by those skilled in the art, but is preferably 50°C or higher and 150°C or lower, more preferably 110°C or higher and 145°C or lower.
• the time for which the alkali metal salt is allowed to act is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.
• reaction with electrophile (G) The metaloxy group-terminated polyoxyalkylene polymer (F) obtained as described above is reacted with an electrophilic agent (G) having a carbon-carbon unsaturated bond to convert the metaloxy group to a carbon - can be converted into structures containing carbon unsaturation.
• an electrophilic agent (G) having a carbon-carbon unsaturated bond As the electrophile (G), it is preferable to first react an epoxy compound (G1) having a carbon-carbon double bond and then react an organic halide (G2) having a carbon-carbon double bond. .
• G1 an epoxy compound having a carbon-carbon double bond
• organic halide (G2) having a carbon-carbon double bond.
• the epoxy compound (G1) having a carbon-carbon double bond reacts with the metaloxy group through a ring-opening addition reaction of the epoxy group to form an ether bond, thereby forming a carbon-carbon double bond in the polyoxyalkylene polymer. Structures containing bonds and hydroxyl groups can be introduced.
• one or more epoxy compounds (G1) are added to one metaloxy group by adjusting the amount of the epoxy compound (G1) used for the metaloxy group and the reaction conditions. can be made.
• the hydrolyzable silyl group is introduced after adding the epoxy compound (G1), the structure derived from the epoxy compound (G1) becomes the above-described intermediate structure containing the hydrolyzable silyl group.
• the epoxy compound (G1) having a carbon-carbon double bond is, but not limited to, the following general formula (3):
• R 3 and R 4 are the same groups as R 3 and R 4 described above for general formula (2), respectively.
• epoxy compound (G1) having a carbon-carbon double bond examples include, but are not limited to, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide, 1,4-cyclopentadiene mono Epoxide is preferred from the viewpoint of reaction activity, and allyl glycidyl ether is particularly preferred.
• the amount of the epoxy compound (G1) having a carbon-carbon double bond to be added can be any amount in consideration of the introduction amount and reactivity of the carbon-carbon double bond to the polymer.
• the molar ratio of the epoxy compound (G1) to the hydroxyl groups of the polyoxyalkylene polymer (E) is preferably 0.2 or more, more preferably 0.5 or more.
• the molar ratio is preferably 5.0 or less, more preferably 2.0 or less.
• the reaction temperature for the ring-opening addition reaction of the epoxy compound (G1) having a carbon-carbon double bond to the metaloxy group-terminated polyoxyalkylene polymer (F) is 60° C. or higher and 150° C. or lower. is preferred, and 110° C. or higher and 140° C. or lower is more preferred.
• the epoxy compound (G1) having a carbon-carbon double bond is allowed to act on the metaloxy group-terminated polyoxyalkylene polymer (F), a new metaloxy group is generated due to the ring opening of the epoxy group. do. Therefore, after reacting the epoxy compound (G1), the organic halide (G2) having a carbon-carbon double bond can be reacted continuously.
• Organic halide (G2) having a carbon-carbon double bond reacts with the metaloxy group through a halogen substitution reaction to form an ether bond, thereby forming a carbon-carbon at the molecular chain end of the polyoxyalkylene polymer. Double bonds can be introduced.
• organic halide (G2) having a carbon-carbon double bond examples include, but are not limited to, vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, Examples include allyl iodide and methallyl iodide. Allyl chloride and methallyl chloride are preferred for ease of handling. Moreover, methallyl chloride, methallyl bromide, and methallyl iodide are preferable because the number of hydrolyzable silyl groups introduced to the ends of the molecular chains described above is improved.
• the addition amount of the organic halide (G2) having a carbon-carbon double bond is not particularly limited, but the molar ratio of the organic halide (G2) to the hydroxyl group of the polyoxyalkylene polymer (E) is 0. 0.7 or more is preferable, and 1.0 or more is more preferable. Moreover, the molar ratio is preferably 5.0 or less, more preferably 2.0 or less.
• the temperature at which the metaloxy group-terminated polyoxyalkylene polymer (F) is reacted with the organic halide (G2) having a carbon-carbon double bond is preferably 50° C. or higher and 150° C. or lower, and 110° C. 140° C. or less is more preferable.
• the reaction time is preferably 10 minutes to 5 hours, more preferably 30 minutes to 3 hours.
• the epoxy compound (G1) having a carbon-carbon double bond is reacted with the metaloxy group-terminated polyoxyalkylene polymer (F), and then the organic halide having a carbon-carbon double bond is obtained.
• the organic halide having a carbon-carbon double bond is obtained.
• the hydrolyzable silyl group described below is introduced into the polyoxyalkylene polymer (H), the structure represented by the general formula (2) can be formed.
• the structure in which a hydrolyzable silyl group is introduced from the epoxy compound (G1) corresponds to the intermediate structure described above, and the structure in which a hydrolyzable silyl group is introduced from the organic halide (G2) is the molecular chain. at the end.
• the structure derived from the epoxy compound (G1), that is, the hydrolyzable silyl group contained in the intermediate structure does not correspond to the hydrolyzable silyl group located at the end of the dispersed chain, as described above.
• the hydrolyzable silyl group contained in the structure derived from the organic halide (G2) corresponds to the hydrolyzable silyl group located at the end of the dispersed chain.
• reaction with the alkali metal salt and the reaction with the electrophilic agent (G) described above are repeated multiple times in order to increase the introduction rate of the carbon-carbon unsaturated bond to the polymer (H).
• the reactants (alkali metal salt or electrophile having a carbon-carbon unsaturated bond (G)) used in each step may be the same. , can be different.
• the polyoxyalkylene polymer (H) having a carbon-carbon unsaturated bond at each of the molecular chain ends and the intermediate structure thus obtained is subjected to a hydrosilylation reaction with a hydrosilane compound (I) having a hydrolyzable silyl group.
• a hydrolyzable silyl group can be introduced into the polymer.
• the structure represented by the general formula (2) is formed, and a polyoxyalkylene polymer having a hydrolyzable silyl group at each of the molecular chain terminal and the intermediate structure can be produced.
• the hydrosilylation reaction has the advantage that it can be easily carried out, the amount of hydrolyzable silyl groups to be introduced can be easily adjusted, and the physical properties of the obtained polymer are stable.
• hydrosilane compound (I) having a hydrolyzable silyl group examples include trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloro halosilanes such as methyl)chlorosilane, (methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, Ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysi
• alkoxysilanes alkoxysilanes; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; isopropenyloxysilanes (deacetone type) such as silane, (chloromethyl)diisopropenyloxysilane, (methoxymethyl)diisopropenyloxysilane, and the like;
• the amount of the hydrosilane compound (I) having a hydrolyzable silyl group used depends on the amount of carbon-carbon unsaturated bonds possessed by the polyoxyalkylene polymer (H) and the desired hydrolyzability to the end of the molecular chain. It may be appropriately set in consideration of the number of silyl groups to be introduced.
• the hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst in order to promote the reaction.
• a hydrosilylation catalyst metals such as cobalt, nickel, iridium, platinum, palladium, rhodium, ruthenium, and complexes thereof are known, and these can be used.
• platinum-phosphine complexes [eg Ph(PPh 3 ) 4 , Pt(PBu 3 ) 4 ]; platinum-phosphite complexes [eg Pt ⁇ P(OPh) 3 ⁇ 4 ]; be done.
• platinum catalysts such as chloroplatinic acid and platinum-vinylsiloxane complexes are preferred.
• the hydrosilylation reaction is preferably carried out in the presence of a quinone compound in addition to the hydrosilylation catalyst.
• the quinone compound can further improve promotion of the hydrosilylation reaction by the hydrosilylation catalyst.
• Specific examples of quinone compounds include 1,4-benzoquinone, 2-tert-butyl-1,4-benzoquinone, tetramethylbenzoquinone, 2,5-di-tert-butyl-1,4-benzoquinone, 2,6- di-tert-butyl-1,4-benzoquinone, 1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, 2-methoxy-1,4-naphthoquinone, 9,10-anthraquinone, 1-ethylanthraquinone, and 2-(1,2-dimethylpropyl)-9,10-anthraquinone and the like.
• the hydrosilylation reaction can be carried out without using a solvent, but for the purpose of uniformly dissolving the polyoxyalkylene polymer (H), hydrosilane compound (I), and hydrosilylation catalyst, In order to easily control the temperature of the system and add the hydrosilylation catalyst, an organic solvent may be added.
• the temperature conditions for the hydrosilylation reaction are not particularly limited and can be appropriately set by those skilled in the art. However, in order to reduce the viscosity of the reaction system and improve the reactivity, the reaction is preferably performed under heating conditions. , the reaction at 50°C to 150°C is more preferred, and the reaction at 70°C to 120°C is even more preferred.
• the reaction time may also be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that an unintended condensation reaction between polymers does not proceed. Specifically, the reaction time is preferably 30 minutes or more and 5 hours or less, more preferably 3 hours or less.
• the hydrosilylation reaction may be carried out in the presence of an orthocarboxylic acid trialkyl ester. This can suppress thickening during the hydrosilylation reaction and improve the storage stability of the resulting polymer.
• orthocarboxylic acid trialkyl esters examples include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, and triethyl orthoacetate. Preferred are trimethyl orthoformate and trimethyl orthoacetate.
• the amount thereof is not particularly limited, but it is preferably about 0.1 to 10 parts by weight, more preferably 0.1 to 3 parts by weight, relative to 100 parts by weight of the polyoxyalkylene polymer. degree is more preferred.
• the mixture according to this embodiment contains a polyoxyalkylene polymer (A) having a hydrolyzable silyl group and a polyoxyalkylene polymer (B) having a hydrolyzable silyl group.
• the mixture according to this embodiment refers to a mixture substantially containing only the polyoxyalkylene polymers (A) and (B). Since the polyoxyalkylene polymers (A) and (B) each have a hydrolyzable silyl group, the mixture exhibits curability based on hydrolysis and dehydration condensation reaction of the hydrolyzable silyl group.
• the hydrolyzable silyl group-containing polyoxyalkylene-based polymer (A) contained in the mixture according to the present embodiment among the polyoxyalkylene-based polymers according to the first aspect, the polyoxyalkylene-terminated polymer (a ) (that is, among the polyoxyalkylene-based polymers according to the first aspect, each molecule has two or more molecular chain ends containing a hydrolyzable silyl group or a reactive group capable of introducing a hydrolyzable silyl group polyoxyalkylene polymer) can be used.
• the hydrolyzable silyl group-containing polyoxyalkylene polymer (B) contained in the mixture according to the present embodiment has one molecular chain end containing a hydrolyzable silyl group or a reactive group capable of introducing a hydrolyzable silyl group. It is a polymer having one in the molecule.
• the polyoxyalkylene polymer (B) is a polymer generally known as a reactive diluent, and may be a conventionally known one, or the polyoxyalkylene polymer according to the first aspect. It may be one corresponding to the single-reactive terminal polymer (b) among the polymer.
• the polymer skeleton of the polyoxyalkylene polymer (B) may be linear or branched. is preferred.
• the linear polymer skeleton in the polyoxyalkylene polymer (B) can be formed by using an initiator having only one hydroxyl group in one molecule in the polymerization method for forming the polymer skeleton. .
• Details of the polymer backbone of the polyoxyalkylene polymer (B) and the initiator are described in the polymer backbone of the polyoxyalkylene polymer according to the first aspect and the production of the monoreactive terminal polymer (b). are the same as the details of the initiator used in .
• the polyoxyalkylene-based polymer (B) refers to a polymer having only one molecular chain end containing a hydrolyzable silyl group or a reactive group capable of introducing a hydrolyzable silyl group in one molecule. That is, when the polyoxyalkylene polymer (B) has a linear polymer skeleton, (iv) one molecular chain end containing a hydrolyzable silyl group and one non-reactive molecular chain end and (v) one molecular chain end containing a reactive group capable of introducing a hydrolyzable silyl group and one non-reactive molecular chain end. It corresponds to the polymer (B).
• the number of hydrolyzable silyl groups introduced to the molecular chain end in the polyoxyalkylene polymer (B) is not particularly limited, but from the viewpoint of the mechanical properties exhibited by the mixture according to the present embodiment, the polyoxyalkylene polymer
• the average ratio of the number of hydrolyzable silyl groups located at the molecular chain ends to the number of molecular chain ends containing a hydrolyzable silyl group or a reactive group capable of introducing a hydrolyzable silyl group possessed by (B) 0.30 or more and 1.00 or less.
• the lower limit is more preferably 0.50 or more, more preferably 0.60 or more, and particularly preferably 0.70 or more.
• the upper limit is more preferably 0.99 or less, even more preferably 0.98 or less.
• the number of hydrolyzable silyl groups introduced to the molecular chain ends in the polyoxyalkylene polymer (B) is the number of hydrolyzable silyl groups or hydrolyzed silyl groups without considering the number of non-reactive molecular chain ends. It is the average ratio of the number of hydrolyzable silyl groups located at the molecular chain terminus to the number of molecular chain termini containing a reactive group capable of introducing a silyl group.
• the hydrolyzable silyl group possessed by the polyoxyalkylene polymer (B) can be represented by the general formula (1).
• the hydrolyzable silyl group possessed by the polyoxyalkylene polymer (A) and the hydrolyzable silyl group possessed by the polyoxyalkylene polymer (B) may be the same or different. good.
• a in the general formula (1) is preferably 1 because the resulting cured product has improved mechanical properties.
• the hydrolyzable silyl group possessed by the polyoxyalkylene polymer (B) includes, for example, a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, and a methyldimethoxysilyl group.
• methyldiethoxysilyl group dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N, N -diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group and the like.
• a methyldimethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, and (N,N-diethylaminomethyl)dimethoxysilyl group are preferred.
• trimethoxysilyl group, (chloromethyl)dimethoxysilyl group, and (methoxymethyl)dimethoxysilyl group are more preferable.
• a methyldimethoxysilyl group and a methyldiethoxysilyl group are more preferable.
• a methyldimethoxysilyl group is more preferable because it is easy to produce.
• the number average molecular weight of the polyoxyalkylene polymer (B) is smaller than the number average molecular weight of the polyoxyalkylene polymer (A) in order to reduce the viscosity of the mixture according to the second aspect.
• the polystyrene equivalent molecular weight in GPC is preferably 10,000 or less, more preferably 8,500 or less. In order to further reduce the viscosity of the mixture, the number average molecular weight is preferably 7,000 or less.
• the lower limit of the number average molecular weight of component (B) is not particularly limited, it may be, for example, 1,000 or more, preferably 1,200 or more, and more preferably 1,500 or more.
• the number average molecular weight can be determined in terms of polystyrene by GPC measurement.
• the molecular weight distribution (Mw/Mn) of the polyoxyalkylene polymer (B) is not particularly limited, it is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, still more preferably 1.5 or less, and particularly preferably 1.4 or less. Moreover, from the viewpoint of improving various mechanical properties such as improving the durability and elongation of the cured product, it is preferably 1.2 or less.
• the molecular weight distribution (Mw/Mn) can be calculated from the number-average molecular weight and the weight-average molecular weight obtained in terms of polystyrene by GPC measurement.
• the weight ratio of the polyoxyalkylene polymer (A):(B) in the mixture according to the present embodiment is preferably 95:5 to 30:70.
• the ratio is more preferably 90:10 to 40:60, even more preferably 80:20 to 50:50.
• the mixture according to the present embodiment has a low viscosity, specifically, a viscosity of 30 Pa.s measured at 23°C. It is preferred to indicate less than s. More preferably, 25 Pa.s. s or less, more preferably 20 Pa.s or less. s or less.
• the viscosity is measured at 23° C. with an E-type viscometer (RE-85U manufactured by Tokyo Keiki, measurement cone: 3° ⁇ R14).
• the polyoxyalkylene polymer (B) can be synthesized alone, or as described above, can be synthesized simultaneously with the polyoxyalkylene polymer (A) in one system.
• the polyoxyalkylene polymer (B) is the polyoxyalkylene polymer according to the first aspect. , which corresponds to the monoreactive terminal polymer (b).
• a case of synthesizing only the polyoxyalkylene polymer (B) will be described below.
• the polyoxyalkylene polymer (B) utilizes the reactivity of the hydroxyl group to introduce a carbon-carbon unsaturated bond into the hydroxyl-terminated polyoxyalkylene polymer (E), and then the carbon-carbon unsaturated bond. It can be produced by reacting a hydrolyzable silyl group-containing compound having reactivity with a bond to introduce a hydrolyzable silyl group.
• a hydrolyzable silyl group-containing compound having reactivity with a bond to introduce a hydrolyzable silyl group.
• the polymer skeleton of the polyoxyalkylene-based polymer (B) can be formed by polymerizing an epoxy compound with an initiator having a hydroxyl group by a conventionally known method.
• a polymer (E) is obtained.
• the details are as described in detail for the polyoxyalkylene polymer according to the first aspect, but an initiator having one hydroxyl group may be used as the initiator.
• the terminal hydroxyl group into a metaloxy group by reacting an alkali metal salt on the hydroxyl group-terminated polyoxyalkylene polymer (E).
• a double metal cyanide complex catalyst can also be used instead of the alkali metal salt.
• the metaloxy group-terminated polyoxyalkylene-based polymer (F) is thus formed. Details of the reaction are as described in detail for the polyoxyalkylene polymer according to the first aspect.
• reaction with electrophile (G) The metaloxy group-terminated polyoxyalkylene polymer (F) obtained as described above is reacted with an electrophilic agent (G) having a carbon-carbon unsaturated bond to convert the metaloxy group to a carbon - can be converted into structures containing carbon unsaturation. As a result, a polyoxyalkylene polymer (H) having a carbon-carbon unsaturated bond at the molecular chain end can be formed.
• the electrophilic agent (G) having a carbon-carbon unsaturated bond reacts with the metaloxy group possessed by the polyoxyalkylene polymer (F) to add a carbon-carbon unsaturated bond to the polyoxyalkylene polymer.
• G1 an epoxy compound having a carbon-carbon double bond
• G2 organic halide
• G3 an organic compound having a carbon-carbon triple bond Halides
• Organic halide (G3) having a carbon-carbon triple bond reacts with the metaloxy group through a halogen substitution reaction to form an ether bond, resulting in a carbon-carbon triple bond at the molecular chain end of the polyoxyalkylene polymer. Coupling can be introduced.
• Organic halides (G3) having a carbon-carbon triple bond include, but are not limited to, the following general formula (5): ZR 5 -C ⁇ CR 6 (5) can be expressed as In the formula, R 5 represents a direct bond or a divalent hydrocarbon group having 1 to 4 carbon atoms. Specific examples of R 5 include the same groups as R 1 described above for general formula (2).
• R 6 represents hydrogen or an alkyl group having 1 to 10 carbon atoms, preferably hydrogen or an alkyl group having 1 to 8 carbon atoms.
• alkyl group include methyl group, ethyl group, propyl group, butyl group and the like. Hydrogen is particularly preferred as R6 .
• Z represents a halogen atom.
• organic halides (G3) having a carbon-carbon triple bond include, but are not limited to, propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne.
• the addition amount of the organic halide (G3) having a carbon-carbon triple bond is not particularly limited. 7 or more is preferable, and 1.0 or more is more preferable. Moreover, the molar ratio is preferably 5.0 or less, more preferably 2.0 or less.
• the temperature at which the organic halide (G3) having a carbon-carbon triple bond is reacted with the metaloxy group-terminated polyoxyalkylene polymer (F) is preferably 50° C. or higher and 150° C. or lower, and 50° C. or higher. 80° C. or lower is more preferable.
• the reaction time is preferably 10 minutes to 5 hours, more preferably 30 minutes to 3 hours.
• both the organic halide having a carbon-carbon double bond (G2) and the organic halide having a carbon-carbon triple bond (G3) are reacted with the metaloxy group-terminated polyoxyalkylene polymer (F). You can let me. In that case, the organic halide (G2) having a carbon-carbon double bond or the organic halide (G3) having a carbon-carbon triple bond may be reacted simultaneously or sequentially. In the case of sequential reaction, the order may be irrelevant, and any one may be reacted first. As a result, a polyoxyalkylene polymer (H) having both carbon-carbon double bonds and carbon-carbon triple bonds at the molecular chain ends can be synthesized.
• a compound having a hydrolyzable silyl group and an isocyanate group in one molecule (J ) to form a urethane bond and introduce a hydrolyzable silyl group.
• a polyoxyalkylene polymer (B) having a hydrolyzable silyl group can also be produced by this method.
• an isocyanate group capable of a urethanization reaction with the hydroxyl group of the polyoxyalkylene polymer (E) and a hydrolyzable silyl group in one molecule examples include (3-isocyanatopropyl)trimethoxysilane, (3-isocyanatopropyl)dimethoxymethylsilane, and (3-isocyanatopropyl)triethoxysilane.
• the polyoxyalkylene polymer (H) having a carbon-carbon unsaturated bond at the molecular chain end of the polyoxyalkylene polymer (H) has a carbon-carbon
• a polyoxyalkylene polymer having a double bond is reacted with a compound (K) having a hydrolyzable silyl group and a mercaptan group in one molecule to form a sulfide by addition of the mercaptan group to the carbon-carbon double bond.
• a method of forming a bond to introduce a hydrolyzable silyl group can also be applied.
• a polyoxyalkylene polymer (B) having a hydrolyzable silyl group can also be produced by this method.
• the compound (K) having a hydrolyzable silyl group and a mercaptan group in one molecule includes a mercaptan group capable of addition reaction to the carbon-carbon double bond of the polyoxyalkylene polymer (H), It is not particularly limited as long as it is a compound having both a decomposable silyl group in one molecule, but specific examples include (3-mercaptopropyl)methyldimethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl ) methyldiethoxysilane, (3-mercaptopropyl)triethoxysilane, (mercaptomethyl)methyldimethoxysilane, (mercaptomethyl)trimethoxysilane, (mercaptomethyl)methyldiethoxysilane, (mercaptomethyl)triethoxysilane, etc. mentioned.
• ⁇ Curable composition> it is possible to provide a curable composition containing the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect.
• the curable composition according to the present embodiment preferably contains a silanol condensation catalyst for the purpose of promoting the reaction of hydrolyzing and condensing the hydrolyzable silyl groups possessed by the polyoxyalkylene polymer, that is, the curing reaction. .
• silanol condensation catalyst conventionally known ones can be used. Specifically, organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, etc. can be used.
• organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dibutyltin oxide and silicate compounds.
• dioctyltin diacetate dioctyltin dilaurate
• dioctyltin bis(ethyl maleate) dioctyltin bis(octyl maleate)
• dioctyltin bis(acetylacetonate) phosphate dioctyltin oxide and a silicate compound, and the like.
• Dioctyltin compounds are preferred due to recent heightened environmental concerns.
• carboxylate metal salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and cesium carboxylate.
• carboxylic acid group the following carboxylic acid and various metals can be combined.
• amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine; pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1, Nitrogen-containing heterocyclic compounds such as 5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine and diphenylguanidine; biguanides such as phenyl biguanide; amino group-containing silane coupling agents; ketimine compounds;
• carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.
• alkoxy metals include titanium compounds such as tetrabutyl titanate titanium tetrakis (acetylacetonate), diisopropoxytitanium bis (ethylacetoacetate), aluminum tris (acetylacetonate), and diisopropoxyaluminum ethylacetoacetate. and zirconium compounds such as zirconium tetrakis (acetylacetonate).
• fluorine anion-containing compounds As other silanol condensation catalysts, fluorine anion-containing compounds, photoacid generators, and photobase generators can also be used.
• the silanol condensation catalyst may be used in combination of two or more different catalysts.
• the combination of the amine compound and carboxylic acid or the amine compound and alkoxy metal may improve reactivity. have a nature.
• the amount of the silanol condensation catalyst is, from the viewpoint of improving the condensation reaction rate and workability at the time of curing, 100 parts by weight of the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect. On the other hand, 0.001 to 20 parts by weight is preferable, 0.01 to 15 parts by weight is more preferable, and 0.01 to 10 parts by weight is particularly preferable. Furthermore, some silanol condensation catalysts may ooze out or contaminate the surface of the cured product after the curable composition is cured. In such a case, by setting the amount of the silanol condensation catalyst to 0.01 to 3.0 parts by weight, it is possible to maintain good surface conditions of the cured product while ensuring curability.
• the curable composition according to the present embodiment preferably further contains a (meth)acrylate polymer (D) having a hydrolyzable silyl group. Further containing the (meth)acrylate polymer (D) tends to improve the weather resistance of the cured product.
• the position of the hydrolyzable silyl group in the (meth)acrylic acid ester polymer (D) may be at the end of the main chain of the polymer or in the middle of the main chain.
• the (meth)acrylic acid ester monomer constituting the main chain of the (meth)acrylic acid ester polymer (D) is not particularly limited, and various types can be used. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate.
• tert-butyl (meth)acrylate n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-(meth)acrylate -octyl, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, (meth)acrylate Benzyl acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate , glycidyl (meth)acrylate, (3
• Examples of monomer units other than the above include acrylic acid such as acrylic acid and methacrylic acid; amide groups such as N-methylol acrylamide and N-methylol methacrylamide; epoxy groups such as glycidyl acrylate and glycidyl methacrylate; , diethylaminoethyl methacrylate, and the like.
• the (meth)acrylate polymer (D) a polymer obtained by copolymerizing a (meth)acrylate monomer and a vinyl monomer copolymerizable therewith can also be used.
• the vinyl-based monomer is not particularly limited, and examples thereof include styrene-based monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; perfluoroethylene, perfluoropropylene, vinylidene fluoride, and the like.
• Fluorine-containing vinyl monomers Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; Maleic anhydride, maleic acid, maleic acid monoalkyl esters and dialkyl esters; Fumaric acid, fumaric acid monoalkyl esters and dialkyl esters; maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile groups such as acrylonitrile and methacrylonitrile Containing vinyl-based monomers; amide group-containing vinyl-based monomers such as acrylamide and methacrylamide; vinyl ester-based monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl
• the average number of hydrolyzable silyl groups in the (meth)acrylic acid ester polymer (D) is preferably 0.3 to 5.0 per molecule, and the mechanical properties of the curable composition during curing From the viewpoint of , 0.5 or more is more preferable, and from the viewpoint of the stability of the (meth)acrylic acid ester polymer (D), 3.0 or less is more preferable.
• the method of introducing a hydrolyzable silyl group into the (meth)acrylic acid ester polymer is not particularly limited, and for example, the following method can be used.
• (vi) A method of copolymerizing a compound having a polymerizable unsaturated group and a hydrolyzable silyl group together with the aforementioned monomers. Using this method, hydrolyzable silyl groups tend to be randomly introduced into the backbone of the polymer.
• (vii) A method of polymerizing a (meth)acrylate polymer using a mercaptosilane compound having a hydrolyzable silyl group as a chain transfer agent. Using this method, a hydrolyzable silyl group can be introduced at the polymer terminal.
• a method of reacting an aminosilane compound having a silyl group can be exemplified.
• a method of modifying a terminal functional group of a (meth)acrylic acid ester-based polymer synthesized by a living radical polymerization method to introduce a hydrolyzable silyl group A (meth)acrylic acid ester-based polymer obtained by a living radical polymerization method can easily introduce a functional group at the polymer terminal, and by modifying this, a hydrolyzable silyl group can be introduced at the polymer terminal.
• Examples of silicon compounds that can be used to introduce hydrolyzable silyl groups into the (meth)acrylic acid ester polymer using the above method include the following compounds.
• Compounds having a polymerizable unsaturated group and a hydrolyzable silyl group used in method (vi) include 3-(trimethoxysilyl)propyl (meth)acrylate and 3-(dimethoxymethylsilyl)acrylate (meth)acrylate.
• Mercaptosilane compounds having a hydrolyzable silyl group used in method (vii) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, mercaptomethyltriethoxysilane and the like.
• Compounds having a functional group reactive with the hydrolyzable silyl group and the V group used in method (viii) include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltriethoxysilane, isocyanatosilane compounds such as isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, isocyanatomethyldimethoxymethylsilane, isocyanatomethyldiethoxymethylsilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, Epoxysilane compounds such as 3-glycidoxypropyldimethoxymethylsilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyldimethoxymethylsilane, gly
• any modification reaction can be used.
• a method of introducing a double bond to the end of a polymer using a compound having a functional group capable of reacting with a functional group and a double bond and then introducing a hydrolyzable silyl group thereon by hydrosilylation or the like can be used.
• hydrolyzable silyl group possessed by the (meth)acrylic acid ester polymer (D) examples include the same hydrolyzable silyl groups possessed by the polyoxyalkylene polymer (A) and/or (B). be done. Among them, a methyldimethoxysilyl group, a methyldiethoxysilyl group, a trimethoxysilyl group and a triethoxysilyl group are preferable.
• a methyldimethoxysilyl group is more preferable, and the curability of the composition and its A trimethoxysilyl group is more preferable because it can improve the restorability of the cured product.
• the monomer composition of the (meth)acrylic acid ester polymer (D) is generally selected according to the application and purpose among those skilled in the art.
• the glass transition temperature (Tg) is relatively low, preferably -100°C or higher and 100°C or lower, more preferably -60°C or higher and 0°C or lower.
• the number average molecular weight of the (meth)acrylic acid ester polymer (D) is not particularly limited, but the polystyrene equivalent molecular weight by GPC measurement is preferably 500 to 100,000, more preferably 1,000 to 50,000, and 2 ,000 to 30,000 are particularly preferred.
• a method of blending a polyoxyalkylene polymer and a (meth)acrylic acid ester polymer is disclosed in JP-A-59-122541, JP-A-63-112642, JP-A-6-172631, and JP-A-11-116763. No. 5, 2003, etc.
• a method of polymerizing a (meth)acrylic acid ester-based monomer in the presence of a polyoxypropylene-based polymer having a hydrolyzable silyl group can be used.
• This production method is specifically disclosed in each publication such as JP-A-59-78223, JP-A-60-228516 and JP-A-60-228517.
• the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect and the (meth)acrylic acid ester polymer (D) can be blended by a similar method, but are not limited thereto. .
• the ratio of the polyoxyalkylene polymer according to the first aspect of the present embodiment or the mixture according to the second aspect: the (meth)acrylic acid ester polymer (D) is not particularly limited, but the weight ratio is 95:5 to 10:90 is preferred, 90:10 to 20:80 is more preferred, and 80:20 to 40:60 is particularly preferred.
• the polyoxyalkylene-based polymer according to the first aspect or the mixture and the (meth)acrylic acid ester-based polymer (D) according to the second aspect may each be used alone, or two or more kinds may be used. may be used together.
• the curable composition according to the present embodiment contains other additives such as a silicon compound, an adhesion imparting agent, a plasticizer, a solvent, a diluent, a silicate, a filler, an anti-sagging agent, an antioxidant, and a light stabilizer. , UV absorbers, physical property modifiers, tackifier resins, compounds containing epoxy groups, photo-curing substances, oxygen-curing substances, surface property modifiers, epoxy resins, other resins, flame retardants, foaming agents. can be In addition, various additives may be added to the curable composition according to the present embodiment as necessary for the purpose of adjusting various physical properties of the curable composition or cured product. Examples of such additives include curability modifiers, radical inhibitors, metal deactivators, antiozonants, phosphorus peroxide decomposers, lubricants, pigments, antifungal agents, and the like. be done.
• additives such as a silicon compound, an adhesion imparting agent, a plasticizer, a solvent
• Fillers include ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, active zinc white, PVC powder, PMMA powder, glass fiber and filament, and the like.
• the above fillers may be used alone or in combination of two or more.
• the amount of filler used is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, with respect to 100 parts by weight of the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect. .
• Organic balloons and inorganic balloons may be added for the purpose of weight reduction (lower specific gravity) of the composition.
• the balloon is hollow inside with a spherical filler, and is made of inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran. materials. Only one kind of balloon may be used, or a mixture of two or more kinds may be used.
• the amount of the balloon used is preferably 0.1 to 100 parts by weight, more preferably 1 to 20 parts by weight, with respect to 100 parts by weight of the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect. preferable.
• the curable composition according to the present embodiment may contain an adhesion imparting agent.
• a silane coupling agent or a reactant of the silane coupling agent can be added as the adhesion imparting agent.
• silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ - Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane; ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane; isocyanate group-containing silanes such as ethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatomethyltrimethoxysilane, ⁇ -isocyan
• the amount of adhesion-imparting agent used is preferably 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight is more preferred.
• plasticizer can be added to the curable composition according to the present embodiment.
• plasticizers include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), phthalate compounds such as butylbenzyl phthalate; bis(2-ethylhexyl )-terephthalate compounds such as 1,4-benzenedicarboxylate; non-phthalate compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, Aliphatic polyvalent carboxylic acid ester compounds such as tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl ole
• polymer plasticizer can be used.
• polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more; polyethers such as derivatives converted to polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like.
• the amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, with respect to 100 parts by weight of the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect. , 20 to 100 parts by weight is more preferable.
• a plasticizer may be used individually and may use 2 or more types together.
• Solvents and diluents that can be used include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers.
• the boiling point of the solvent is preferably 150°C or higher, more preferably 200°C or higher, and even more preferably 250°C or higher, because of the problem of air pollution when the composition is used indoors. .
• the above solvents or diluents may be used alone or in combination of two or more.
• the curable composition according to the present embodiment may optionally contain an anti-sagging agent to prevent sagging and improve workability.
• the anti-sagging agent is not particularly limited, but examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.
• the amount of anti-sagging agent used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect.
• the curable composition according to the present embodiment may contain an antioxidant (antiaging agent).
• an antioxidant can enhance the weather resistance of the cured product.
• antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.
• the amount of antioxidant used is preferably 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, with respect to 100 parts by weight of the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect. Parts by weight are more preferred.
• a light stabilizer can be added to the curable composition according to the present embodiment.
• the use of a light stabilizer can prevent photo-oxidative deterioration of the cured product.
• Benzotriazole-based, hindered amine-based, and benzoate-based compounds can be exemplified as light stabilizers, and hindered amine-based compounds are particularly preferred.
• the amount of light stabilizer used is preferably 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, with respect to 100 parts by weight of the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect. Parts by weight are more preferred.
• the curable composition according to this embodiment may contain an ultraviolet absorber.
• the use of an ultraviolet absorber can enhance the surface weather resistance of the cured product.
• UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferred.
• Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (manufactured by BASF).
• the amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, with respect to 100 parts by weight of the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect. Parts by weight are more preferred.
• a physical property modifier for adjusting the tensile properties of the resulting cured product may be added to the curable composition according to the present embodiment, if necessary.
• the physical property modifier is not particularly limited, for example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane.
• arylalkoxysilanes such as; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, ⁇ -glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as silyl)borate; silicone varnishes; polysiloxanes;
• the physical property modifier By using the physical property modifier, the hardness of the cured composition can be increased, or conversely, the hardness can be decreased and elongation at break can be obtained. For example, by adding diphenyldimethoxysilane, it is possible to maintain the restorability while lowering the hardness when the composition is cured.
• the physical property modifiers may be used alone or in combination of two or more.
• a compound that produces a compound having a monovalent silanol group in the molecule by hydrolysis has the effect of lowering the modulus of the cured product without worsening the surface stickiness of the cured product.
• Compounds that generate trimethylsilanol are particularly preferred.
• Examples of compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis include alcohol derivatives such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, which are hydrolyzed to produce silane monovalent groups. Mention may be made of silicon compounds that produce ols.
• the amount of the physical property modifier used is preferably 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, with respect to 100 parts by weight of the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect. Parts by weight are more preferred.
• a tackifying resin can be added to the curable composition according to the present embodiment for the purpose of enhancing the adhesiveness or adhesion to a substrate, or for other purposes.
• the tackifying resin there is no particular limitation, and those commonly used can be used.
• terpene-based resins aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenolic resins, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin-based Resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and hydrogenated products thereof, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, and the like. These may be used alone or in combination of two or more.
• petroleum resins e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C
• the amount of the tackifying resin used is preferably 2 to 100 parts by weight, preferably 5 to 50 parts by weight, with respect to 100 parts by weight of the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect. is more preferred, and 5 to 30 parts by weight is even more preferred.
• a compound containing an epoxy group can be blended in the curable composition according to the present embodiment.
• the use of a compound having an epoxy group can enhance the restorability of the cured product.
• Examples of compounds having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof.
• epoxidized soybean oil epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxyoctyl stearate , epoxy butyl stearate and the like.
• the epoxy compound is preferably used in a range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect.
• a photocurable substance can be blended in the curable composition according to the present embodiment.
• a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved.
• Many compounds such as organic monomers, oligomers, resins, or compositions containing them are known as this type of compound. Unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, etc., which are monomers, oligomers, or mixtures thereof can be used.
• the photocurable substance is preferably used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect, more preferably is in the range of 0.5 to 10 parts by weight.
• the curable composition according to this embodiment may contain an oxygen-curable substance.
• oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, and react with oxygen in the air to form a hardened film near the surface of the cured product, which causes the surface to become sticky and dust on the surface of the cured product. and prevent the adhesion of dust.
• Specific examples of oxygen-curable substances include drying oils such as paulownia oil and linseed oil, various alkyd resins obtained by modifying these compounds; acrylic polymers modified with drying oils, and epoxy resins.
• silicone resins 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc.
• diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc.
• liquid polymers These may be used alone or in combination of two or more.
• the amount of the oxygen-curable substance used is preferably in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect. , more preferably 0.5 to 10 parts by weight.
• the oxygen-curable substance is preferably used in combination with the photo-curable substance.
• Epoxy resin can be blended into the curable composition according to the present embodiment.
• a composition containing an epoxy resin is particularly preferred as an adhesive, especially an adhesive for exterior wall tiles.
• epoxy resins include bisphenol A type epoxy resins and novolac type epoxy resins.
• the proportion of these epoxy resins and the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect is the weight ratio of the polyoxyalkylene polymer according to the first aspect or the second It is preferable that the mixture/epoxy resin according to the embodiment is in the range of 100/1 to 1/100.
• a curing agent that cures the epoxy resin can be used in combination with the curable composition according to the present embodiment.
• the epoxy resin curing agent that can be used is not particularly limited, and generally used epoxy resin curing agents can be used.
• the amount used is preferably in the range of 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.
• the curable composition according to the present embodiment can also be prepared as a one-component type in which all the ingredients are previously mixed and sealed and cured by moisture in the air after application, and a silanol condensation It can also be prepared as a two-component type in which components such as a catalyst, a filler, a plasticizer, and water are blended and the blending materials and the organic polymer composition are mixed before use. From the viewpoint of workability, the one-component type is preferred.
• the curable composition is of a one-component type
• all the ingredients are pre-blended, so the ingredients containing water are dehydrated and dried in advance before use, or dehydrated by decompression or the like during blending and kneading. is preferred.
• Storage stability is further improved by adding an alkoxysilane compound such as silane.
• the amount of the dehydrating agent, especially the silicon compound capable of reacting with water such as vinyltrimethoxysilane, is 0 per 100 parts by weight of the polyoxyalkylene polymer according to the first aspect or the mixture according to the second aspect. It is preferably used in the range of 0.1 to 20 parts by weight, more preferably in the range of 0.5 to 10 parts by weight.
• the curable composition according to the present embodiment includes adhesives, sealing materials for buildings, ships, automobiles, roads, etc., adhesives, waterproofing materials, coating film waterproofing materials, molding agents, vibration-proof materials, vibration-damping materials, Can be used as soundproofing material, foaming material, paint, spraying material.
• a cured product obtained by curing the curable composition according to the present embodiment is excellent in flexibility and adhesiveness, and thus can be suitably used as a sealant or an adhesive.
• the curable composition according to the present embodiment is an electrical/electronic component material such as a solar cell backside sealing material, an electrical/electronic component such as an insulating coating material for electric wires and cables, an electrical insulating material for devices, an acoustic insulation Materials, Elastic Adhesives, Binders, Contact Adhesives, Spray Sealants, Crack Repair Materials, Tile Adhesives, Asphalt Waterproofing Adhesives, Powder Coatings, Casting Materials, Medical Rubber Materials, Medical Use Adhesives, medical adhesive sheets, sealing materials for medical equipment, dental impression materials, food packaging materials, joint sealing materials for exterior materials such as sizing boards, coating materials, anti-slip coating materials, cushioning materials, primers, electro-conductive materials for shielding electromagnetic waves materials, thermally conductive materials, hot-melt materials, potting agents for electrical and electronic devices, films, gaskets, concrete reinforcing materials, adhesives for temporary fixing, various molding materials, wire glass and laminated glass edge (cut) protection
• sealing materials such as a solar
• the curable composition according to the present embodiment is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiling, an adhesive for stone, a ceiling finishing adhesive, a floor finishing adhesive, a wall Finishing adhesives, vehicle panel adhesives, electrical, electronic and precision equipment assembly adhesives, adhesives for bonding leather, textiles, fabrics, paper, boards and rubber, reactive post-crosslinking pressure sensitive adhesives , a sealant for direct glazing, a sealant for double glazing, a sealant for SSG construction, a sealant for working joints in buildings, a material for civil engineering, and a bridge. Furthermore, it can be used as an adhesive material such as an adhesive tape and an adhesive sheet.
• the present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
• the "components at both ends” referred to below are hydrolyzable silyl groups and/or reactive groups capable of introducing hydrolyzable silyl groups at both ends of linear polyoxypropylene (e.g., hydroxyl groups , allyl group, methallyl group).
• the term "single-end component" refers to a hydrolyzable silyl group and/or a reactive group capable of introducing a hydrolyzable silyl group at only one of both ends of linear polyoxypropylene.
• both terminal components may correspond to the polyreactive terminal polymer (a) or the polymer (A) when certain points are satisfied.
• a “single-end component” may correspond to a homoreactive end polymer (b) or a polymer (B) when certain points are satisfied.
• a number average molecular weight is a GPC molecular weight measured under the following conditions.
• Liquid delivery system Tosoh HLC-8420GPC Column: TSKgel SuperH series manufactured by Tosoh Solvent: THF Molecular weight: Polystyrene equivalent Measurement temperature: 40°C
• the viscosity is the viscosity measured at 23°C with an E-type viscometer (RE-85U manufactured by Tokyo Keiki, measurement cone: 3° x R14).
• the number of hydrolyzable silyl groups introduced to the molecular chain ends was 0.95.
• the polyoxypropylene-based polymer (A-1) also has a methyldimethoxysilyl group at a site (intermediate structure) other than the molecular chain end, and the number thereof is 0 when converted to one molecular chain end. .80.
• the total number of hydrolyzable silyl groups introduced (average ratio of the total number of hydrolyzable silyl groups to the number of molecular chain ends). was 1.75.
• 100 ppm of a platinum divinyldisiloxane complex (3 mass% isopropyl alcohol solution in terms of platinum) is added to 100 parts by weight of the resulting methallyl group/allyl group mixed-terminated polyoxypropylene mixture.
• 1000 ppm of 2,5-di-t-butyl-1,4-benzoquinone, and 1.3 equivalents of methyldimethoxysilane with respect to the total of methallyl groups/allyl groups were added and reacted at 100° C. for 5 hours.
• a polyoxypropylene polymer containing only both terminal components and having a methyldimethoxysilyl group at the molecular chain terminal and having a number average molecular weight of 28,000. (C-2) was obtained.
• the "number of hydrolyzable silyl groups introduced to the molecular chain end" of the polyoxypropylene-based polymer (C-2) was 0.75.
• the polyoxypropylene-based polymer (C-2) also has methyldimethoxysilyl groups at sites other than the ends of the molecular chain, and the number thereof is 0.75 when converted to one end of the molecular chain. rice field.
• the "total number of hydrolyzable silyl groups introduced” was 1.50 when added together with the number of hydrolyzable silyl groups introduced to the ends of the molecular chains.
• a methanol solution of sodium methoxide is added in an amount of 0.4 equivalents relative to the hydroxyl group of (E-2), methanol is distilled off at 130°C, and then 0.8 equivalents of allyl chloride is added at 130°C. to convert the remaining terminal hydroxyl groups to allyl groups.
• 100 ppm of a platinum divinyldisiloxane complex (3 mass% isopropyl alcohol solution in terms of platinum) is added to 100 parts by weight of the resulting methallyl group/allyl group mixed-terminated polyoxypropylene mixture.
• the "number of hydrolyzable silyl groups introduced to the molecular chain end" of the polyoxypropylene-based polymer (A-2) was 0.95.
• the polyoxypropylene-based polymer (A-2) also has methyldimethoxysilyl groups at sites other than the ends of the molecular chain, and the number thereof is 0.80 when converted to one end of the molecular chain. rice field.
• the "total number of hydrolyzable silyl groups introduced" was 1.75 when added together with the number of hydrolyzable silyl groups introduced to the ends of the molecular chains.
• 100 ppm of a platinum divinyldisiloxane complex (3 mass% isopropyl alcohol solution in terms of platinum) is added to 100 parts by weight of the resulting methallyl group/allyl group mixed-terminated polyoxypropylene mixture.
• 1000 ppm of 2,5-di-t-butyl-1,4-benzoquinone, and 1.3 equivalents of methyldimethoxysilane with respect to the total of methallyl groups/allyl groups were added and reacted at 100° C. for 5 hours.
• a methanol solution of sodium methoxide is added in an amount of 0.4 equivalents relative to the hydroxyl group of (E-2), methanol is distilled off at 130°C, and then 0.8 equivalents of allyl chloride is added at 130°C. to convert the remaining terminal hydroxyl groups to allyl groups.
• 50 ppm of a platinum divinyldisiloxane complex (3 mass% isopropyl alcohol solution in terms of platinum) and methyldimethoxysilane are added to 100 parts by weight of the resulting allyl group-terminated polyoxypropylene mixture. 3.4 parts by weight is added and reacted at 90° C.
• the "number of hydrolyzable silyl groups introduced to the molecular chain end" of the polyoxypropylene polymer (C-4) was 0.75.
• the polyoxypropylene-based polymer (C-4) also has methyldimethoxysilyl groups at sites other than the ends of the molecular chain, and the number thereof is 0.75 when converted to one end of the molecular chain. rice field.
• the "total number of hydrolyzable silyl groups introduced” was 1.50 when added together with the number of hydrolyzable silyl groups introduced to the ends of the molecular chains.
• 100 ppm of a platinum divinyldisiloxane complex (3 mass% isopropyl alcohol solution in terms of platinum) is added to 100 parts by weight of the resulting methallyl group/allyl group mixed-terminated polyoxypropylene mixture.
• 1000 ppm of 2,5-di-t-butyl-1,4-benzoquinone, and 1.3 equivalents of methyldimethoxysilane with respect to the total of methallyl groups/allyl groups were added and reacted at 100° C. for 5 hours.
• the polyoxypropylene-based polymer (B-3) also has methyldimethoxysilyl groups at sites other than the ends of the molecular chain, and the number thereof is 0.60 when converted to one end of the molecular chain. rice field.
• the "total number of hydrolyzable silyl groups introduced" was 1.30 when added together with the number of hydrolyzable silyl groups introduced to the ends of the molecular chains.
• 100 ppm of a platinum divinyldisiloxane complex (3 mass% isopropyl alcohol solution in terms of platinum) is added to 100 parts by weight of the resulting methallyl group/allyl group mixed-terminated polyoxypropylene mixture.
• 1000 ppm of 2,5-di-t-butyl-1,4-benzoquinone, and 1.3 equivalents of methyldimethoxysilane with respect to the total of methallyl groups/allyl groups were added and reacted at 100° C. for 5 hours.
• the "number of hydrolyzable silyl groups introduced to the molecular chain end" of the polyoxypropylene-based polymer mixture (AB-1) was 0.95.
• the polyoxypropylene-based polymer mixture (AB-1) also has methyldimethoxysilyl groups at sites other than the molecular chain ends, and the number thereof is 0.80 when converted to one molecular chain end. there were.
• the "total number of hydrolyzable silyl groups introduced” was 1.75 when added together with the number of hydrolyzable silyl groups introduced to the ends of the molecular chains.
• the weight ratio of both end components/one end component in the polyoxypropylene polymer mixture (AB-1) was about 6/4.
• the number average molecular weights of both terminal components/one terminal component estimated from the peak top in GPC and its chromatogram shape were 10,000 and 2,000, respectively.
• the number average molecular weights of both end components/one end components contained in the polymer mixture, which will be described hereinafter, are similarly estimated from the peak tops in GPC and their chromatogram shapes.
• the polyoxypropylene-based polymer mixture (AB-1) contains both the polyoxyalkylene-based polymer (A) and the polyoxyalkylene-based polymer (B). Each polymer contained in the polymer mixture can be separately referred to as polymer (A) and polymer (B). -1). Further, since the polyoxyalkylene polymers (A) and (B) contained in the polyoxypropylene polymer mixture (AB-1) are terminally modified at the same time, the polymers (A) and (B) The "number of hydrolyzable silyl groups introduced to the molecular chain ends" can be considered the same, and the "total number of hydrolyzable silyl groups introduced" of the polymers (A) and (B) can be considered the same. can think. The same applies to each polymer mixture (AB-2), (AB-3), (CB-1), and (CB-2) shown below.
• the “total number of hydrolyzable silyl groups introduced” was 1.35 when added together with the number of hydrolyzable silyl groups introduced to the ends of the molecular chains.
• the weight ratio of both terminal components/single terminal component in the polyoxypropylene-based polymer mixture (AB-2) is about 6/4, and the number average molecular weight of each of both terminal components/single terminal component is 10,000 and 2,000.
• allyl chloride 0.6 equivalents was added to convert the remaining terminal hydroxyl groups to allyl groups.
• 100 ppm of a platinum divinyldisiloxane complex (3 mass% isopropyl alcohol solution in terms of platinum) is added to 100 parts by weight of the resulting methallyl group/allyl group mixed-terminated polyoxypropylene mixture.
• 1000 ppm of 2,5-di-t-butyl-1,4-benzoquinone, and 1.3 equivalents of methyldimethoxysilane with respect to the total of methallyl groups/allyl groups were added and reacted at 100° C. for 5 hours.
• devolatilization under reduced pressure is performed to remove excess methyldimethoxysilane, thereby containing both terminal components and one terminal component, having a methyldimethoxysilyl group at both or one molecular chain terminal, and having a number average molecular weight of 4,000. to obtain a polyoxypropylene-based polymer mixture (CB-1).
• the polyoxypropylene-based polymer mixture (CB-1) has no hydrolyzable silyl groups at sites other than the molecular chain terminals, and the "number of hydrolyzable silyl groups introduced to the molecular chain terminals" and The “total number of hydrolyzable silyl groups introduced” was 0.95 for each.
• the weight ratio of both terminal components/single terminal component in the polyoxypropylene-based polymer mixture (CB-1) is about 6/4, and the number average molecular weight of each of both terminal components/single terminal component is 10,000 and 2,000.
• the "number of hydrolyzable silyl groups introduced to the molecular chain end" of the polyoxypropylene-based polymer mixture (AB-3) was 0.95.
• the polyoxypropylene-based polymer mixture (AB-3) also has methyldimethoxysilyl groups at sites other than the molecular chain ends, and the number thereof is 0.80 when converted to one molecular chain end. there were.
• the "total number of hydrolyzable silyl groups introduced” was 1.75 when added together with the number of hydrolyzable silyl groups introduced to the ends of the molecular chains.
• the weight ratio of both terminal components/single terminal component in the polyoxypropylene-based polymer mixture (AB-3) is about 6/4, and the number average molecular weight of each of both terminal components/single terminal component is 28,000 and 8,500.
• a platinum divinyldisiloxane complex (3 mass% isopropyl alcohol solution in terms of platinum) and methyldimethoxysilane are added to 100 parts by weight of the resulting allyl group-terminated polyoxypropylene mixture. 2.2 parts by weight are added and reacted at 90° C. for 2 hours to obtain a compound containing both terminal components and one terminal component, having a methyldimethoxysilyl group at both or one of the molecular chain terminals, and having a number average molecular weight of 15,000. to obtain a polyoxypropylene-based polymer mixture (CB-2).
• CB-2 polyoxypropylene-based polymer mixture
• the "number of hydrolyzable silyl groups introduced to the molecular chain end" of the polyoxypropylene-based polymer mixture (CB-2) was 0.75.
• the polyoxypropylene-based polymer mixture (CB-2) also has methyldimethoxysilyl groups at sites other than the molecular chain ends, and the number thereof is 0.90 when converted to one molecular chain end. there were.
• the "total number of hydrolyzable silyl groups introduced" was 1.65 when added together with the number of hydrolyzable silyl groups introduced to the ends of the molecular chains.
• the weight ratio of both terminal components/single terminal component in the polyoxypropylene-based polymer mixture (CB-2) is about 6/4, and the number average molecular weight of each of both terminal components/single terminal component is 28,000 and 8,500.
• a plasticizer, a filler, titanium oxide, an anti-sagging agent, a light stabilizer, and an ultraviolet absorber were thoroughly mixed and thoroughly kneaded, and then passed through three paint rolls to disperse. Thereafter, the mixture was dehydrated under reduced pressure at 120° C. for 2 hours using a planetary mixer, cooled to 50° C. or less, added with a dehydrating agent, and kneaded in a substantially moisture-free state. After degassing under reduced pressure, it was sealed in a cartridge, which is a moisture-proof container, to obtain a masterbatch composition.
• each polymer or each polymer mixture, an adhesion imparting agent, and a silanol condensation catalyst are added to the masterbatch composition, thoroughly mixed, and uniformly kneaded and degassed using a rotation-revolution mixer. , to prepare each curable composition.
• various test specimens were prepared under a constant temperature and constant humidity atmosphere at 23° C. and a relative humidity of 50%, and various evaluations were performed.
• the following additives were used in the evaluation of the composition physical properties of all Examples and Comparative Examples.
• the blending amount is the number of parts by weight per 100 parts by weight of each polymer or each polymer mixture that is the base polymer.
• Plasticizer diisononyl phthalate (DINP, manufactured by J-Plus Co., Ltd.), 90 parts by weight Filler: (i) Fatty acid-treated precipitated calcium carbonate (Hakuenka CCR, manufactured by Shiraishi Kogyo Co., Ltd.), 160 parts by weight (ii) Heavy calcium carbonate (Whiten SB Red, manufactured by Shiraishi Calcium Co., Ltd.), 54 parts by weight Titanium oxide: Typaque R-820, manufactured by Ishihara Sangyo Co., Ltd., 5 parts by weight Anti-sagging agent: Fatty acid amide wax (Disparon #6500, Kusumoto Kasei Co., Ltd.), 2 parts by weight Light stabilizer: Bis(2,2,6,6) -Tetramethyl-4-piperidyl) sebacate (tinuvin 770, manufactured by BASF), 1 part by weight UV absorber: 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol (tinu
• the curable composition was filled into a 3 mm thick sheet form. After curing for 3 days at 23° C. and 50% relative humidity, it was aged for 4 days in a drier at 50° C. to obtain a sheet-like cured product. The obtained cured product was punched into a No. 3 dumbbell shape according to JIS K 6251 to obtain a test piece. Using the obtained test piece, a tensile test (tensile speed of 200 mm/min) was performed using an autograph at 23° C. and a relative humidity of 50% to measure the stress at 100% elongation and the stress at break.
• the sheet-like cured product was punched into a No. 7 dumbbell shape to obtain a dumbbell-shaped test piece.
• Two marked lines were drawn at intervals of 10 mm centering on the constricted portion of the dumbbell-shaped test piece.
• the dumbbell-shaped test piece was stretched and fixed so that the interval between the marked lines was 20 mm, and allowed to stand in a drier at 50°C.
• the fixation was released after 24 hours, and the recovery rate was obtained by measuring the interval between the marked lines after 24 hours at 23° C. and a relative humidity of 50%.
• Tables 1 to 4 show the results obtained as described above.
• Table 1 shows the evaluation results of the polymer (A-1), (C-1), or (C-2) synthesized using the polymer (E-1), and the polymer (E-2). It shows the evaluation results of the polymers (A-2), (C-3), and (C-4) synthesized using. Both polymers contain only terminal components. Polymers (A-1) and (A-2) satisfy the requirements of "the number of hydrolyzable silyl groups introduced to the molecular chain ends" and "the total number of hydrolyzable silyl groups introduced".
• Polymers (C-1) and (C-3) do not satisfy the requirement for "total number of introduced hydrolyzable silyl groups", and polymers (C-2) and (C-4) have "molecular chain ends does not satisfy the requirement of "number of hydrolyzable silyl groups introduced into Example 1 using the polymer (A-1) has the same stress at break as compared to Comparative Examples 1 and 2 using the polymer (C-1) or (C-2), but the recovery rate showed high results. The same is true when comparing Example 2 using the polymer (A-2) with Comparative Examples 3 and 4 using the polymers (C-1) and (C-2).
• Tables 2-1 and 2-2 show the polymer (A-1), (C-1), or (C-2) of both terminal components synthesized using the polymer (E-1). It shows the evaluation results when any one of the terminal component polymers (B-1) to (B-4) is mixed.
• a polyoxyalkylene polymer (A-1) that satisfies the requirements of "the number of hydrolyzable silyl groups introduced to the molecular chain end” and “the total number of hydrolyzable silyl groups introduced” to the polymer (B-1) ) is mixed, compared with Comparative Examples 5 and 6 in which the polymer (B-1) is mixed with the polymer (C-1) or (C-2) that does not satisfy any of the requirements, Both the stress at break and the recovery rate showed good results.
• Example 3 using a mixture of polymer (A-1) and polymer (B-1) shows that the polymer ( A-1) It can be seen that the rate of decrease in stress at break and the rate of decrease in resilience relative to Example 1 alone are small.
• Comparative Examples 5 or 6 using a mixture of the polymer (C-1) or (C-2) and the polymer (B-1) the polymer (C-1) or (C-2) alone It can be seen that the reduction rate of the stress at break and the reduction rate of the recovery rate based on Comparative Example 1 or Comparative Example 2 are large.
• Example 4 is a comparison of Example 4 with Comparative Examples 7 and 8, a comparison of Example 5 with Comparative Examples 9 and 10, a comparison of Example 6 with Comparative Examples 11 and 12, and a comparison of Example 7 with Comparative Examples.
• the same is true in comparison with 13 and 14. Even if the mixing ratio of the polymer (A) and the polymer (B) is changed, the same result is obtained. gives better results.
• Table 3 shows the polymer (A-2), (C-3), or (C-4) of both terminal components synthesized using the polymer (E-2), the polymer (B -1), (B-2), and (B-5) are shown.
• Tables 2-1 and 2-2 a polyoxyalkylene polymer that satisfies the requirements for "the number of hydrolyzable silyl groups introduced to the molecular chain ends" and "the total number of hydrolyzable silyl groups introduced”
• each polymer (B) was mixed with polymer (C-3) or (C-4) that does not satisfy any of the requirements Both the stress at break and the recovery rate showed good results as compared with the comparative example.
• Table 4 shows evaluation results of polymer mixtures synthesized using polymer (E), which is a mixture of both terminal components and one terminal component.
• Example 13 compares with Comparative Example 22 using a polymer mixture (CB-2) in which both terminal components contained do not satisfy the requirement of "the number of hydrolyzable silyl groups introduced to the molecular chain terminals", Both the stress at break and the recovery rate showed good results.
• the polyoxyalkylene polymer that satisfies the requirements of "the number of hydrolyzable silyl groups introduced to the molecular chain end" and “the total number of hydrolyzable silyl groups introduced” has low viscosity and , after curing, it can be suitably used as a base polymer for various elastic materials that require good stress at break and good recovery rate.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Polyethers (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=82653500

Family Applications (1)

Country Status (2)

Cited By (2)

Citations (9)

• 2022
  • 2022-01-24 WO PCT/JP2022/002346 patent/WO2022163563A1/ja not_active Ceased
  • 2022-01-24 JP JP2022578355A patent/JPWO2022163563A1/ja active Pending

Patent Citations (9)

Also Published As

Similar Documents

Legal Events