JP5074095B2 - Method for producing organic polymer having trimethoxysilyl group at terminal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method of an organic polymer having a trimethoxysilyl group at a terminal end, proceeding exchange reaction to methoxy in a short time with a small catalyst amount, low in thickening due to side reaction in methoxy exchange reaction, low in thickening in polymer storage after trimethoxysilyl exchange and excellent in storage stability. <P>SOLUTION: The organic polymer having a trimethoxysilyl group at a terminal end is provided by reacting methanol with an organic polymer having a silicon group at a terminal end in the presence of a catalyst, which silicon group has three hydrolyzable groups including at least one hydrolyzable group other than methoxy on one silicon atom and which catalyst can be removed from the organic polymer and/or deactivated, and removing and/or deactivating the catalyst. The organic polymer excellent in storage stability and having a trimethoxysilyl group at a terminal is provided by adding a metal coordination compound in the above production steps on an optional timing. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a method for producing an organic polymer having a terminal trimethoxysilyl group.

  Various organic polymers having a silicon-containing group having a hydroxyl group or a hydrolyzable group directly bonded to silicon (hereinafter also referred to as a hydrolyzable group-containing silicon group) are cured and used as a sealing agent, an adhesive, etc. How to do is well known. For example, an organic polymer having a methyldimethoxysilyl group terminal and an organic polymer having a trimethoxysilyl group terminal are widely used as raw materials for moisture-curable compositions.

  Examples of the method for producing an organic polymer having a hydrolyzable group-containing silicon group at the end include, for example, a polymer having an ether type unsaturated group at the end having a hydrolyzable group-containing silicon group in the presence of a group VIII transition metal. A method of reacting with a silicon hydride compound is known (Patent Document 1). When an organic polymer having a trimethoxysilyl group at the end is produced by this method, trimethoxysilane is used as a raw material. However, since trimethoxysilane is a very unstable compound, it causes a disproportionation reaction and has a low boiling point. In addition, it may produce pyrophoric monosilane. In addition, trimethoxysilane has a problem that it is difficult to handle because it is extremely dangerous for the human body, particularly the eyes, and is difficult to obtain.

As other production methods, a method of reacting a silyl ether and a hydroxyl group-containing compound in the presence of a Lewis base catalyst (Patent Document 2), or a method of reacting a silyl ether and a hydroxyl group-containing compound in the presence of a tin catalyst or a titanium catalyst ( Patent Document 3) and a method of reacting a hydroxyl group-containing polyether with an isocyanate group terminal-containing compound (Patent Document 4) are known. However, the organic polymer having a trimethoxysilyl group at the end produced by these methods has problems such as an increase in viscosity during storage.
Japanese Patent Laid-Open No. 58-132022 JP 60-188390 A WO02 / 068501 Japanese Patent Laid-Open No. 9-124922

  An object of this invention is to provide the method of manufacturing the organic polymer which has the trimethoxysilyl group excellent in the storage stability from the easily available raw material.

As a result of intensive studies to solve the above problems, the present inventors have
Silicon in which three hydrolyzable groups containing at least one hydrolyzable group other than a methoxy group are bonded in the presence of a catalyst having a specific structure that can be removed and / or deactivated from the organic polymer (I) By reacting an organic polymer (II) having an atom at the end with methanol, an organic polymer having a trimethoxysilyl group at the end without using trimethoxysilane which is difficult to obtain and is difficult to obtain as a raw material What you can get.
-By adopting the above production method, the exchange reaction to the methoxy group proceeds in a short time even with a small amount of catalyst, and the viscosity increase due to the side reaction during the methoxy group exchange reaction is small.
・ The cause of the increase in viscosity of the organic polymer terminated with trimethoxysilyl group during storage is that the influence of metal impurities introduced by polymerization catalyst, neutralizing agent, reactor corrosion, etc. Addition of metal coordinating compounds such as ascorbic acid and / or its derivatives is effective to suppress the adverse effects of impurities.
-Even if a metal coordination compound is added at an arbitrary timing in the production process, the effect should be manifested.
As a result, the present invention has been completed.

That is, the present invention
A method for producing an organic polymer (I) having a trimethoxysilyl group end containing a metal coordination compound from an organic polymer (II) , which can be removed and / or deactivated from the organic polymer (I) In the presence of a catalyst, after reacting methanol with an organic polymer (II) having a terminal silicon atom bonded to three hydrolyzable groups containing at least one hydrolyzable group other than a methoxy group, Any of the production steps characterized in that the organic polymer (I) having a trimethoxysilyl group terminal is obtained by removal and / or deactivation, and the organic polymer (I) is obtained from the organic polymer (II) A metal coordinating compound is added at this timing .

  According to the production method of the present invention, an exchange reaction to a methoxy group proceeds in a short time even with a small amount of catalyst, and there is little increase in viscosity due to side reactions during the methoxy group exchange reaction. It is possible to produce an organic polymer having a trimethoxysilyl group at the terminal and excellent in storage stability with little thickening during storage of the organic polymer.

The present invention is a method for producing an organic polymer (I) having a trimethoxysilyl group at its end containing a metal coordination compound from the organic polymer (II) . Organic having terminal silicon atom bonded to three hydrolyzable groups containing at least one hydrolyzable group other than methoxy group in the presence of a catalyst that can be removed and / or deactivated from organic polymer (I) The catalyst is removed and / or deactivated after the polymer (II) is reacted with methanol and converted to a trimethoxysilyl group, and the organic polymer (I) is obtained from the organic polymer (II). The metal coordinating compound is added at an arbitrary timing in the manufacturing process at an arbitrary timing in the manufacturing process.

  The hydrolyzable group-containing silicon group at the end of the organic polymer (II) used in the production method of the present invention must have three hydrolyzable groups bonded to one silicon atom. The three hydrolyzable groups may be the same or different. However, since the present invention relates to a production method for converting a hydrolyzable group-containing silicon group other than a trimethoxysilyl group into a trimethoxysilyl group, all three hydrolyzable groups are methoxy groups. Not included in coalescence (II). That is, it is necessary that the three hydrolyzable groups bonded to one silicon atom include at least one hydrolyzable group other than the methoxy group. Specific examples of hydrolyzable groups other than methoxy group include, for example, halogen functional group, alkoxy group, acyloxy group, amide group, acid amide group, aminooxy group, ketoximate group, amino group, carbamoyl group, mercapto group, alkenyloxy. Examples include groups.

  Of these, the number of carbon atoms of the hydrolyzable group having a carbon atom is preferably 10 or less. In particular, a lower alkoxy group or an alkenyloxy group having 4 or less carbon atoms is preferable, and among them, an ethoxy group, a propoxy group, a butoxy group, a propenyloxy group, and the like are preferable from the viewpoint of storage stability and availability. More preferred is an ethoxy group.

  The number of hydrolyzable group-containing silicon groups at the end of the organic polymer (II) used in the present invention is not particularly limited, and even if it is at one end of the linear organic polymer (II), The organic polymer (II) having a branch may have any one or more of a plurality of ends.

  As the organic polymer (II) used in the present invention, a conventionally known main chain skeleton can be selected without any particular limitation. Specific examples include, but are not limited to, polyesters, polyethers, polyolefins, polyurethanes, polysiloxanes, poly (meth) acrylates, polycarbonates, and the like. From the viewpoint that the obtained organic polymer (I) having a trimethoxysilyl group terminal exhibits physical properties suitable for applications such as a sealing agent and an adhesive, preferably the main chain is essentially a polyether, polyolefin, polyurethane, poly An organic polymer composed of siloxane and poly (meth) acrylate, particularly preferably an organic polymer whose main chain is essentially a polyether. Of these, polyethers having polyoxypropylene and / or polyoxyethylene in the main chain are particularly preferred.

  Weight average molecular weight (Mw) and number average molecular weight of organic polymer (II) having a silicon atom at the terminal to which three hydrolyzable groups including at least one hydrolyzable group other than methoxy group used in the present invention are bonded The ratio (Mw / Mn) of (Mn) is not particularly limited, but it is 1.8 or less to increase the viscosity due to side reaction during methoxy exchange reaction and / or organic after exchange to trimethoxysilyl group. The polymer (I) is preferred because it has little thickening during storage. More preferably, it is 1.5 or less, Especially preferably, it is 1.4 or less.

  The molecular weight is not particularly limited, but Mn is preferably 5,000 to 50,000. When Mn is 5,000 or less, the cured product obtained from the organic polymer (I) having a trimethoxysilyl group terminal obtained becomes brittle, and when it is 50,000 or more, the viscosity becomes too high and handling becomes difficult. . Further, the number average molecular weight is particularly preferably from 10,000 to 35,000 from the viewpoint of the viscosity of the organic polymer (I) having a terminal trimethoxysilyl group.

  In the present invention, Mw and Mn mean polystyrene-converted Mn and Mw measured using tetrahydrofuran as a solvent by gel permeation chromatography (GPC).

In the case of an organic polymer whose main chain is essentially a polyether, a cesium compound, a metal porphyrin catalyst (Japanese Patent Laid-Open No. 61-197631), a double metal cyanide complex catalyst (US 3278457, US 3278458, US 32784596, US 3427256, US Pat. No. 4,055,188, US Pat. No. 4,721,818), a compound catalyst having a P═N bond (Japanese Patent Laid-Open No. 11-106500, H10-36499, H11-302371), an initiator such as a hydroxy compound having at least one hydroxyl group, an alkylene oxide, etc. Can be produced by polymerization. Among these catalysts, it is preferable to use a cesium compound, a composite metal cyanide complex catalyst or a compound catalyst having a P = N bond, which can obtain an oxyalkylene polymer having a high molecular weight and no color, and in particular, a composite metal cyanide complex catalyst is used. preferable. Further, among _double metal cyanide complex catalysts, an alcohol such as tert-butyl alcohol and / or ethylene glycol dimethyl ether (hereinafter referred to as “zinc ₃ [Co (CN) ₆ ] _2” (that is, zinc hexacyanocobaltate complex) is used as a catalyst skeleton. And those having a structure in which an ether such as glyme) is coordinated as an organic ligand.

  In addition, when using an oxyalkylene polymer having a relatively low molecular weight terminal hydroxyl group produced using a commonly used alkaline catalyst such as potassium hydroxide, it is possible to react with a polyvalent halogen compound such as methylene chloride. It is preferable to use a multimer of oxyalkylene polymers obtained by extending the molecular chain.

  The production method of the organic polymer (II) used in the present invention is not particularly limited, and a conventionally known production method can be selected. For example, a triethoxysilyl group-terminated polyether which is a preferred example of the organic polymer (II) used in the present invention is an unsaturated group such as an allyl group and / or a methallyl group at the end in the presence of a platinum catalyst and triethoxysilane. Can be obtained by hydrosilylation.

  The method for introducing an unsaturated group is not particularly limited, but the compound having an unsaturated group and a functional group is reacted with an active hydrogen group of an organic polymer to form an ether bond, an ester bond, a urethane bond, or a carbonate bond. And a method of introducing an unsaturated group into a side chain by adding an unsaturated group-containing epoxy compound such as allyl glycidyl ether and copolymerizing it when polymerizing alkylene oxide.

  The unsaturated group present at the terminal, for example, the allyl group and / or the methallyl group is 85% or more of the total molecular terminal to suppress an increase in viscosity during storage of the organic polymer (I) having a trimethoxysilyl group terminal. Therefore, it is preferably 90% or more, more preferably 95% or more.

  The amount of water in the reaction mixture when reacting methanol with the organic polymer (II) having a silicon atom bonded to the end of three hydrolyzable groups containing at least one hydrolyzable group other than a methoxy group, 1,000 ppm or less is preferable, more preferably 500 ppm or less, and still more preferably 300 ppm or less. Moisture reacts with hydrolyzable groups to form highly reactive silanol groups, which may cause an increase in the viscosity of the organic polymer (I, II) during the reaction and an increase in the viscosity during storage. Is preferred.

  Moreover, since methanol is a water-soluble organic solvent, it is very easy to absorb moisture, and the amount of water in methanol easily increases. Accordingly, the amount of water in methanol used in the present invention is preferably such that the amount of water in the reaction mixture after addition of methanol does not exceed the amount described above. In particular, 5,000 ppm or less is preferable, more preferably 2,000 ppm or less, still more preferably 1,000 ppm or less, and particularly preferably 500 ppm or less. The sufficiently dehydrated methanol can be used in the reaction without performing a dehydration treatment before charging. On the other hand, when methanol with insufficient dehydration is used and / or a reaction mixture with insufficient dehydration is subjected to dehydration treatment using various dehydrating agents, it can be used for the reaction. ) And methanol can also be present in the presence of a dehydrating agent.

  Dehydrating agents that adsorb water molecules (activated alumina, molecular sieves and other zeolites, magnesium sulfate and other inorganic salts), azeotropic with water and exhibit dehydrating effects (hexane, toluene, xylene, etc.), water and Chemical reaction (metal such as sodium metal, organometallic compound such as organolithium reactant, acid anhydride, acid halide, polyphosphoric acid, phosphorous compound such as diphosphorus pentoxide, orthoester compound such as orthoformate methyl ester, etc. And hydrolyzable group-containing silicon compounds such as acetal compounds and methyl silicates), but are not limited thereto, and those having a dehydrating ability can be used for dehydration of various raw materials and / or dehydration in a reaction mixture. .

  The amount of methanol used can be arbitrarily varied according to the methoxy exchange rate of the target organic polymer (I) having a trimethoxysilyl group at the end. That is, in order to obtain an organic polymer (I) having a trimethoxysilyl group having a high methoxy exchange rate at the terminal, a large amount of methanol is used, and an organic polymer having a trimethoxysilyl group having a low methoxy exchange rate at the terminal ( In order to obtain I), the amount of methanol used may be reduced.

  The amount of methanol used is not particularly limited. For example, the amount of methanol used is 3 to 30 parts in terms of viscosity during methoxy exchange reaction and / or methanol recovery time after methoxy exchange and / or methoxy exchange reaction rate. More preferred is 5 to 25 parts, and still more preferred is 10 to 20 parts. In addition, the amount of catalyst used may be varied according to the amount of methanol to stabilize the methoxy exchange reaction rate and / or to suppress the increase in viscosity during storage of the organic polymer (I) having a trimethoxysilyl group at the end. Is possible.

  The catalyst used in the present invention needs to be able to be removed and / or deactivated from the organic polymer (I). If the amount of the catalyst remaining in the organic polymer (I) after methoxy exchange is large, the viscosity tends to increase during storage, and it is necessary to remove and / or deactivate the catalyst to reduce the remaining amount. The amount of catalyst remaining in the organic polymer (I) after methoxy exchange is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 2 ppm or less, and particularly preferably 1 ppm or less.

  As a catalyst for converting a hydrolyzable group of a hydrolyzable group-containing silicon group into another hydrolyzable group, generally an acid, a base, a metal alkoxide, and the like are known, but in the present invention, Among these known catalysts, an acid, particularly a strong acid such as a Bronsted acid, is preferred because it can be exchanged for a methoxysilyl group in a short time even with a small amount of use.

  Specific examples of such catalysts include hydrogen chloride, hydrogen bromide hydrogen halide compounds, sulfuric acid, nitric acid, trihaloacetic acid such as trifluoromethanesulfonic acid, trifluoroacetic acid, and perchloric acid. Examples include, but are not limited to, compounds that dissociate. In addition, it is preferably a catalyst that can be removed from the organic polymer (I) by devolatilization under reduced pressure, since the catalyst remaining in a trace amount in the organic polymer (I) can be further removed even after the catalyst is deactivated. Its boiling point under atmospheric pressure is 150 ° C. or less, more preferably 100 ° C. or less, and particularly preferably 70 ° C. or less. From the viewpoint of high activity and few side reactions, hydrogen halide compounds such as hydrogen chloride and hydrogen bromide are preferred, and hydrogen chloride is particularly preferred.

  As a method for adding the catalyst used in the present invention, a conventionally known method can be selected without any particular limitation. Specific examples of the catalyst addition method include a method of adding a liquid and / or solid catalyst, a method of blowing a gaseous catalyst, a method of generating a catalyst in a reaction mixture, and the like. Not.

  When the catalyst is added, the catalyst and / or catalyst precursor is dissolved in an organic solvent to reduce the concentration of the catalyst, thereby increasing the local thickening of the organic polymer (II) immediately after the addition of the catalyst. It is preferable in terms of suppression. When the catalyst is added without being diluted with an organic solvent or the like, rapid thickening, that is, gelation may occur at a local high concentration catalyst site immediately after the catalyst addition. The catalyst concentration is not particularly limited as long as local gelation can be suppressed, but the preferred catalyst concentration is 5 wt% or less, more preferably 2 wt% or less, further preferably 1 wt% or less, particularly Preferably it is 0.5 wt% or less.

  Specific examples of the solvent include non-reactive organic solvents such as hexane and toluene that do not have exchange activity with hydrolyzable groups, and methanol as a raw material that has exchange activity with hydrolyzable groups. When the solvent forms an azeotropic composition, it is desirable that the solvent has an azeotropic temperature that can be removed from the organic polymer (I) by devolatilization under reduced pressure.

  Specific examples of the method for generating the catalyst used in the present invention in the reaction mixture include, for example, coexistence of halosilanes when reacting the organic polymer (II) having a hydrolyzable group-containing silicon group at the terminal with methanol. Examples of the method include reacting a raw material and / or a trace amount of water in the organic polymer (II) with halosilanes and / or generating hydrogen halide in the reaction mixture by reaction of methanol and halosilanes. . In the present invention, halosilanes refer to compounds in which a halogen functional group is bonded to a silicon atom. The halosilanes can already be present when the organic polymer (II) having a hydrolyzable group-containing silicon group at the terminal is produced. For example, when triethoxysilane is used as a hydrolyzable group-containing silicon compound, trichlorosilane which is a raw material for synthesizing triethoxysilane, dichloroethoxysilane which is a synthesis intermediate, monochlorodiethoxysilane, etc. are allowed to coexist. It is also possible to keep it. In addition, when reacting with a trace amount of water in the raw material and / or organic polymer, halosilanes are also preferable in that they can function as a dehydrating agent and can suppress thickening during and / or after the methoxy exchange reaction. Specific examples of halosilanes include, but are not limited to, chloroalkylsilanes such as monochlorosilane, dichlorosilane, and trichlorosilane having various alkyl groups. In order to suppress the increase in viscosity of the organic polymer (I, II) during the reaction and the increase in viscosity during storage, monohalotrialkylsilanes having one hydrolyzable group are preferred, and particularly monochlorotrialkylsilane is preferred. preferable.

  The amount of catalyst used in the present invention is preferably 500 ppm or less, more preferably 300 ppm or less, still more preferably 100 ppm or less, and particularly preferably 50 ppm or less. When a large amount of the catalyst is used, the viscosity of the organic polymer (I, II) is likely to increase during the reaction, and surprisingly, the organic polymer (I) is removed even after the catalyst is removed and / or deactivated from the organic polymer (I). It tends to cause an increase in viscosity during storage of the combined (I). For this reason, it is preferable that the used amount and / or generated amount of the catalyst used is small.

  Specific examples of the method for removing the catalyst from the organic polymer (I) include devolatilization under reduced pressure and a method of deactivating the catalyst vapor volatilized to the gas phase part by heating in the gas phase part. It is not limited.

  Specific examples of the method for deactivating the catalyst include reaction with an epoxy compound, reaction with a basic compound, and the like, but are not limited thereto. A step of producing an organic polymer (II) having a terminal silicon atom to which three hydrolyzable groups including at least one hydrolyzable group other than a methoxy group are bonded, and the organic polymer (II) and methanol Is carried out in the same reactor, the basic group VIII transition metal catalyst used in the production of the organic polymer (II) having a hydrolyzable group-containing silicon group at the terminal is not deactivated. It is preferable to deactivate by reaction with an epoxy compound rather than a deactivator.

  Specific examples of the epoxy compound include aliphatic epoxy compounds such as propylene oxide, ethylene oxide, 2,3-butylene oxide, and isobutylene oxide, methyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and 2-ethyl. Epoxidation having 4 to 30 carbon atoms represented by glycidyl ethers such as xylglycidyl ether and polypropylene glycol diglycidyl ether, bicolox 10, bicolox 12, bicolox 14, bicolox 16 and bicolox 18 (all of which are manufactured by Arkema). Terpen oxides such as α-olefins, α-pinene oxide, limonene monooxide, limonene dioxide, epoxidized soybean oil, epoxidized sub-oxide Epoxidized vegetable oils such as linseed oil, sansosizer E-6000, sansosizer E-4030 (all of which are manufactured by Shin Nippon Rika Co., Ltd.) and the like, epoxidized fatty acid esters, sansosizer E-PS, sansosizer Examples thereof include alicyclic epoxy compounds represented by E-PO, Sansizer nE-PS (all of which are manufactured by Shin Nippon Chemical Co., Ltd.). These may be used alone or in combination of two or more. Of these, epoxy compounds synthesized by an oxidation reaction such as epoxidized α-olefins, epoxidized vegetable oils, epoxidized fatty acid esters, and alicyclic epoxy compounds are preferable for suppressing thickening during storage. . In particular, epoxidized vegetable oils are preferable in view of toxicity of the epoxy compound.

  It is considered that the epoxy compound used for deactivation is preferably used in a large excess with respect to the catalyst amount in order to deactivate the catalyst efficiently. Furthermore, it is expected that thickening during storage of the organic polymer (I) having a trimethoxysilyl group at the terminal can be suppressed by efficiently deactivating the catalyst. Surprisingly, however, in the present invention, it is found that excessive use of the epoxy compound used for deactivation tends to cause thickening during storage of the organic polymer (I) having a trimethoxysilyl group at the terminal. It was. Accordingly, the amount of the epoxy compound used for deactivation is preferably 100 mole equivalents or less, more preferably 50 mole equivalents or less, and even more preferably 25, of the oxirane oxygen of the epoxy compound with respect to the catalyst use amount. It is not more than molar equivalent, and particularly preferably not more than 10 molar equivalent.

  In the present invention, it is stored that the residual amount of the catalyst is managed by measuring the pH of the organic polymer (I) having a trimethoxysilyl group at the end obtained after the catalyst is removed and / or deactivated. It is preferable for suppressing thickening inside. The pH of the organic polymer (I) having a trimethoxysilyl group at the end as used herein can be measured by a method based on JIS K1557. It is preferable to remove and / or deactivate the catalyst so that the pH measured by a method based on JIS K1557 is 6-8.

  In the present invention, an acid can be used as a catalyst, but the acid may cause corrosion of the reactor. It has been found that when the reactor corrodes, metal impurities generated by the corrosion are mixed in the organic polymer (I), and the organic polymer (I) may thicken during storage due to the metal impurities. When the reaction is carried out in a reactor made of stainless steel such as SUS316, which is generally used commercially, corrosion of the reactor proceeds depending on conditions such as catalyst type and / or concentration, reaction temperature and / or time. The iron element, which is the main element of stainless steel, elutes and is mixed as an impurity in the organic polymer (I) having a trimethoxysilyl group at its terminal. Thereafter, the iron compound mixed in as a metal impurity functions as a curing catalyst and is considered to cause thickening during storage. Therefore, the amount of the iron element contained in the organic polymer (I) having a trimethoxysilyl group at the terminal is preferably 6 ppm or less, more preferably 3 ppm or less, still more preferably 1 ppm or less, particularly Preferably it is 0.1 ppm or less.

  Therefore, when the trimethoxysilyl group-terminated organic polymer (I) is produced in an environment that corrodes a reactor made of stainless steel or the like, in the present invention, in the reaction vessel in which the inner surface of the reactor is made of a corrosion-resistant material. It is preferable to produce an organic polymer (I) having a trimethoxysilyl group at the end. The corrosion resistant material is preferably a pure metal having corrosion resistance against acids such as nickel, titanium, molybdenum, chromium, tantalum, or various alloys containing these metal elements. Of these, nickel-chromium-molybdenum alloys such as Hastelloy C276 and nickel-molybdenum alloys such as Hastelloy B are preferred in terms of corrosion resistance, durability, and thermal conductivity. It is also possible to line the reactor inner surface with a corrosion-resistant material such as glass or fluororesin to make the reactor inner surface a corrosion-resistant material, which is particularly advantageous in terms of cost. Moreover, it is also possible to use these materials in combination.

  In the present invention, a step of producing an organic polymer (II) having a terminal silicon atom bonded to three hydrolyzable groups containing at least one hydrolyzable group other than a methoxy group and the organic polymer ( The step of reacting II) and methanol may be performed in different reaction vessels or in the same reaction vessel. From the viewpoint of equipment cost, it is preferable to carry out in the same reaction vessel.

Reaction of methanol with an organic polymer (II) having a terminal silicon atom bonded with three hydrolyzable groups containing at least one hydrolyzable group other than a methoxy group is, for example, a triethoxysilyl group is terminated. In the case of the reaction with the organic polymer (II) contained in 1H-NMR, it can be traced with the disappearance rate of the ethoxysilyl group peak using ¹ H-NMR. Moreover, it is also possible to obtain | require the exchange rate to a methoxy group by quantifying hydrolysable groups other than a methoxy group as alcohol by the gas chromatograph (GC) analysis of the organic polymer (I) alcohol solution after reaction. . The methoxy exchange rate of the organic polymer (I) having a trimethoxysilyl group at the end of the present invention may not be 100%, preferably 50% or more, more preferably 75% or more, particularly preferably 85% or more. is there.

  In applications where an improvement in the curing rate of the organic polymer (I) is required, it is preferably 90% or more, particularly preferably 95% or more.

  The organic polymer (I) having a trimethoxysilyl group at the end obtained by the present invention contains a metal coordination compound as an essential component.

Here, the metal coordinating compound is a compound capable of coordinating with a metal ion or a metal atom. Coordination is defined as “donation of an electron pair from an electron pair donor to an electron pair acceptor” as described in the Dictionary of Chemistry (1st edition; published by Tokyo Kagaku Doujin). . The book also states that “usually the term coordination is used when a metal ion or metal atom is an electron-pair acceptor. An entity that acts as an electron-pair donor is called a ligand. As what can be obtained, there are molecules having lone electron pairs such as NH ₃ , P (C ₆ H ₅ ) ₃ , S (CH ₃ ) ₂ and anions such as Cl ⁻ and NCS ⁻ . Yes. Therefore, the metal coordinating compound used in the present invention is a compound serving as a ligand or a compound including a structure that can serve as a ligand with respect to a metal ion or a metal atom. As such a metal coordination compound, a chelating agent, a hydroxyl group-containing compound, or a compound having a phenolic hydroxyl group is preferable. The chelating agent referred to here is, as described in the Chemical Dictionary (1st edition; published by Tokyo Kagaku Doujin), “having a plurality of donor atoms that bind to a metal ion to form a chelate compound. Defined as "reagent". According to the same book, chelation refers to “a compound in which two ligand atoms exist in a ligand and both coordinate to one ion or atom (usually a metal ion or a metal atom) to form a cyclic compound. (Chelate compound) is formed, not only when a monocyclic compound is made, but also when there are 3 or more coordination atoms (two or more rings can be formed).

The chelating agent is represented by the general formula (1) in terms of coordination ability to metal and availability.
RC (O) CH ₂ C (O) R (1)
(In the formula, each R independently represents at least one selected from the group consisting of a monovalent alkyl group, cycloalkyl group, aryl group, heterocyclic group, or aralkyl group, and in these functional groups, A compound represented by (which may have a substituent such as a halogen group) is preferred.

  Such chelating agents include acetylacetone, benzoyltrifluoroacetone, dipivaloylmethane, furoyltrifluoroacetone, hexafluoroacetylacetone, hexafluorobutanoylpivaloylmethane, pivaloyltrifluoroacetone, trifluoroacetylacetone, Examples include thienoyl trifluoroacetone. Examples of the compound having a phenolic hydroxyl group include catechol, 8-quinolinol, nitrophenol, dinitrophenol, and trinitrophenol.

  The metal coordinating compound used in the present invention is preferably a compound that does not contain a carboxyl group because it is highly effective in suppressing thickening during storage of the organic polymer (I) having a trimethoxysilyl group at the end. In the case of a compound containing a carboxyl group, as the amount added increases, the possibility that protons with high acidity will function as a curing catalyst for the organic polymer (I) having a trimethoxysilyl group end increases. The effect of suppressing thickening during storage of the organic polymer (I) at the end may be reduced.

  Specific examples of the metal coordination compound containing no carboxyl group include carboxylic anhydrides such as succinic anhydride, phthalic anhydride, itaconic anhydride, maleic anhydride, glutaric anhydride, benzoic anhydride, ascorbic acid or the like. Derivatives are mentioned, but ascorbic acid or a derivative thereof that does not generate a carboxyl group by hydrolysis is particularly preferable. Ascorbic acid or a derivative thereof includes L-ascorbic acid, isoascorbic acid which is a structural isomer thereof, and ester derivatives thereof (specifically, L-ascorbyl luminate, L-ascorbyl stearate, 2-ethylhexanoic acid) L-ascorbyl, isoascorbyl palmitate, isoascorbyl stearate or isoascorbyl 2-ethylhexanoate), their phosphate derivatives (specifically, L-ascorbic acid monophosphate, L-ascorbic acid diphosphate) Esters, L-ascorbic acid triphosphates, isoascorbic acid monophosphates, isoascorbic acid diphosphates, or isoascorbic acid triphosphates), their ether derivatives (specifically, L-ascorbic acid-2) Glucoside or isoascorbic acid-2-glucoside) and alkali metals such as sodium and potassium, alkaline earth metal salts such as magnesium, calcium and barium, and various metals such as polyvalent metal salts such as aluminum Among them, L-ascorbic acid, isoascorbic acid, or a metal salt thereof is particularly preferable.

  The addition method of the metal coordination compound is not particularly limited, but it may be added as it is or may be added after being dissolved in a solvent. In the case of a solid, it may be added by heating and melting at a temperature equal to or higher than the melting point, or after addition as a solid, the organic polymer (I, II) may be heated and dissolved. Moreover, it is preferable to heat-process after adding a metal coordinating compound, in order to raise the effect which suppresses the thickening in storage of the organic polymer (I) which has a trimethoxysilyl group at the terminal. When heat-treating, the heating temperature is preferably 50 to 150 ° C, more preferably 70 to 110 ° C. When the heating temperature is less than 50 ° C., the effect of suppressing the thickening during storage of the organic polymer (I) having a trimethoxysilyl group at the end may not be sufficient. When the heating temperature exceeds 150 ° C., the organic polymer ( Thermal degradation of I, II) may occur.

  The metal coordination compound can be added at an arbitrary timing in the production process. However, the step after the step of removing and / or deactivating the catalyst is particularly preferable because the effect of suppressing the thickening during storage of the organic polymer (I) having a trimethoxysilyl group terminal is large.

  Although the addition amount of the metal coordination compound used in the present invention is not particularly limited, it is preferably 1 ppm to 500 ppm, more preferably 5 ppm to 200 ppm with respect to the organic polymer (I) having a trimethoxysilyl group at the terminal. Furthermore, 10 ppm to 150 ppm is particularly preferable. If it is 1 ppm or less, the effect of suppressing the thickening during storage of the organic polymer (I) having a trimethoxysilyl group at the terminal is small, and if it is 500 ppm or more, there is a problem that the organic polymer (I) is colored. In addition, the metal coordination compound which can be used by this invention may be used independently, and may be used in combination of multiple.

  Examples of the metal component of the metal impurity contained in the organic polymer (I) having a trimethoxysilyl group at the terminal include, for example, an organic polymer whose main chain is essentially a polyether, and a composite metal cyanide used as a polymerization catalyst. Such as zinc and cobalt components in the fluoride complex catalyst, and iron, molybdenum, nickel, etc. in the equipment materials mixed by corrosion of the reactor when synthesizing the organic polymer (I) having a trimethoxysilyl group at the terminal A metal is mentioned. Metals such as iron and molybdenum in equipment materials mixed due to corrosion of the reactor may function as a curing catalyst that causes thickening during storage of the organic polymer (I) terminated with a trimethoxysilyl group. Therefore, when a metal coordinating compound is added to the organic polymer (I) having a trimethoxysilyl group at its end containing such a metal impurity, the metal coordinating compound is coordinated with the metal impurity and / or It is considered that the function as a curing catalyst for metal impurities is reduced by chelation, and the effect of suppressing thickening during storage is brought about.

  The organic polymer (I) having a trimethoxysilyl group at the end obtained in the present invention is particularly useful as a raw material for an elastic sealant and an adhesive, and by incorporating a curing agent and various fillers, It can be used as a sealant and adhesive for automobiles and roads.

  It can be used as a raw material for contact adhesives as well as ordinary adhesives. Furthermore, it is also useful as a raw material for food packaging materials, cast rubber materials, molding materials, paints and the like.

Next, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. Below, a part shows the weight part with respect to an organic polymer. Further, as described above, Mn and Mw / Mn are obtained as polystyrene-converted values measured by tetrahydrofuran using GPC as a solvent, and the ratio of unsaturated groups present at the terminals is assumed that the terminal structure is a hydroxyl group and an unsaturated group. Then, the amount of hydroxyl groups was determined by a method based on JIS K1557, and the amount of unsaturated groups was determined by a method based on JIS K0070, and the ratio of unsaturated groups present at the terminals was determined based on the respective values. Also, exchange rate to methoxy groups was determined by the disappearance rate of ethoxy silyl group using ^{1 H-NMR.}

The pH was measured by a method according to JIS K1557. Specifically, 10 g of an organic polymer or 10 g of an organic polymer methanol solution was measured in terms of an organic polymer, and this was 50 ml of isopropanol / water = 100/30 ( (Vol ratio) It was dissolved in a mixed solvent, and the pH value of the organic polymer was measured.
The viscosity was measured at 23 ° C. using an E-type viscometer, and the viscosity increase ratio after storage was evaluated as a viscosity ratio before and after storing an organic polymer having a trimethoxysilyl group at the terminal at 80 ° C. for 2 weeks.

Example 1
Using polyoxypropylene triol with Mn = 3,700 as an initiator, propylene oxide was polymerized using a zinc hexacyanocobaltate complex catalyst to obtain polyoxypropylene triol. A sodium methoxide / methanol solution is added thereto to alkoxide the end, and then allyl chloride is added and reacted to convert the terminal hydroxyl group to an allyloxy group. Hexane and water were added to and mixed with this terminal allyloxy group polyoxypropylene triol for desalting and purification, and then hexane was distilled off under reduced pressure to obtain an allyl group-terminated polyoxypropylene having an allylation rate of 98%. Furthermore, triethoxysilane was reacted using a divinyltetramethylsiloxane platinum complex as a catalyst, and Mn = 26,000, Mw / Mn = 1.28 having an average of 2.2 triethoxysilylpropyl groups per molecule at the terminal. Organic polymer A was synthesized.

(Example 2)
100 parts of the organic polymer A and 2 parts of hexane were added to a glass pressure-resistant reaction vessel containing a metal part made of SUS316 in the reaction vessel, and azeotropic dehydration was performed at 90 ° C. for 1 hour. Thereafter, 600 ppm (12 ppm as hydrogen chloride) of 2 wt% hydrogen chloride-methanol solution prepared by diluting 20 parts of methanol and 36 wt% hydrochloric acid aqueous solution with methanol was added to the organic polymer A at 90 ° C. Was allowed to react for 1 hour while controlling the temperature to be 70 ° C. to obtain a methanol solution of an organic polymer A1 having a pH of 5.3. Thereafter, 580 ppm of epoxidized soybean oil (Sanso Sizer E-2000H manufactured by Shin Nippon Rika Co., Ltd.) was added (equivalent to 7.4 mol of oxirane oxygen with respect to hydrogen chloride), and the catalyst was deactivated by stirring for 1 hour. After obtaining a methanol solution of organic polymer A1 having a pH of 7.0, it was devolatilized under reduced pressure at 90 ° C. for 1 hour, and then 30 ppm of ascorbic acid (special grade reagent manufactured by Nacalai Tesque Co., Ltd.) was added. 95% of organic polymer A1 was obtained.

(Example 3)
A reaction was performed in the same manner as in Example 2 except that the amount of ascorbic acid to be added was 150 ppm, to obtain an organic polymer A2.

(Comparative Example 1)
Except not adding ascorbic acid, it reacted like Example 2 and obtained organic polymer A3.

Example 4
100 parts of the organic polymer A and 2 parts of hexane were added to a glass pressure-resistant reaction vessel in which the amount of metal parts made of SUS316 was small compared to Example 2, and azeotropic dehydration was performed at 90 ° C. for 1 hour. Thereafter, after adding 60 ppm (12 ppm as hydrogen chloride) of 2 wt% hydrogen chloride-methanol solution prepared by diluting methanol 20 parts and 36 wt% hydrochloric acid aqueous solution with methanol to 90 ° C. organic polymer A, 30 ppm of ascorbic acid (special grade reagent manufactured by Nacalai Tesque Co., Ltd.) was added and reacted for 1 hour while controlling the temperature so that the internal temperature became 70 ° C., thereby obtaining a methanol solution of organic polymer B1 having a pH of 5.3. Thereafter, 580 ppm of epoxidized soybean oil (Sanso Sizer E-2000H manufactured by Shin Nippon Rika Co., Ltd.) was added (equivalent to 7.4 mol of oxirane oxygen with respect to hydrogen chloride), and the catalyst was deactivated by stirring for 1 hour. After obtaining a methanol solution of organic polymer B1 having a pH of 7.0, it was devolatilized at 90 ° C. for 1 hour to obtain organic polymer B1 having a methoxy exchange rate of 95%.

(Example 5)
Except that the timing of ascorbic acid addition was after catalyst deactivation, the reaction was carried out in the same manner as in Example 4 to obtain an organic polymer B2.

(Example 6)
A reaction was performed in the same manner as in Example 5 except that the amount of ascorbic acid to be added was 10 ppm, to obtain an organic polymer B3.

(Comparative Example 2)
Except not adding ascorbic acid, it reacted like Example 4 and obtained organic polymer B4.

Claims (5)

A method for producing an organic polymer (I) having a terminal trimethoxysilyl group containing a metal coordination compound from the organic polymer (II) ,
Organic having terminal silicon atom bonded to three hydrolyzable groups containing at least one hydrolyzable group other than methoxy group in the presence of a catalyst that can be removed and / or deactivated from organic polymer (I) After reacting the polymer (II) with methanol, the catalyst is removed and / or deactivated to obtain an organic polymer (I) having a trimethoxysilyl group terminal, and this organic polymer ( II) A metal coordinating compound is added at an arbitrary timing in the production process for obtaining the organic polymer (I) from II .   The production method according to claim 1, wherein the organic polymer (I) having a trimethoxysilyl group at the terminal contains a metal impurity. The production method according to claim 1 or 2, wherein the metal coordination compound is a compound having no carboxyl group.   The method according to any one of claims 1 to 3, wherein the metal coordination compound is ascorbic acid and / or a derivative thereof.   The method according to any one of claims 1 to 4, wherein a heat treatment at 50 ° C or higher is performed after the metal coordination compound is added.