Oxirane polymer, method for producing the same, curable composition, cured product

Abstract

The present invention relates to an oxyalkylene polymer having a polyoxyalkylene chain containing oxyethylene groups and a reactive silicon group, the reactive silicon group being bonded to the aforementioned polyoxyalkylene chain by means of an organic group containing 1 -C(=O)NH- represented group, the number average molecular weight of the oxyalkylene polymer being 3000 to 150000, the molecular weight distribution being 2.00 or less, the content of the aforementioned oxyethylene groups being 3 to 90 mass%, and the number of the aforementioned reactive silicon groups per 1 molecule being 0.5 or more.

Description

Technical Field

[0001] The present invention relates to an oxidized olefin polymer having reactive silicon groups, a method for manufacturing the aforementioned oxidized olefin polymer, a curable composition comprising the aforementioned oxidized olefin polymer, and a cured product of the aforementioned curable composition.

[0002] This application claims priority to Japanese Patent Application No. 2020-205019 filed in Japan on December 10, 2020, and Japanese Patent Application No. 2021-107746 filed in Japan on June 29, 2021, the contents of which are incorporated herein by reference. Background Technology

[0003] Oxide polymers with reactive silicon groups are cured through hydrolysis to form a soft, rubbery cured material, which is used as a curing component in sealants, adhesives, etc.

[0004] In these applications, low viscosity, good workability, and good strength and elongation after curing are required. In addition, depending on the coating area, the ability to fully cure from the surface to the depths due to moisture in the air is required (deep curing property).

[0005] Patent Document 1 describes an example of manufacturing an oxidized olefin polymer with reactive silicon groups suitable for sealing materials and adhesives. Specifically, it describes an example of reacting a polyether polyol with a diisocyanate compound to generate a urethane prepolymer with isocyanate groups at the ends, and then introducing reactive silicon groups into the resulting urethane prepolymer via urea bonds to manufacture a polymer.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2001-31757 Summary of the Invention

[0009] The problem the invention aims to solve

[0010] However, the viscosity of the oxidized olefin polymer produced using the above method tends to increase.

[0011] The present invention provides an oxidized olefin polymer capable of producing a curable composition with low viscosity, good deep curing properties, and good strength and elongation of the cured product, and a method for manufacturing the same; as well as a curable composition comprising the aforementioned oxidized olefin polymer and the cured product thereof.

[0012] Solution for solving the problem

[0013] The present invention has the following aspects.

[0014] [1] An oxidized olefin polymer having a polyoxyethylene chain comprising an oxyethylene group and a reactive silicon group as shown in formula (1), wherein the reactive silicon group is bonded to the aforementioned polyoxyethylene chain by means of an organic group comprising one group as shown in formula (i), wherein the number average molecular weight of the oxidized olefin polymer is 3,000 to 150,000, the molecular weight distribution is 2.00 or less, the content of the aforementioned oxyethylene group is 3 to 90% by mass, and the number of the aforementioned reactive silicon groups in an average of 1 molecule is 0.5 or more.

[0015] -C(=O)NH- (i)

[0016] -SiX a R 3-a (1)

[0017] In the aforementioned formula (1), R represents a monovalent organic group with 1 to 20 carbon atoms, and is an organic group other than a hydrolyzable group; X represents a hydroxyl group, a halogen atom, or a hydrolyzable group; a represents an integer from 1 to 3. When a is 1, R can be chosen to be the same or different from each other. When a is 2 or 3, X can be chosen to be the same or different from each other.

[0018] [2] According to [1], the oxidized olefin polymer does not contain urea bonds.

[0019] [3] A curable composition comprising the oxidized olefin polymer of [1] or [2] above.

[0020] [4] According to the curable composition of [3], the content of the aforementioned oxidized olefin polymer is 5 to 90% by mass relative to the total mass of the curable composition.

[0021] [5] The curable composition according to [3] or [4] further comprises a plasticizer.

[0022] [6] The curable composition according to [5], wherein the content of the aforementioned plasticizer is 1 to 350 parts by mass relative to 100 parts by mass of the aforementioned oxidized olefin polymer.

[0023] [7] A curable composition according to any one of [3] to [6], which is used as a sealing material or adhesive.

[0024] [8] A cured product, which is a cured product of any of the curable compositions of [3] to [7] above.

[0025] [9] A method for manufacturing an oxidized olefin polymer, wherein a precursor polymer is reacted with a compound of formula (2) such that the number of reactive silicon groups of formula (1) in an average of 1 molecule is 0.5 or more, to obtain an oxidized olefin polymer, wherein the precursor polymer has a polyoxyethylene chain containing oxyethylene groups and groups containing active hydrogens bonded to the aforementioned polyoxyethylene chain, the number average molecular weight of the precursor polymer is 3,000 to 150,000, the molecular weight distribution is 2.00 or less, and the content of the aforementioned oxyethylene groups is 3 to 90% by mass.

[0026] -SiX a R 3-a (1)

[0027] In the aforementioned formula (1), R represents a monovalent organic group with 1 to 20 carbon atoms, and is an organic group other than a hydrolyzable group; X represents a hydroxyl group, a halogen atom, or a hydrolyzable group; a represents an integer from 1 to 3. When a is 1, R can be chosen to be the same or different from each other. When a is 2 or 3, X can be chosen to be the same or different from each other.

[0028] O = C = NQ 1 -SiX a R 3-a (2)

[0029] In the aforementioned equation (2), Q 1 It is a divalent organic group with 1 to 20 carbon atoms, and R, X, a are the same as those in the aforementioned formula (1).

[0030]

[10] According to the manufacturing method of [9], the total unsaturation of the aforementioned precursor polymer is less than 0.1 meq / g.

[0031]

[11] The aforementioned precursor polymer is manufactured according to the manufacturing method of [9] or

[10] , wherein a cyclic ether containing ethylene oxide is polymerized with an initiator in the presence of a complex metal cyanide complex.

[0032]

[12] The manufacturing method according to [9] or

[10] wherein, in the presence of a complex metal cyanide complex, a cyclic ether is polymerized with an initiator, and ethylene oxide is further polymerized in the presence of an alkali metal hydroxide to produce the aforementioned precursor polymer.

[0033] The effects of the invention

[0034] According to the present invention, an oxidized olefin polymer capable of achieving a curable composition with low viscosity, good deep curing properties, and good strength and elongation of the cured product is obtained, as well as a curable composition comprising the aforementioned oxidized olefin polymer and the cured product thereof. Detailed Implementation

[0035] The meanings and definitions of the terms used in this specification are as follows.

[0036] The range of values ​​indicated by “~” refers to the range of values ​​with the values ​​before and after the “~” as the lower and upper limits.

[0037] "Polymer" refers to substances with an index-average molecular weight of 1000 or higher.

[0038] "Oxyolefin polymers" refers to polymers having polyoxyolefin chains formed from units based on cyclic ethers.

[0039] "A group containing active hydrogen" is at least one group selected from the group consisting of a monovalent functional group obtained by removing one hydrogen atom from a hydroxyl, carboxyl, amino, or primary amine bonded to a carbon atom and a sulfonyl group.

[0040] "Active hydrogen" refers to hydrogen atoms based on the aforementioned groups containing active hydrogen and hydrogen atoms based on water-based hydroxyl groups.

[0041] The "initiator" is a compound containing the aforementioned active hydrogen.

[0042] The number-average molecular weight (Mn) and mass-average molecular weight (Mw) of the polymer are the converted molecular weights of polystyrene obtained by GPC determination. The molecular weight distribution is a value calculated based on Mw and Mn, and is the ratio of Mw to Mn (Mw / Mn).

[0043] The total unsaturation of the polymer was determined using the iodine titration method based on JIS K1557-3:2007.

[0044] The content of oxyvinyl groups in oxidized olefin polymers can be determined by... 1 The determination was performed using H-NMR.

[0045] The average number of reactive silicon groups in one polymer molecule can be determined by... 1 The internal standard method of H-NMR was used for determination.

[0046] The number of -C(=O)NH- groups (hereinafter also referred to as "group (i)") in an average polymer molecule can be determined by GPC, NMR, or other analytical methods after dissociating the urethane and urea bonds using analytical methods described, for example, Japanese Patent Application Publication Nos. 2000-227430 and 2001-141726. Based on the number of group (i) obtained by this method and the number-average molecular weight of the polymer, the average number of group (i) per molecule can be calculated.

[0047] Oxidized olefin polymers

[0048] The oxidized olefin polymer of this embodiment (hereinafter also referred to as "polymer A") has a polyoxyethylene chain containing oxyethylene and a reactive silicon group shown in formula (1) below (hereinafter also simply referred to as "reactive silicon group").

[0049] The reactive silicon group is bonded to the aforementioned polyoxyethylene chain via an organic group (hereinafter also referred to as "organic group A"). Organic group A comprises one group (i) as shown in formula (i).

[0050] -C(=O)NH- (i)

[0051] -SiX a R 3-a (1)

[0052] In formula (1), R represents a monovalent organic group with 1 to 20 carbon atoms. R does not contain hydrolyzable groups.

[0053] As R, examples include hydrocarbon groups, halogenated hydrocarbon groups, and triorganosylsiloxy groups.

[0054] R is preferably alkyl, cycloalkyl, aryl, 1-chloroalkyl, and triorganosilyl. More preferably, it is at least one group selected from the group consisting of straight-chain or branched alkyl, cyclohexyl, phenyl, benzyl, 1-chloromethyl, trimethylsiloxy, triethylsiloxy, and triphenylsiloxy groups having 1 to 4 carbon atoms. From the viewpoint of good curability of polymers having reactive silicon groups and good stability of curable compositions, methyl or ethyl groups are preferred. From the viewpoint of fast curing speed of cured products, 1-chloromethyl groups are preferred. From the viewpoint of easy availability, methyl groups are particularly preferred.

[0055] In formula (1), X represents a hydroxyl group, a halogen atom, or a hydrolyzable group. A hydrolyzable group is a group that can react with water to form a silanol group.

[0056] Examples of hydrolyzable groups include alkoxy, acyloxy, ketoxime, amino, amide, acid amide, aminooxy, sulfonyl, and alkenyloxy.

[0057] From the viewpoint of hydrolytic stability and ease of handling, alkoxy group is preferred as X. The alkoxy group is preferably methoxy, ethoxy, or isopropoxy, and more preferably methoxy or ethoxy. If the alkoxy group is methoxy or ethoxy, it readily and rapidly forms siloxane bonds, resulting in a cross-linked structure in the cured product, thus improving the physical properties of the cured product.

[0058] In equation (1), a represents an integer from 1 to 3. When a is 1, R can be any number of the same or different. When a is 2 or more, X can be any number of the same or different.

[0059] a is preferably 2 or 3, and a is more preferably 2.

[0060] Examples of reactive silicon groups represented by formula (1) include trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, tri(2-propenoxy)silyl, triacetoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethoxyethylsilyl, diisopropoxymethylsilyl, chloromethyldimethoxysilyl, and chloromethyldiethoxysilyl. From the viewpoint of high reactivity and good curability, trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, and diethoxymethylsilyl are preferred, and dimethoxymethylsilyl and trimethoxysilyl are more preferred.

[0061] The average number of reactive silicon groups in one molecule of polymer A is 0.5 or more, preferably 0.8 to 8.0, more preferably 1.0 to 6.0, and even more preferably 1.2 to 4.0. If the number is above the lower limit of the aforementioned range, the deep curing properties are excellent; if the number is below the upper limit, the elongation properties of the cured product are excellent.

[0062] Polyoxyolefin chains contain units based on cyclic ethers.

[0063] Examples of cyclic ethers include ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, and other epoxide-alkane; and tetrahydrofuran and other cyclic ethers other than epoxide-alkane. Epoxide-alkane is preferred as a cyclic ether.

[0064] Polymer A has a polyoxyethylene chain that is a copolymer chain having units based on ethylene oxide (oxyethylene) and other units based on cyclic ethers other than ethylene oxide. The copolymer chain can be a block copolymer chain, a random copolymer chain, or a combination thereof.

[0065] Other units are preferably units based on alkyl epoxides (olefin oxides), and more preferably units based on propylene oxides (propylene oxide oxides).

[0066] As one aspect of the invention, the polyoxyethylene chain of polymer A preferably contains only oxyethylene and oxypropylene groups.

[0067] The polyoxyethylene chain of polymer A is preferably, for example, a random copolymer chain containing oxyethylene and oxypropylene groups, a block copolymer chain having block chains formed by oxypropylene groups and block chains formed by oxyethylene groups, or a molecular chain having a random copolymer chain containing oxyethylene and oxypropylene groups and a block chain formed by oxyethylene groups.

[0068] The polyoxyethylene chain of polymer A preferably has oxyethylene groups at least at the ends on the reactive silicon group side. For example, in the case of block chains formed of oxyethylene groups, it is preferred that the aforementioned block chains are present at least at the ends on the reactive silicon group side of the polyoxyethylene chain.

[0069] The content of oxyethylene (hereinafter also referred to as "EO content") relative to the total mass of polymer A is 3 to 90% by mass, preferably 4 to 85% by mass, and more preferably 6 to 80% by mass. If it is above the lower limit of the aforementioned range, the deep curing properties are excellent, and if it is below the upper limit, the viscosity is easily reduced.

[0070] In polymer A, the organic group A present between the polyoxyethylene chain and the reactive silicon group is derived from the organic group of compound 2 described later, which is used to introduce reactive silicon groups into an oxyethylene polymer (precursor polymer) that does not have reactive silicon groups. Organic group A contains one group (i) as shown in formula (i).

[0071] -C(=O)NH- (i)

[0072] Group (i) is a divalent group derived from the isocyanate group contained in compound 2. If compound 2 contains one isocyanate group, then group (i) contained in organic group A becomes one.

[0073] Group (i) preferably forms a polyoxyolefin chain and a urethane bond (-OC(=O)NH-, -O- represents the terminal oxygen atom of the polyoxyolefin chain). That is, in polymer A, there is preferably one urethane bond between the polyoxyolefin chain and the reactive silicon group. Polymer A preferably does not contain urea bonds (-NH-C(=O)NH-).

[0074] When the aforementioned compound 2 contains one isocyanate group and one reactive silicon group, the number of reactive silicon groups per molecule of polymer A is the same as the number of groups (i) per molecule.

[0075] In organic group A, it is preferable to have a divalent organic group Q sandwiched between group (i) and the reactive silicon group. 1 Q 1 Preferably, it is a divalent hydrocarbon group, more preferably an alkylene group having 1 to 20 carbon atoms. Organic group Q 1 The preferred method will be explained in equation (2) below.

[0076] The Mn of polymer A is 3,000 to 150,000, preferably 4,000 to 100,000, more preferably 5,000 to 80,000, and even more preferably 8,000 to 60,000. If it is above the lower limit of the aforementioned range, the elongation property of the cured product is excellent; if it is below the upper limit, the viscosity is easily reduced.

[0077] The Mw / Mn ratio of polymer A is 2.00 or less, preferably 1.50 or less, more preferably 1.45 or less, and even more preferably 1.40 or less. If it is below the aforementioned upper limit value, the viscosity is easily reduced. Furthermore, the elongation properties of the cured product are easily improved. The lower limit value is not particularly limited. For example, it is 1.00 or more, preferably 1.01 or more. The above lower and upper limits can be combined arbitrarily. For example, the Mw / Mn ratio of polymer A is preferably 1.00 or more and 2.00 or less, more preferably 1.00 or more and 1.50 or less, even more preferably 1.01 or more and 1.45 or less, and particularly preferably 1.01 or more and 1.40 or less.

[0078] The viscosity of polymer A at 25°C is preferably 0.1–50.0 Pa·s, more preferably 0.3–40.0 Pa·s, even more preferably 0.8–35.0 Pa·s, and most preferably 1.0–25.0 Pa·s. Workability is further improved if the viscosity falls within the aforementioned range.

[0079] Manufacturing Methods of Oxide-Based Polymers

[0080] Polymer A can be manufactured by reacting a precursor polymer (hereinafter also referred to as "precursor polymer B") having a polyoxyethylene chain containing oxyethylene and a group containing active hydrogen bonded to the aforementioned polyoxyethylene chain with a compound shown in formula (2) (hereinafter also referred to as "compound 2").

[0081] Precursor polymer B can be produced by polymerizing an initiator with a cyclic ether containing ethylene oxide in the presence of a ring-opening polymerization catalyst.

[0082] The number of active hydrogen atoms in the initiator is preferably 1 to 8, more preferably 1 to 6, and even more preferably 2 to 4. It is preferably selected based on the number of reactive silicon groups per molecule of the desired polymer A on average.

[0083] Initiators can be used alone or in combination of two or more.

[0084] The initiator preferably has a hydroxyl group as the group containing active hydrogen.

[0085] Examples of initiators having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, and low molecular weight polyoxypropylene glycol.

[0086] Examples of initiators having three hydroxyl groups include glycerol, trimethylolpropane, trimethylolethane, and low molecular weight polyoxyglycerol.

[0087] Examples of initiators having four or more hydroxyl groups include pentaerythritol, sucrose, sorbitol, dipentaerythritol, trehalose, and diglycerides.

[0088] The cyclic ether can be selected based on the structural units of the polyoxyolefin chains of the desired precursor polymer B and polymer A. The cyclic ether contains at least ethylene oxide.

[0089] The content of oxyvinyl groups relative to the total mass of precursor polymer B is 3 to 90% by mass, preferably 4 to 85% by mass, and more preferably 6 to 80% by mass.

[0090] The unit other than oxyvinyl group is preferably oxyalkenyl group, and more preferably oxypropylene group.

[0091] As one aspect of the invention, the polyoxyethylene chain of the precursor polymer B preferably contains only oxyethylene and oxypropylene groups.

[0092] Examples of ring-opening polymerization catalysts include complex metal cyanide complexes and alkali metal hydroxides (such as potassium hydroxide).

[0093] Based on the viewpoints that the molecular weight distribution of precursor polymer B tends to decrease and the total unsaturation of precursor polymer B tends to decrease, it is preferable to use a complex metal cyanide complex.

[0094] The complex metal cyanide complex can be made using existing known compounds. Compounds and manufacturing methods disclosed, for example, in International Publication No. 2003 / 062301, International Publication No. 2004 / 067633, Japanese Patent Application Publication No. 2004-269776, Japanese Patent Application Publication No. 2005-15786, International Publication No. 2013 / 065802, and Japanese Patent Application Publication No. 2015-010162 can be used.

[0095] The composite metal cyanide complex is preferably a composite metal cyanide complex with glycol dimethyl ether and tert-butanol as organic ligands coordinated on the catalyst framework. The catalyst framework is more preferably Zn3[Co(CN)6]2 (i.e., zinc hexacyanocobaltate complex). A composite metal cyanide complex using tert-butanol as the organic ligand is particularly preferred.

[0096] When it is desired that the polyoxyethylene chains of the precursor polymer B and polymer A are random copolymer chains, the preferred method is to polymerize a cyclic ether containing ethylene oxide with an initiator in the presence of a complex metal cyanide complex to produce the precursor polymer B.

[0097] For example, a preferred method is to react a mixture of ethylene oxide and propylene oxide with an initiator in the presence of a complex metal cyanide complex to obtain precursor polymer B.

[0098] When the desired precursor polymer B and polymer A have polyoxyethylene chains that are block chains or random copolymer chains formed by oxyethylene groups other than oxyethylene groups, the preferred method is to polymerize a cyclic ether with an initiator in the presence of a complex metal cyanide complex, and further polymerize ethylene oxide in the presence of an alkali metal hydroxide to produce precursor polymer B.

[0099] For example, a preferred method is to polymerize propylene oxide with an initiator in the presence of a complex metal cyanide complex, followed by polymerizing ethylene oxide in the presence of an alkali metal hydroxide to obtain precursor polymer B.

[0100] Alternatively, the preferred method is to react a mixture of ethylene oxide and propylene oxide with an initiator in the presence of a complex metal cyanide complex, followed by polymerization of the ethylene oxide in the presence of an alkali metal hydroxide to obtain precursor polymer B.

[0101] In precursor polymer B, if oxyethylene groups are present at least at the ends of the reactive silicon groups in the polyoxyethylene chain, it is preferred from the viewpoint of better deep curing properties.

[0102] The Mn of the precursor polymer B is 3,000 to 150,000, preferably 4,000 to 100,000, more preferably 5,000 to 80,000, and even more preferably 8,000 to 60,000. Preferably, it is set according to the desired Mn of the polymer A.

[0103] The Mw / Mn ratio of precursor polymer B is preferably set such that the Mw / Mn ratio of polymer A is 2.00 or less. For example, the Mw / Mn ratio of precursor polymer B is preferably 1.50 or less, more preferably 1.45 or less, and even more preferably 1.40 or less. The lower limit value is not particularly limited. For example, it is 1.00 or more, preferably 1.01 or more. The above lower and upper limits can be combined arbitrarily. For example, the Mw / Mn ratio of precursor polymer B is preferably 1.00 or more and 2.00 or less, more preferably 1.00 or more and 1.50 or less, even more preferably 1.01 or more and 1.45 or less, and particularly preferably 1.01 or more and 1.40 or less.

[0104] The total unsaturation degree of precursor polymer B is preferably 0.1 meq / g or less, more preferably 0.05 meq / g or less, even more preferably 0.03 meq / g or less, and most preferably 0.01 meq / g or less. If it is below the aforementioned upper limit value, the deep curing properties are excellent. The lower limit value is not particularly limited. For example, it is preferably 0.0001 meq / g or more. The total unsaturation degree of precursor polymer B is preferably 0.0001 to 0.1 meq / g, more preferably 0.0001 to 0.05 meq / g, even more preferably 0.0001 to 0.03 meq / g, and most preferably 0.0001 to 0.01 meq / g.

[0105] Compound 2, which reacts with precursor polymer B, is represented by the following formula (2).

[0106] O = C = NQ 1 -SiX a R 3-a (2)

[0107] In equation (2), R, X, and a, including their preferred forms, are the same as R, X, and a in equation (1).

[0108] Q 1 It is a divalent organic group with 1 to 20 carbon atoms. Q 1 Preferably, it is a divalent hydrocarbon group, more preferably an alkylene group. Q 1 The number of carbon atoms is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8.

[0109] Examples of compound 2 include isocyanate methyltrimethoxysilane, isocyanate methyltriethoxysilane, isocyanate methylmethyldimethoxysilane, 1-isocyanate propylmethyldimethoxysilane, 3-isocyanate propyltrimethoxysilane, 3-isocyanate propylmethyldimethoxysilane, and 3-isocyanate propyltriethoxysilane.

[0110] From the viewpoint that the cured product of the curing composition has better deep curing properties, 3-isocyanate propyltrimethoxysilane, 3-isocyanate propylmethyldimethoxysilane, 1-isocyanate propylmethyldimethoxysilane, and 3-isocyanate propyltriethoxysilane are preferred.

[0111] A reactive silicon group is introduced into the precursor polymer B by reacting the active hydrogen of the precursor polymer B with the isocyanate group of compound 2.

[0112] When the active hydrogen-containing group of precursor polymer B is a hydroxyl group, a reactive silicon group is obtained via a urethane bond and an organic group (-Q). 1 -) and bonded to the polyoxyethylene chain (-(R 1 O) n -;R 1 Polymer A (where n represents the molar number of alkylene groups and n represents the number of oxidized alkenyl groups) is formed. That is, it forms a -(R... 1 O) n -C(=O)NH-Q 1 -SiX a R 3-a The connection structure shown.

[0113] The reaction between precursor polymer B and compound 2 can be carried out using known methods. When the active hydrogen-containing group of precursor polymer B is a hydroxyl group, a known carbamate catalyst can be used in the reaction (carbamate reaction) between precursor polymer B and compound 2. Examples of carbamate catalysts include organotin compounds, bismuth compounds, organometallic alkoxides, complexes containing metals other than tin, organic amines, and complex metal cyanide complexes with organic ligands. Preferred carbamate catalysts include dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin diisooctylthioglycol, and bismuth octanoate.

[0114] The molar ratio of the total number of isocyanate groups in compound 2 to the total number of active hydrogens in precursor polymer B is preferably set according to the number of reactive silicon groups per molecule of polymer A to be obtained. Compound 2 is reacted such that the number of reactive silicon groups per molecule of the obtained polymer A is at least 0.5.

[0115] For example, when the active hydrogen-containing group of precursor polymer B is a hydroxyl group, the NCO / OH ratio, which represents the molar ratio of the total number of isocyanate groups (NCO) of compound 2 to the total number of active hydrogens of precursor polymer B, is preferably 0.5 to 1.2, more preferably 0.6 to 1.1, and even more preferably 0.8 to 1.0. If the value is above the lower limit of the aforementioned range, the strength of the cured product is excellent; if the value is below the upper limit, the elongation of the cured product is excellent.

[0116] As a method for manufacturing polymer A, if a method is used to react precursor polymer B with compound 2, it is preferable from the viewpoint that no impurities with unsaturated groups are generated as byproducts. Furthermore, it is preferable from the viewpoint of minimizing the number of manufacturing steps. The total unsaturation of polymer A obtained by this method is less than or equal to the total unsaturation of precursor polymer B. In a specific example, the total unsaturation of polymer A is preferably 0.1 meq / g or less, more preferably 0.05 meq / g or less, further preferably 0.03 meq / g or less, and most preferably 0.01 meq / g or less. If it is below the aforementioned upper limit value, the strength of the cured product is superior. The lower limit value is not particularly limited. For example, it is preferably 0.0001 meq / g or more. The total unsaturation of polymer A is preferably 0.0001 to 0.1 meq / g, more preferably 0.0001 to 0.05 meq / g, further preferably 0.0001 to 0.03 meq / g, and most preferably 0.0001 to 0.01 meq / g.

[0117] Curing compositions / cured products

[0118] The curable composition of this embodiment comprises polymer A. Preferably, it also comprises one or more plasticizers.

[0119] The curable composition may contain one or more polymers A. When using two or more polymers A, the preferred ranges for the Mn and EO content, the average number of reactive silicon groups per molecule, the Mw / Mn ratio, and the viscosity of the aforementioned polymers A are preferred ranges for each polymer. The content of polymer A relative to the total mass of the curable composition is preferably 5 to 90% by mass, more preferably 10 to 60% by mass, and even more preferably 15 to 50% by mass. If the content is above the lower limit of the above range, the modulus of the cured product of the curable composition tends to be in a favorable range, and if it is below the upper limit, the elongation of the cured product of the curable composition tends to be favorable.

[0120] As a plasticizer, it may contain polymers (Mn 1000 or more) that do not have reactive silicon groups. Examples include (meth)acrylate polymers and oxidized olefin polymers. Examples of (meth)acrylate polymers include polymers or copolymers containing monomers of (meth)acrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate. "(Methacryl acrylate)" refers to one or both of acrylates and methacrylates. Examples of commercially available (meth)acrylate polymers include ARUFON (registered trademark) UP-1000, ARUFON UP-1110, and ARUFON UP-1171 (all manufactured by Toa Synthetic Co., Ltd.). ARUFON (registered trademark) UP-1171 is preferred as a (meth)acrylate polymer.

[0121] Examples of olefin oxide polymers used as plasticizers include polyolefin oxide polyols and derivatives obtained by converting the hydroxyl groups of the aforementioned polyolefin oxide polyols into esters or ethers.

[0122] The aforementioned polyoxyethylene polyol has polyoxyethylene chains and hydroxyl groups. For example, the aforementioned precursor polymer B can be used as the aforementioned polyoxyethylene polyol. The number of hydroxyl groups in one molecule of the aforementioned polyoxyethylene polyol is preferably two or three. The polyoxyethylene chains of the aforementioned polyoxyethylene polyol preferably contain oxyethylene groups, and more preferably contain oxyethylene and oxypropylene groups. When the polyoxyethylene chains contain oxyethylene and oxypropylene groups, they can be random copolymer chains, block copolymer chains, or combinations thereof.

[0123] The content of oxyethylene is preferably 3 to 90% by mass, more preferably 4 to 85% by mass, and even more preferably 6 to 80% by mass, relative to the total mass of the oxyethylene polymer used as a plasticizer.

[0124] The Mn of the oxidized olefin polymer used as a plasticizer is preferably 3,000 to 150,000, more preferably 4,000 to 100,000, even more preferably 5,000 to 80,000, and most preferably 8,000 to 60,000.

[0125] Commercially available olefin polymers can be used as plasticizers. Examples include PREMINOL (registered trademark) S3011, PREMINOL S4012, and PREMINOL S4013F (all manufactured by AGC).

[0126] As a plasticizer, it may contain one or more low molecular weight (Mn or formula weight less than 1000) plasticizers. Examples of low molecular weight plasticizers include phthalate compounds such as dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, and diisononyl phthalate; aliphatic carboxylic acid ester compounds such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate, butyl oleate, and 1,2-cyclohexanedicarboxylic acid-diisononyl ester; alcohol ester compounds such as pentaerythritol esters; phosphate ester compounds such as trioctyl phosphate and tricresyl phosphate; epoxy plasticizers such as epoxidized soybean oil, dioctyl 4,5-epoxyhexahydrophthalate, and benzyl epoxy stearate; chlorinated paraffin; and polyester plasticizers such as polyesters formed by reacting diacids with diols.

[0127] As a low molecular weight plasticizer, preferred plasticizers include phthalate compounds such as diisononyl phthalate and aliphatic carboxylic acid ester compounds such as 1,2-cyclohexanedicarboxylic acid-diisononyl phthalate.

[0128] When the curable composition contains a plasticizer, the plasticizer content is preferably 1 to 350 parts by weight, more preferably 2 to 300 parts by weight, further preferably 3 to 200 parts by weight, and particularly preferably 5 to 120 parts by weight, relative to 100 parts by weight of polymer A. If the content is above the lower limit of the aforementioned range, the viscosity of the curable composition becomes lower, and the workability becomes better; if the content is below the upper limit, it is less likely to seep into the cured product of the curable composition.

[0129] The curable composition may contain one or more other components that are not among the aforementioned polymer A and the aforementioned plasticizer.

[0130] Other components may include additives suitable for the intended use of the curable composition, such as fillers, thixotropic agents, antioxidants, UV absorbers, light stabilizers, dehydrating agents, adhesive agents, amine compounds, modulus modulators, oxygen-curing compounds, photocuring compounds, and curing catalysts. Other components may be used in combination without limitation with substances already known and disclosed in International Publication Nos. 2013 / 180203, 2014 / 192842, 2016 / 002907, Japanese Patent Application Publication Nos. 2014-88481, 2015-10162, 2015-105293, 2017-039728, and 2017-214541.

[0131] The curable composition is obtained by adding the desired ingredients to polymer A and mixing them.

[0132] Curing compositions can be single-component types in which all components are pre-mixed and sealed, and then cured by moisture in the air after application.

[0133] Alternatively, it can be a two-component composition in which a main agent composition containing at least a component having reactive silicon groups and a curing agent composition containing at least a curing catalyst are stored separately, and the curing agent composition is mixed with the main agent composition and cured before use.

[0134] The single-component curable composition is preferably free of moisture. Preferably, the water-containing components are pre-dehydrated and dried, or dehydrated under reduced pressure during compounding.

[0135] In two-component curable compositions, the curing agent composition may contain water. While the main component composition is unlikely to gel even with small amounts of water, from a storage stability perspective, it is preferable to pre-dehydrate and dry the compounding components.

[0136] To improve storage stability, a dehydrating agent can be added to a single-component curable composition or a two-component main agent composition.

[0137] As a curable composition, it is suitable for use as a sealing material (e.g., elastic sealing material for building, sealing material for multilayer glass, rust-proof / waterproof sealing material for glass ends, back sealing material for solar cells, sealing material for buildings, sealing material for ships, sealing material for automobiles, sealing material for roads), electrical insulation material (insulating covering material for wires / cables), adhesive, and potting material.

[0138] The curable composition of this embodiment exhibits excellent deep curing properties. For example, in the deep curing test described in the examples below, deep curing properties can be achieved with a cured portion thickness of 7 mm or more after 3 days and a cured portion thickness of 12 mm or more after 7 days. Preferably, deep curing properties can be achieved with a cured portion thickness of 8 mm or more after 3 days and a cured portion thickness of 13 mm or more after 7 days. There is no particular limitation on the upper limit values. An example of the upper limit value for the cured portion thickness after 3 days is 55 mm. An example of the upper limit value for the cured portion thickness after 7 days is 55 mm. Preferably, the cured portion thickness after 3 days is 7 to 55 mm and the cured portion thickness after 7 days is 12 to 55 mm; more preferably, the cured portion thickness after 3 days is 8 to 55 mm and the cured portion thickness after 7 days is 13 to 55 mm.

[0139] The curable composition of this embodiment is easily converted to a low viscosity, resulting in good workability. For example, the viscosity of the curable composition at 25°C can reach 0.1 to 1000 Pa·s, preferably 1.0 to 500 Pa·s, and more preferably 1.0 to 200 Pa·s. If within the aforementioned range, its workability is excellent when used, for example, as a sealant or adhesive.

[0140] The cured composition of this embodiment exhibits excellent strength. For example, the maximum point cohesion (Tmax) in the tensile test described in the later examples can reach 0.50 N / mm. 2 The above-mentioned preferred option is one that can achieve 1.00 N / mm. 2 The above applies. If the strength is within the aforementioned range, it exhibits excellent performance as, for example, a sealing material or adhesive. There is no particular upper limit. An example of an upper limit is 5.00 N / mm. 2 Tmax is preferably 0.50~5.00N / mm 2 More preferably, it is 1.00 to 5.00 N / mm 2 .

[0141] The cured composition of this embodiment exhibits excellent elongation properties. For example, the maximum point elongation (E) in the tensile test described in the later examples can reach 50% or more, preferably 60% or more. If it is above the aforementioned lower limit, it has excellent elongation properties as, for example, a sealing material or adhesive. The upper limit is not particularly limited. As an example of an upper limit, 300% can be shown. E is preferably 50 to 300%, more preferably 60 to 300%.

[0142] Example

[0143] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

[0144] <Determination Method>

[0145] [Mn and Mw / Mn of the polymer]

[0146] The HLC-8220GPC (Tosoh Corporation product name) was used, along with the TSKgel Supermultipore HZ-M column (Tosoh Corporation product name). Tetrahydrofuran was used as the solvent. The sample pump and reference pump were both set to 0.350 mL / min, the detector temperature was set to 40 °C, and the collection time was set to 6 to 15 minutes. Peaks collected between 6 and 11 minutes were analyzed to determine Mw, Mn, and Mw / Mn.

[0147] [Number of hydroxyl groups in the precursor polymer]

[0148] The number of hydroxyl groups in a molecule of precursor polymer was determined as follows: the hydroxyl groups were esterified using a pyridine solution of phthalic anhydride, and the determination was performed by titration using a sodium hydroxide (NaOH) solution (according to JIS K1557:2007).

[0149] [Viscosity]

[0150] The viscosity of the olefin polymer A was measured using a Type E viscometer, VISCOMETER TV-22 (Toki Sangyo Co., Ltd.), at a measurement temperature of 25°C.

[0151] The viscosity of the curable composition was determined as follows: using a Type B viscometer VISCOMETER TV-25H (Toki Sangyo Co., Ltd.), the viscometer was rotated at 10 rpm for 1 minute and the measurement was performed at a temperature of 25°C.

[0152] [other]

[0153] The total degree of unsaturation of precursor polymer B, the content of oxyvinyl groups in the polymer, and the number of reactive silicon groups and -C(=O)NH- groups per molecule of polymer A were determined using the methods described above.

[0154] <Evaluation Methods>

[0155] [Deep Curing Test]

[0156] In an atmosphere of 23°C and 50% relative humidity, the curing composition to be tested was filled into a polyethylene tube with a diameter of 24 mm and a height of 55 mm without trapping air bubbles. The excess curing composition overflowing from the open end of the tube was scraped off with a spatula to flatten the surface, resulting in a test specimen. The specimen was then placed in the aforementioned atmosphere with the surface of the curing composition horizontal, and the degree of curing from the surface inwards was investigated after 1 day, 3 days, and 7 days. Specifically, the cured surface layer (cured portion) of the curing composition was peeled off, the uncured portion was removed, and the thickness of the cured portion (in mm) was measured using calipers. A greater thickness of the cured portion indicates better deep curing performance.

[0157] [Tensile test (M50, Tmax, E)]

[0158] The curable composition to be tested was filled into a mold with a thickness of 2 mm and cured for 7 days at a temperature of 23°C and a relative humidity of 50%, and then cured for 7 days at a temperature of 50°C and a relative humidity of 65%. The resulting cured product was punched using a dumbbell-shaped frame to obtain test pieces.

[0159] For the obtained test pieces, a tensile test was conducted at a tensile speed of 500 mm / min, and the stress at 50% elongation was measured (M50, unit: N / mm). 2 Maximum point cohesion (Tmax, unit: N / mm) 2 Tensile properties of maximum point elongation (E, unit: %).

[0160] (Manufacturing Example 1: Manufacturing of Precursor Polymer B1)

[0161] A slurry containing a zinc hexacyanocobaltate-glycol dimethyl ether complex (hereinafter referred to as "Gly-DMC catalyst") and polyoxypropylene glycol (hereinafter referred to as "Initiator A") with a Mn of 3000, obtained by polymerizing propylene oxide (hereinafter referred to as "PO") with glycerol as an initiator, were added to a pressure-resistant reaction vessel equipped with a stirrer and a nitrogen inlet pipe to prepare a reaction solution. The amount of the aforementioned slurry added was set such that the metal concentration of the Gly-DMC catalyst in the reaction solution was 46 ppm by mass.

[0162] Next, after purging the pressure-resistant reaction vessel with nitrogen, the reaction liquid was heated while being stirred, and PO was supplied to the pressure-resistant reaction vessel at 135°C in a manner that achieved the target molecular weight, and the reaction was initiated.

[0163] Next, after confirming that the temperature rise of the reaction solution had stopped, it was cooled to 120°C. Then, 48% KOH catalyst was added to the resulting reaction solution at an effective component concentration of 0.3% by mass, followed by dehydration to achieve alkoxideization. Then, ethylene oxide (hereinafter also referred to as "EO") was supplied to the pressure-resistant reaction vessel at the target content, and the reaction was initiated.

[0164] After confirming that the internal pressure no longer changed and the reaction was complete, the catalyst was neutralized and removed using a synthetic adsorbent (KYOWAAD 600S, manufactured by Kyowa Chemical Industry Co., Ltd.) to obtain precursor polymer B1. The number of hydroxyl groups, Mn, Mw / Mn, EO content, and total unsaturation of one molecule of the obtained precursor polymer are shown in Table 1 (the same applies below).

[0165] (Manufacturing Example 2: Manufacturing of Precursor Polymer B2)

[0166] A slurry containing zinc hexacyanocobaltate-tert-butanol complex (hereinafter referred to as "TBA-DMC catalyst") and initiator A were added to a pressure-resistant reaction vessel identical to that used in Manufacturing Example 1 to prepare a reaction solution. The amount of slurry added was set such that the metal concentration of the TBA-DMC catalyst was 46 ppm by mass.

[0167] Next, after purging the pressure-resistant reaction vessel with nitrogen, the reaction solution was heated while being stirred, and the mixture of PO and EO was supplied to the pressure-resistant reaction vessel at 135°C to react in a manner that achieves the target molecular weight, thereby obtaining the precursor polymer B2 (PO / EO mass ratio of 80 / 20).

[0168] (Manufacturing Example 3: Manufacturing of Precursor Polymer B3)

[0169] In Manufacturing Example 2, initiator A was changed to Mn3400 polyoxyethylene oxypropylene triol obtained by polymerizing a mixture of PO / EO with a PO / EO mass ratio of 35 / 65 using glycerol as the initiator. The PO / EO ratio of the PO / EO mixture was changed so that the PO / EO mass ratio of the resulting precursor polymer was 35 / 65. Otherwise, the same procedure as in Manufacturing Example 2 was followed to obtain precursor polymer B3.

[0170] (Manufacturing Example 4: Manufacturing of Precursor Polymer B4)

[0171] In Manufacturing Example 2, initiator A was changed to polyoxyethylene oxypropylene triol with a Mn of 3400, obtained by polymerizing a mixture with a PO / EO mass ratio of 20 / 80 using glycerol as the initiator. The PO / EO ratio of the PO / EO mixture was changed so that the PO / EO mass ratio of the resulting precursor polymer was 20 / 80. Otherwise, the same procedure as in Manufacturing Example 2 was followed to obtain precursor polymer B4.

[0172] (Manufacturing Example 5: Manufacturing of Precursor Polymer B5)

[0173] In Manufacturing Example 2, initiator A was changed to polyoxypropylene glycol with an Mn of 3000, obtained by polymerizing PO using dipropylene glycol as the initiator. Otherwise, the same procedure as in Manufacturing Example 2 was followed to obtain precursor polymer B5.

[0174] (Manufacturing Example 6: Manufacturing of Precursor Polymer B6)

[0175] In Manufacturing Example 2, the target Mn was changed. Otherwise, the same procedures as in Manufacturing Example 2 were followed to obtain the precursor polymer B6.

[0176] (Manufacturing Example 7: Manufacturing of Precursor Polymer B7)

[0177] In Manufacturing Example 1, the target molecular weight was changed, and the supply amounts of PO and EO were varied so that the PO / EO mass ratio of the resulting precursor polymer was 80 / 20. Otherwise, the same procedure as in Manufacturing Example 1 was followed to obtain precursor polymer B7.

[0178] (Manufacturing Example 8: Manufacturing of Precursor Polymer B8)

[0179] In Manufacturing Example 1, the target molecular weight was changed, and the supply amounts of PO and EO were varied so that the PO / EO mass ratio of the resulting precursor polymer was 80 / 20. Otherwise, the same procedure as in Manufacturing Example 1 was followed to obtain precursor polymer B8.

[0180] (Manufacturing Example 9: Manufacturing of Precursor Polymer B'9 (Comparative Example))

[0181] In Manufacturing Example 2, initiator A was replaced with polyoxypropylene glycol with a Mn of 1000, obtained by polymerizing PO using glycerol as an initiator, instead of the mixture of PO and EO. PO was supplied to a pressure-resistant reaction vessel to react in a manner that achieved the target molecular weight. Otherwise, the same procedure as in Manufacturing Example 2 was followed to obtain precursor polymer B'9.

[0182] (Manufacturing Example 10: Manufacturing of Precursor Polymer B'10 (Comparative Example))

[0183] In Manufacturing Example 2, initiator A was replaced with polyoxyethylene glycerol with a Mn of 3000 obtained by polymerizing EO using glycerol as an initiator, instead of the mixture of PO and EO. EO was supplied to a pressure-resistant reaction vessel to react in a manner that achieved the target molecular weight. Otherwise, the same procedure as in Manufacturing Example 2 was followed to obtain precursor polymer B'10.

[0184] (Manufacturing Example 11: Manufacturing of Precursor Polymer B'11 (Comparative Example))

[0185] In Manufacturing Example 2, the target molecular weight was changed. Otherwise, the same procedures as in Manufacturing Example 2 were followed to obtain the precursor polymer B'11.

[0186] (Manufacturing Example 12: Manufacturing of Precursor Polymer B12)

[0187] In Manufacturing Example 2, initiator A was changed to a polyoxypropylene polyol with a molecular weight of 1000 obtained by polymerizing PO using sorbitol as an initiator. The target molecular weight was changed, and the PO / EO ratio of the mixture of PO and EO was changed so that the PO / EO mass ratio of the resulting precursor polymer was 95 / 5. Otherwise, the same procedure as in Manufacturing Example 2 was followed to obtain precursor polymer B12.

[0188] [Table 1]

[0189]

[0190] (Example 1: Manufacturing of polymer A1)

[0191] The reactor containing precursor polymer B1 was purged with nitrogen, and the internal temperature was maintained at 50°C. 3-Isocyanate propyltrimethoxysilane was added as a catalyst at an NCO / OH molar ratio of 0.97, along with dioctyltin bisisooctylthioglycol (NEOSTANN U-860: Nitto Kasei Corporation). The temperature was then raised to 80°C and maintained at 80°C with stirring. Analysis was performed using a Fourier transform infrared spectrophotometer until the reaction between the hydroxyl and isocyanate groups was confirmed to be complete, yielding polymer A1. 0.06 parts by mass of 3-mercaptopropyltrimethoxysilane (KBM-803: Shin-Etsu Chemical Co., Ltd.) was added as a storage stabilizer to 100 parts by mass of precursor polymer B1, resulting in a mixture containing polymer A1.

[0192] The number of reactive silicon groups in an average of 1 molecule of polymer A1, the number of groups i (-C(=O)NH-) in an average of 1 molecule, Mn, Mw / Mn, EO content and viscosity are shown in Table 2 (the same applies below).

[0193] (Example 1-1: Preparation of curable compositions)

[0194] A curable composition is prepared by mixing 100 parts by weight of the mixture containing polymer A1 with additive 1 shown in Table 3. The proportions shown in Table 3 are values ​​(parts by weight) relative to 100 parts by weight of the mixture containing polymer A (the same applies hereinafter).

[0195] The viscosity of the obtained curable composition, the results of the deep curing test, and the determination results of M50, Tmax and E of the cured product are shown in Table 4 (the same applies below).

[0196] (Example 1-2: Preparation of curable compositions)

[0197] In Example 1-1, additive 1 is replaced with additive 8. Otherwise, the curable composition is prepared in the same manner as in Example 1-1.

[0198] (Example 2: Preparation of polymer A2-1 and curable composition)

[0199] In Example 1, precursor polymer B1 was replaced with the same mass of precursor polymer B2. Otherwise, the same procedure as in Example 1 was followed to produce a mixture and a curable composition comprising polymer A2-1.

[0200] (Example 3: Preparation of polymer A2-2 and curable composition)

[0201] In Example 2, 3-isocyanate propyltrimethoxysilane was replaced with 3-isocyanate propylmethyldimethoxysilane. Otherwise, the same procedure as in Example 2 was followed to obtain a mixture containing polymer A2-2.

[0202] A curable composition is prepared by mixing 100 parts by weight of a mixture containing polymer A2-2 with additive 2 as shown in Table 3.

[0203] (Example 4: Preparation of polymer A2-3 and curable composition)

[0204] In Example 2, 3-isocyanate propyltrimethoxysilane was replaced with 1-isocyanate propylmethyldimethoxysilane. Otherwise, the same procedure as in Example 2 was followed to obtain a mixture containing polymers A2-3.

[0205] A curable composition is prepared by mixing 100 parts by weight of a mixture containing polymer A2-3 with additive 1 shown in Table 3.

[0206] (Examples 5-9: Preparation of polymers A3-A7 and curable compositions)

[0207] In Example 1, precursor polymer B1 was replaced with the same mass of precursor polymers B3 to B7. Otherwise, the same procedure as in Example 1 was followed to obtain a mixture containing polymers A3 to A7.

[0208] A curable composition is prepared by mixing 100 parts by weight of each of the mixtures containing polymers A3 to A7 with additive 1 shown in Table 3.

[0209] (Example 10: Preparation of polymer A'1 (comparative example) and curable composition)

[0210] In this example, a comparative polymer is produced by bonding reactive silyl groups to polyoxyethylene chains via urethane and urea bonds.

[0211] The TDI used in this example is toluene diisocyanate, and "TDI-80" is a mixture of 2,4-TDI / 2,6-TDI = 80 / 20 (mass ratio) (product name, manufactured by Nippon Polyurethane Co., Ltd.).

[0212] 2EHA is 2-ethylhexyl acrylate, and KBM602 (product name, manufactured by Shin-Etsu Chemical Co., Ltd.) is N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane.

[0213] First, the precursor polymer B1 was added to a pressure reactor, heated to 110°C, and subjected to vacuum dehydration. Then, after purging the reactor with nitrogen, the temperature was lowered to 80°C, and TDI-80 and dibutyltin dilaurate (DBTDL) were added, allowing the reaction to proceed for 7 hours. After confirming the NCO content to be 1.18 by titration, the reactor was cooled to room temperature to obtain a prepolymer with urethane bonds.

[0214] The molar ratio (NCO / OH) of the total number of isocyanate groups in TDI to the total number of hydroxyl groups in the precursor polymer B1 used is 2.

[0215] Next, according to Example 3 described in Japanese Patent Application Publication No. 11-100427, the aforementioned prepolymer was cooled to 50°C and mixed in a ratio of 2EHA:KBM602 = 184:206 (parts by mass). 25 parts by mass of the mixture, which had been kept at 60°C for 5 days, were added and reacted at 50°C for 1 hour under a nitrogen atmosphere. After confirming the disappearance of the isocyanate peak using a Fourier transform infrared spectrophotometer, the mixture was cooled to room temperature to obtain polymer A'1. 100 parts by mass of polymer A'1 were mixed with additive 1 shown in Table 3 to prepare a curable composition. The resulting curable composition had high viscosity and poor workability; therefore, no further investigation was conducted.

[0216] (Example 11: Preparation of polymer A'8 (comparative example) and curable composition)

[0217] In Example 10, the precursor polymer B1 was replaced with the same mass of precursor polymer B8. Otherwise, the same procedure as in Example 10 was followed to obtain polymer A'8.

[0218] A curable composition was prepared by mixing 100 parts by weight of polymer A'8 with additive 1 shown in Table 3.

[0219] (Examples 12-14: Preparation of polymers A'9-A'11 (comparative examples) and curable compositions)

[0220] In Example 1, the precursor polymer B1 was replaced with the same mass of precursor polymers B'9 to B'11. Otherwise, the same procedure as in Example 1 was followed to obtain a mixture containing polymers A'9 to A'11.

[0221] The polymer A'10 obtained in Example 13 was a solid at 25°C, and its viscosity could not be determined. Therefore, no further investigation was conducted.

[0222] In Examples 12 and 14, 100 parts by weight of each mixture containing polymer A'9 or A'11 were mixed with additive 1 shown in Table 3 to prepare curable compositions.

[0223] (Example 15: Preparation of polymer A16 and curable composition)

[0224] In Example 1, precursor polymer B1 was replaced with the same mass of precursor polymer B12. Otherwise, the same procedure as in Example 1 was followed to prepare a mixture and a curable composition containing polymer A16.

[0225] <Other Ingredients>

[0226] The additives listed in Table 3 are shown below.

[0227] WHITEN SB: Heavy calcium carbonate, a product of White Stone Industries.

[0228] CCR: Baiyanhua CCR colloidal calcium carbonate, a product name of Baishi Industrial Company.

[0229] R-820: Titanium oxide, a product name of Ishihara Sangyo Co., Ltd.

[0230] BALLOON 81GCA: Organic hollow spheres, a product name of Matsumoto Oils & Fats Co., Ltd.

[0231] Printex30: Carbon black, a product name from Orion Engineered Carbons.

[0232] CML35: Calcium oxide, a product name of Baishi Industrial Company.

[0233] DINP: Diisononyl phthalate.

[0234] UP-1171: ARUFON UP-1171, an acrylic polymer with a molecular weight of 3000, is the product name of Dong-A Synthetic Co., Ltd.

[0235] Polymer C1: Polypropylene glycol with Mn of 10000 (excluding EO).

[0236] DINCH: 1,2-cyclohexanedicarboxylic acid-diisononyl ester.

[0237] Polymer B1: Precursor polymer B1 obtained in manufacturing example 1.

[0238] SANSO CIZER EPS: 4,5-epoxycyclohexane-1,2-dicarboxylic acid-di-2-ethylhexyl ester, a product name of Shin Nippon Rikka Co., Ltd.

[0239] DISPARLON#6500: Hydrogenated castor oil thixotropic agent, product name of Kusumoto Chemical Co., Ltd.

[0240] IRGANOX 1010: Hindered phenolic antioxidant, a product name of BASF.

[0241] TINUVIN 326: Benzotriazole UV absorber, a product name of BASF.

[0242] TINUVIN 765: A hindered amine light stabilizer containing tertiary amines; a product name from BASF.

[0243] LA-63P: ADEKASTAB LA-63P, a product name of ADEKA company.

[0244] KBM-1003: Vinyltrimethoxysilane, a product name of Shin-Etsu Chemical Co., Ltd.

[0245] KBM-403: 3-glycidoxypropyltrimethoxysilane, a product name of Shin-Etsu Chemical Co., Ltd.

[0246] KBM-603: 3-(2-aminoethylamino)propyltrimethoxysilane, a product name of Shin-Etsu Chemical Co., Ltd.

[0247] Laurylamine: A reagent manufactured by Pure Chemical Company.

[0248] FARMIN CS: Coconut amine, a product name of Kao Corporation.

[0249] DEAPA: 3-Diethylaminopropylamine, manufactured by Tokyo Chemical Industry Co., Ltd.

[0250] TMP-3TMS: Tris(trimethyl)silyl derivative of trimethylolpropane.

[0251] Tung oil: an air-oxidizing and curing compound, manufactured by Kimura Corporation.

[0252] M-309: ARONIX M-309, a product name of Dong-A Synthetic Co., Ltd.

[0253] U-810: Dioctyltin catalyst, a product name of Nitto Kasei Corporation.

[0254] U-220H: Dibutyltin catalyst, a product name of Nitto Kasei Corporation.

[0255] DBTDL: Dibutyltin dilaurate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0256] TC750: Diisopropoxybis(ethylacetoacetic acid) titanium, ORGATIX TC750, a product name of Matsumoto Fine Chemicals Co., Ltd.

[0257] Neodecanoic acid: manufactured by Strem Chemicals.

[0258] Catalyst composition: A composition obtained by mixing 4 parts by mass of a mixture of STANOCT (stannous octanoate, brand name of Jifu Pharmaceutical Co., Ltd.) and laurylamine (reagent, manufactured by Pure Chemical Co., Ltd.) in a mass ratio of 6:1, 6 parts by mass of SANSO CIZER DINP (diisononyl phthalate, brand name of Shin Nippon Rikka Co., Ltd.), 15 parts by mass of WHITEN SB (heavy calcium carbonate, brand name of Baishi Calcium Industry Co., Ltd.), and 5 parts by mass of GROMACS LL (calcined kaolin, brand name of Takehara Chemical Co., Ltd.).

[0259] [Table 2]

[0260]

[0261] [Table 3]

[0262]

[0263] [Table 4]

[0264]

[0265] The curable compositions of Examples 1-1, 1-2, 2-9 and 15 have low viscosity, good workability, excellent deep curing properties, high Tmax and E values ​​of the cured products, and excellent strength and elongation.

[0266] In Examples 1-1, 1-2, 2-9 and 15, the additives can be changed to additives 1-16 shown in Table 3, and the same effect can be obtained.

[0267] (Refer to Example 1: Manufacturing of Polymer A12)

[0268] The reactor containing precursor polymer B1 was purged with nitrogen while maintaining the internal temperature at 50°C. 3-isocyanate propyltrimethoxysilane was added as a catalyst at an NCO / OH molar ratio of 0.97, along with bismuth octanoate (Nikka Octix-bismuth 25%: manufactured by Nippon Kagaku Sangyo Co., Ltd.). The temperature was then raised to 80°C and maintained at 80°C while stirring. The amount of the catalyst added was 0.0010 parts by mass relative to 100 parts by mass of precursor polymer B1. After 5 hours, the isocyanate peak was confirmed to have disappeared using Fourier transform infrared spectroscopy. The reactor was then cooled to room temperature to obtain polymer A12.

[0269] (See Example 2: Manufacturing of Polymer A13)

[0270] Precursor polymer B1 was replaced with the same mass of precursor polymer B'9, and the amount of bismuth octanoate (Nikka Octix-bismuth 25%: manufactured by Nippon Kagaku S.K. Co., Ltd.) added as a catalyst was set to 0.0025 parts by mass relative to 100 parts by mass of precursor polymer B'9. Otherwise, the procedure was the same as in Reference Example 1 to obtain polymer A13. It should be noted that, similar to polymer A12, the isocyanate peak disappeared after 5 hours, as confirmed by Fourier transform infrared spectroscopy.

[0271] (Storage stability)

[0272] Polymers A12 and A13 obtained in Reference Examples 1 and 2 were allowed to stand at 70°C for 7 days, and the increase in viscosity after standing relative to the viscosity before standing (viscosity increase rate) was measured. The viscosity increase rate is an indicator of storage stability; the lower the viscosity increase rate, the better the storage stability of the polymer. If the viscosity increase rate is below 200%, the storage stability is good. The viscosity increase rate of polymer A12 obtained in Reference Example 1 was 36%, and the viscosity increase rate of polymer A13 obtained in Reference Example 2 was 700%. Compared with polymer A12, polymer A13 has a higher viscosity increase rate and poorer storage stability.

[0273] (Refer to Example 3: Manufacturing of Polymer A14)

[0274] In Reference Example 1, the amount of bismuth octanoate (Nikka Octix-bismuth 25%: manufactured by Nippon Kagaku S.A.) added as a catalyst was changed to 0.0050 parts by mass relative to the precursor polymer B1 (100 parts by mass). Otherwise, the same procedure as in Reference Example 1 was followed to obtain polymer A14.

[0275] (Refer to Example 4: Manufacturing of Polymer A15)

[0276] In Reference Example 2, the amount of bismuth octanoate (Nikka Octix-bismuth 25%: manufactured by Nippon Kagaku Sangyo Co., Ltd.) added as a catalyst was changed to 0.0050 parts by mass relative to the precursor polymer B'9 (100 parts by mass). Otherwise, the same procedure as in Reference Example 2 was followed to obtain polymer A15.

[0277] (Reaction Time)

[0278] In Reference Examples 3 and 4, the reaction time was defined as the time from the addition of the catalyst until the reaction between the hydroxyl and isocyanate groups was confirmed to be complete. In Reference Example 3, this was 30 minutes. In Reference Example 4, it was 60 minutes. When an equal amount of catalyst was added relative to precursor polymer B1 or precursor polymer B'9, precursor polymer B1 reacted with the hydroxyl and isocyanate groups more rapidly than precursor polymer B'9.

Claims

1. An oxidized olefin polymer having a polyoxyethylene chain comprising oxyethylene groups and a reactive silicon group as shown in formula (1), wherein the reactive silicon group is bonded to the polyoxyethylene chain by means of an organic group comprising one group as shown in formula (i), wherein the number average molecular weight of the oxidized olefin polymer is 3,000 to 150,000, the molecular weight distribution is 2.00 or less, the oxyethylene content is 3 to 90% by mass, the number of reactive silicon groups per molecule is 0.5 or more on average, and the number of reactive silicon groups per molecule of the oxidized olefin polymer on average is the same as the number of groups represented by formula (i) on average per molecule. -C(=O)NH- (i) -SiX a R 3-a (1) In the formula (1), R represents a monovalent organic group with 1 to 20 carbon atoms, and is an organic group other than a hydrolyzable group; X represents a hydroxyl group or a hydrolyzable group; a represents an integer from 1 to 3. When a is 1, R can be chosen to be the same or different from each other. When a is 2 or 3, X can be chosen to be the same or different from each other.

2. The olefin oxide polymer according to claim 1, wherein it does not contain urea bonds.

3. A curable composition comprising the oxidized olefin polymer of claim 1 or 2.

4. The curable composition according to claim 3, wherein, The content of the oxidized olefin polymer is 5 to 90% by mass relative to the total mass of the curable composition.

5. The curable composition according to claim 3 or 4, further comprising a plasticizer.

6. The curable composition according to claim 5, wherein, The content of the plasticizer is 1 to 350 parts by weight relative to 100 parts by weight of the oxidized olefin polymer.

7. The curable composition according to claim 3 or 4, used as a sealing material or adhesive.

8. A cured product, which is a cured product of the curable composition according to any one of claims 3 to 7.

9. A method for manufacturing an oxidized olefin polymer, wherein, A precursor polymer is reacted with a compound of formula (2) such that the number of reactive silicon groups of formula (1) in an average of 0.5 or more per molecule is obtained to produce an oxidized olefin polymer. The precursor polymer has a polyoxyethylene chain containing oxyethylene groups and groups containing active hydrogen groups bonded to the polyoxyethylene chain. The number average molecular weight of the precursor polymer is 3,000 to 150,000, the molecular weight distribution is 2.00 or less, and the content of oxyethylene groups is 3 to 90% by mass. In the oxidized olefin polymer, the reactive silicon groups are bonded to the polyoxyethylene chain by means of an organic group containing one group of formula (i). The number of reactive silicon groups in an average of 1 molecule of the oxidized olefin polymer is the same as the number of groups represented by formula (i) in an average of 1 molecule. -SiX a R 3-a (1) -C(=O)NH- (i) In formula (1), R represents a monovalent organic group with 1 to 20 carbon atoms, and is an organic group other than a hydrolyzable group; X represents a hydroxyl group or a hydrolyzable group; a represents an integer from 1 to 3. When a is 1, R can be any two or different groups; when a is 2 or 3, X can be any two or different groups. O=C=N-Q 1 -SiX a R 3-a (2) In the above equation (2), Q 1 It is a divalent organic group with 1 to 20 carbon atoms; R, X, and a are the same as those in formula (1).

10. The manufacturing method according to claim 9, wherein, The total unsaturation of the precursor polymer is below 0.1 meq / g.

11. The manufacturing method according to claim 9 or 10, wherein, The precursor polymer is prepared by polymerizing a cyclic ether containing ethylene oxide with an initiator in the presence of a complex metal cyanide complex.

12. The manufacturing method according to claim 9 or 10, wherein, In the presence of a complex metal cyanide complex, a cyclic ether is polymerized with an initiator, and then ethylene oxide is polymerized in the presence of an alkali metal hydroxide to produce the precursor polymer.

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