CN106317099A - Aminoalkylalkoxydisiloxane compound and method for preparing the same - Google Patents

Aminoalkylalkoxydisiloxane compound and method for preparing the same Download PDF

Info

Publication number
CN106317099A
CN106317099A CN201610507105.5A CN201610507105A CN106317099A CN 106317099 A CN106317099 A CN 106317099A CN 201610507105 A CN201610507105 A CN 201610507105A CN 106317099 A CN106317099 A CN 106317099A
Authority
CN
China
Prior art keywords
formula
disiloxane
double
compound
aminoalkylalkoxydisiloxane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610507105.5A
Other languages
Chinese (zh)
Inventor
川上雅人
久保田透
本间孝之
殿村洋
殿村洋一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Chemical Co Ltd
Original Assignee
Shin Etsu Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shin Etsu Chemical Co Ltd filed Critical Shin Etsu Chemical Co Ltd
Publication of CN106317099A publication Critical patent/CN106317099A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1896—Compounds having one or more Si-O-acyl linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silicon Polymers (AREA)

Abstract

The invention relates to an aminoalkylalkoxydisiloxane compound and a method for preparing the same. The invention concretely provides an aminoalkylalkoxydisiloxane compound shown in a formula (1). With the aminoalkylalkoxydisiloxane compound, the effects of amino groups and alkoxy silyl groups are given full play in use, and volatile organic compounds generated in use are reduced, so that the aminoalkylalkoxydisiloxane compound is useful when serving as silane coupling agent, resin additive, surface treatment agent, coating additive, adhesive and the like. (In the formula (1), R1 and R2 are the monovalent hydrocarbon radicals of unsubstituted [ of the carbon numbers 1-20 ], or substitution which may also contain a hetero atom among a formula, it may be respectively the same or different, and R1 and R2 may form a ring with the nitrogen atom which is combined each other and these combine.) R3 is the straight chain shape of the carbon numbers 1-20 which may also contain a hetero atom, and a branched state or annular divalent hydrocarbon group, R4 and R5 are the monovalent hydrocarbon radicals of the carbon numbers 1-10, and n is 0 or 1.

Description

Aminoalkylalkoxy disiloxane compound and manufacture method thereof
Technical field
The present invention relates to the new alkoxyl disiloxane compound with 2 amino and manufacture method thereof.This new change Compound is useful as silane coupler, resin additive, coating additive, bonding agent, fibre finish, surface conditioning agent 's.
Background technology
There is the silane compound of amino as silane coupler, resin additive, coating additive, bonding agent, fiber Inorganic agent, surface conditioning agent are useful.As the silane compound with amino, it is known to 3-aminopropyl trimethoxy Silane etc., but its intramolecular contains multiple water-disintegrable functional group, the VOC (VOC) produced when therefore using Amount is many, worries to cause burden to environment.
In order to solve this problem, exploitation send as an envoy to two molecules 3-aminopropyltrialkoxy silanes condensation 1,3- Double (3-aminopropyl)-1,1,3,3-tetraalkoxy disiloxane (non-patent literature 1).Such alkoxyl disiloxane Compound molecular weight compared with corresponding monomer is big, and therefore volatility reduction is easily processed.Additionally, due in every a part Alkoxyl increases, and therefore, thus produced effect strengthens by expecting (patent documentation 1).And then, the VOC of per unit weight Also reducing compared with monomer, the burden therefore caused to environment is the least.
Prior art literature
Patent documentation
Patent documentation 1: No. 4287326 description of U.S. Patent No.
Non-patent literature
Non-patent literature 1:R.Zhongjie, S.Diaming, L.Huihui, M.Dongge, Z.Jianming, Y.Shouke.Shynthesis of Dibenzothiophene-Containing Ladder Polysilsesquioxane As a Blue Phosphorescent Host Material.Chemistry A European Journal.2012, Vol.18, Issue 13, p.4115-4123.
Summary of the invention
The problem that invention is to be solved
But, up to now, the alkoxyl disiloxane compound developed is the change with primary amino radical or secondary amino group Compound, nitrogen has rich reactive active hydrogen.Therefore, Epoxy Precursors, polyurethane precursor, carbonic ester tree are being added to Cause side reaction etc. time in fat etc., go wrong the most repeatedly.Such as, when adding above-claimed cpd in Epoxy Precursors, Above-claimed cpd self causes epoxy ring-opening, therefore causes resin to solidify.Additionally, at polyurethane precursor, i.e. contain Carbimide. When the compound of ester group adds above-claimed cpd, the skeleton of carbamate resins self is imported into alkoxyl two silica Hydride compounds.And then think, when adding above-claimed cpd in carbonate resin, carbonic ester skeleton is changed into amide backbone, leads Cause resin is decomposed.Therefore, seek to there is the characteristic of alkoxyl disiloxane compound and can be used in the change of multiple use Compound.
The present invention makes in view of the foregoing, its object is to, it is provided that one has alkoxyl disiloxane The characteristic of compound and can be used in aminoalkylalkoxy disiloxane compound and the manufacture method thereof of multiple use.
For solving the means of problem
The present inventor has been repeated further investigation to solve above-mentioned problem, it was found that do not have the ammonia of active hydrogen Yl alkyl alkoxy disiloxane compound can use in multiple use, thus completes the present invention.
Therefore, the present invention provides following shown aminoalkylalkoxy disiloxane compound and manufacture method thereof.
(1) by the aminoalkylalkoxy disiloxane compound shown in following formula (1).
[chemical formula 1]
(in formula, R1、R2For can distinguishing containing the unsubstituted or substituted 1 valency alkyl of heteroatomic carbon number 1～20 Identical or different, R1And R2Ring is formed together with the nitrogen-atoms that can bond together thus be bonded with them.R3Miscellaneous for containing The straight-chain of carbon number 1～20 of atom, branched or ring-type divalent alkyl, R4、R5For 1 valency alkyl of carbon number 1～10, n be 0 or 1。)
(2) described in (1) by the manufacture method of the aminoalkylalkoxy disiloxane compound shown in formula (1), its It is characterised by, makes to be condensed by the amino compound hydrolysis shown in following formula (2).
[chemical formula 2]
(in formula, R1～R5And n is same as described above.)
(3) described in (1) by the manufacture method of the aminoalkylalkoxy disiloxane compound shown in formula (1), its It is characterised by, makes by the haloalkyl alkoxyl disiloxane compound shown in following formula (3) and by following formula (4) Suo Shi Amines reaction.
[chemical formula 3]
(in formula, R3～R5And n is same as described above, X is chlorine, bromine or iodine.)
[chemical formula 4]
(in formula, R1、R2Same as described above.)
The effect of invention
The aminoalkylalkoxy disiloxane compound that the present invention provides can give full play to amino and alkane in use The VOC produced when the effect of epoxide silicyl and use is few, therefore adds as silane coupler, resin It is useful for adding agent, surface conditioning agent, coating additive, bonding agent etc..
Accompanying drawing explanation
Fig. 1 is double (diethyl amino propyl)-1,1,3,3-tetramethoxy two silica of the 1,3-obtained in embodiment 1 The IR spectrogram of alkane.
Fig. 2 is double (diethyl amino propyl)-1,1,3,3-tetramethoxy two silica of the 1,3-obtained in embodiment 1 Alkane1H-NMR spectrum.
Fig. 3 is double (methyl piperazine base propyl group)-1,1,3,3-tetraethoxy two silica of the 1,3-obtained in embodiment 2 The IR spectrogram of alkane.
Fig. 4 is double (methyl piperazine base propyl group)-1,1,3,3-tetraethoxy two silica of the 1,3-obtained in embodiment 2 Alkane1H-NMR spectrum.
Detailed description of the invention
The aminoalkylalkoxy disiloxane compound of the present invention is for by the compound shown in following formula (1).
[chemical formula 5]
(in formula, R1、R2For unsubstituted or substituted the 1 of heteroatomic carbon number 1～20, particularly preferred 1～10 can be contained Valency alkyl, can be the most identical or different, R1And R2Formed together with the nitrogen-atoms that can bond together thus be bonded with them Ring.R3For heteroatomic carbon number 1～20, particularly preferred 1～the straight-chain of 10, branched or ring-type divalent alkyl can be contained, R4、R5For 1 valency alkyl of carbon number 1～10, particularly preferred 1～6, n is 0 or 1.)
Wherein, as R1、R21 valency alkyl of carbon number 1～20, specifically can exemplify: methyl, ethyl, propyl group, butyl, The straight-chain alkyl such as amyl group, hexyl, heptyl, octyl group, decyl；Isopropyl, isobutyl group, sec-butyl, the tert-butyl group, tertiary hexyl, 2-second The branched-chain alkyls such as base hexyl；The cyclic alkyl such as cyclopenta, cyclohexyl；The thiazolinyl such as vinyl, acrylic etc., obtaining from raw material Easiness is set out, particularly preferred ethyl.Additionally, R1、R21 valency alkyl of carbon number 1～20 both can get involved ester group (- COO-), the hetero atom such as ether (-O-), sulfenyl (-S-), it is also possible to these are applied in combination.And then, the hydrogen of these alkyl Atom can partly or entirely be replaced, and as described substituent group, specifically can enumerate such as methoxyl group, ethyoxyl, (different) third The alkoxyls such as epoxide；The halogen atoms such as fluorine atom, chlorine atom, bromine atoms, atomic iodine；Cyano group；Amino；The carbon such as phenyl, tolyl The aryl of several 6～10；The aralkyl of the carbon number such as benzyl, phenethyl 7～10；The acyl group of carbon number 2～10；Each alkyl, each alkoxyl Carbon number be respectively 1～5 trialkylsilkl, trialkoxysilyl, dialkyl group monoalkoxy silicyl, single alkane Base dialkoxy silicyl etc..
Additionally, at R1、R2Form ring structure with them together with the nitrogen-atoms bonded together thus be bonded to form as by following During group shown in formula (5), pyrrolidinyl, piperidyl, piperazinyl, methyl piperazine base, morpholinyl etc. can be exemplified.
[chemical formula 6]
(in formula, R1、R2Same as described above.)
Additionally, as R3Can containing the divalent alkyl of heteroatomic carbon number 1～20, specifically can exemplify methylene, The alkylidene of the straight-chain such as ethylidene, propylidene, butylidene, hexylidene, octylene, decylene；Methyl ethylidene, methyl Asia third The branched alkylidenes such as base；The cycloalkylidenes such as cyclohexylidene；The alkenylenes such as allylidene；The arlydene such as phenylene；Xylene (メ チ レ Application Off ェ ニ レ Application base；Methylene phenylene group), xylene methyl (メ チ レ Application Off ェ ニ レ Application メ チ レ Application base；Methylene phenylene methylene group) etc. sub-aralkyl etc., obtaining from raw material Easiness is set out, particularly preferred methylene.Additionally, R3Divalent alkyl both can get involved ester group (-COO-), ether (- O-), the hetero atom such as sulfenyl (-S-), it is also possible to these are applied in combination.And then, the hydrogen atom of these alkyl can part or All it is replaced, as described substituent group, can enumerate and above-mentioned " R1、R2The hydrogen atom of alkyl can partly or entirely be taken Generation " in the same substituent group of substituent group.
As R4And R51 valency alkyl of carbon number 1～10, specifically can exemplify methyl, ethyl, hexyl, octyl group, decyl Etc. straight-chain alkyl；The branched-chain alkyls such as isopropyl, the tert-butyl group, neopentyl, tertiary hexyl；The cyclic alkyl such as cyclopenta, cyclohexyl； The thiazolinyls such as vinyl, pi-allyl, acrylic；The aryl such as phenyl, tolyl；The aralkyl such as benzyl, phenethyl etc., obtaining from raw material Obtain easiness to set out, particularly preferred alkyl, from the serviceability of product, preferably methyl, ethyl.
As by the aminoalkylalkoxy disiloxane compound shown in above-mentioned formula (1), can exemplify 1,3-is double Double (the dimethylaminopropyl)-1,3-two of (dimethylaminopropyl)-1,1,3,3-tetramethoxy disiloxane, 1,3- Double (dimethylaminopropyl)-1,1,3,3-tetraethoxy two silicon of methoxyl group-1,3-dimethyl-disiloxane, 1,3- Double (the dimethylaminopropyl)-1,3-diethoxy-1,3-dimethyl-disiloxane of oxygen alkane, 1,3-, 1,3-double (two Diethylaminobutyyl)-1,1,3,3-tetramethoxy disiloxane, double (the diethyl amino propyl)-1,3-dimethoxy of 1,3- Double (the diethyl amino propyl)-1,1,3,3-tetraethoxy disiloxane of base-1,3-dimethyl-disiloxane, 1,3-, Double (the diethyl amino propyl)-1,3-diethoxy-1,3-dimethyl-disiloxane of 1,3-, the double (dibutyl of 1,3- Aminopropyl)-1,1,3,3-tetramethoxy disiloxane, double (dibutylamino the propyl group)-1,3-dimethoxy of 1,3-- Double (dibutylamino the propyl group)-1,1,3,3-tetraethoxy disiloxane of 1,3-dimethyl-disiloxane, 1,3-, 1, Double (dibutylamino the propyl group)-1,3-diethoxy-1,3-dimethyl-disiloxane of 3-, the double (morpholino third of 1,3- Base)-1,1,3,3-tetramethoxy disiloxane, double (the morphoinopropyl)-1,3-dimethoxy-1,3-diformazan of 1,3- Double (the morphoinopropyl)-1,1,3,3-tetraethoxy disiloxane of base-disiloxane, 1,3-, the double (morpholino third of 1,3- Base)-1,3-diethoxy-1,3-dimethyl-disiloxane, double (the piperazinopropyl)-1,1,3,3-tetramethyl of 1,3- Epoxide disiloxane, 1,3-double (piperazinopropyl)-1,3-dimethoxy-1,3-dimethyl-disiloxane, 1,3- Double (the piperazinopropyl)-1,3-diethoxy of double (piperazinopropyl)-1,1,3,3-tetraethoxy disiloxane, 1,3- Double (methyl piperazine base the propyl group)-1,1,3,3-tetramethoxy disiloxane of base-1,3-dimethyl-disiloxane, 1,3-, Double (methyl piperazine base the propyl group)-1,3-dimethoxy-1,3-dimethyl-disiloxane of 1,3-, double (the methyl piperazine of 1,3- Piperazine base propyl group)-1,1,3,3-tetraethoxy disiloxane, double (methyl piperazine base the propyl group)-1,3-diethoxy of 1,3-- Double (double (trimethyl silyl) the aminopropyl)-1,1,3,3-tetramethoxy of 1,3-dimethyl-disiloxane, 1,3- Disiloxane, 1,3-double (double (trimethyl silyl) aminopropyl)-1,1,3,3-tetraethoxy disiloxane, 1,3- Double (double (trimethyl silyl) aminopropyl)-1,3-dimethoxy-1,3-dimethyldisiloxane, 1,3-are double (double (trimethyl silyl) aminopropyl)-1,3-diethoxy-1,3-dimethyldisiloxane etc..
By the aminoalkylalkoxy disiloxane compound shown in formula (1) owing to being rich in the active of reactivity on nitrogen Hydrogen, therefore, also will not cause ring-opening polymerisation even if adding in Epoxy Precursors.Even if additionally, with polyurethane precursor, i.e. contain The material mixing having NCO is not reacted with NCO, and additive therefore can be avoided to be imported into resin matrix self In.Even if adding in carbonate resin, also it is not result in carbonic ester skeletal disintegration.Additionally, amino groups and alkoxyl first silicon Alkyl portion is sufficiently far from, and the most each functional group is less to the obstruction of effect each other.
As the manufacture method of the aminoalkylalkoxy disiloxane compound of the present invention, for example, it is possible to make by following Amino compound hydrolysis shown in formula (2) is condensed and manufactures.
[chemical formula 7]
(in formula, R1、R2、R3、R4、R5, n same as described above, example similar to the above can be exemplified.)
As by the amino compound shown in above-mentioned formula (2), dimethylamino can be exemplified Propyl trimethoxy silicane, diethyl amino propyl trimethoxy silane, dibutylamino propyl trimethoxy silicane, piperazinyl Propyl trimethoxy silicane, methyl piperazine base propyl trimethoxy silicane, morphoinopropyl trimethoxy silane, dimethylamino Propyl-triethoxysilicane, diethyl amino propyl triethoxysilane, dibutylamino propyl-triethoxysilicane, piperazinyl Propyl-triethoxysilicane, methyl piperazine base propyl-triethoxysilicane, morphoinopropyl triethoxysilane, dimethylamino Hydroxypropyl methyl dimethoxysilane, diethyl amino propyl methyl dimethoxysilane, dibutylamino hydroxypropyl methyl dimethoxy Base silane, piperazinopropyl methyl dimethoxysilane, methyl piperazine base hydroxypropyl methyl dimethoxysilane, morphoinopropyl first Base dimethoxysilane, dimethylaminopropyl methyldiethoxysilane, diethyl amino propyl methyldiethoxysilane, Dibutylamino hydroxypropyl methyl diethoxy silane, piperazinopropyl methyldiethoxysilane, methyl piperazine base hydroxypropyl methyl Diethoxy silane, morphoinopropyl methyldiethoxysilane, double (trimethyl silyl) aminopropyl trimethoxy silicon Alkane, double (trimethyl silyl) aminopropyltriethoxywerene werene, double (trimethyl silyl) amino propyl methyl diformazan TMOS, double (trimethyl silyl) amino propyl methyl diethoxy silane etc..
Limit the most especially by the match ratio of the amino compound shown in above-mentioned formula (2) with water Fixed, from the viewpoint of reactive, productivity ratio, relative to the compound shown in 1 general Formula (2), preferably water is set to 0.1～ The scope of 4 moles, particularly 0.2～1 mole.
Although hydrolysis-condensation reaction is also carried out under without catalysts conditions but it also may add catalyst and improve reaction speed Degree.As catalyst used, Feldalat NM, Sodium ethylate etc. and alcoholic solution thereof can be enumerated；Feldalat KM, potassium ethoxide, sodium hydroxide, The base catalysts such as potassium hydroxide, Cesium hydrate., calcium hydroxide, magnesium hydroxide, triethylamine, tri-butylamine, trioctylphosphine amine；Chlorine Change the acidity such as hydrogen, hydrogen bromide, sulphuric acid, methanesulfonic acid, benzenesulfonic acid, DBSA, trifluoromethanesulfonic acid, acetic acid, trifluoroacetic acid Catalyst；The quaternary ammonium salts such as 4-propyl bromide, tetrabutyl ammonium bromide, tetrapropyl ammonium iodide, tetrabutylammonium iodide；Tetrapropyl bromination , tetrabutyl phosphonium bromide, tetrapropyl iodate, the quaternary salt etc. such as tetrabutyl iodate.
The usage amount of catalyst is not particularly limited, from the viewpoint of reaction facilitation effect, relative to 1 mole by leading to Compound shown in formula (2), be preferably used 0.001～1.0 mole, particularly 0.001～0.2 mole, especially 0.005～ 0.1 mol catalyst.
Although hydrolysis-condensation reaction is also carried out under condition of no solvent but it also may use solvent.As solvent used, The hydrocarbon system solvents such as pentane, hexane, hexamethylene, heptane, isobutyltrimethylmethane., benzene,toluene,xylene can be exemplified；Methanol, ethanol, different The alcohol series solvents such as propanol；The ether series solvents such as ether, oxolane, dioxane；Acetonitrile, N,N-dimethylformamide, N, N-bis- The aprotic polar solvent such as methylacetamide.These solvents can be used alone, it is also possible to two or more is mixed.In order to anti- Locally lying in of sealing, is especially desired to use aprotic polar solvent, alcohol series solvent.
The reaction temperature of hydrolysis-condensation reaction is not particularly limited, is 20～200 DEG C, particularly preferred 30～100 DEG C；Right Response time is also not particularly limited, and is 1～30 hour, particularly preferred 3～10 hours.
Additionally, as other method, can be by making by the haloalkyl alkoxyl disiloxane shown in following formula (3) Compound and by shown in following formula (4) amines react manufacture by the aminoalkyl alcoxyl shown in above-mentioned formula (1) Base disiloxane compound.
[chemical formula 8]
(in formula, R3、R4、R5, n same as described above, example similar to the above can be shown.X is chlorine, bromine or iodine.)
[chemical formula 9]
(in formula, R1、R2Same as described above, example similar to the above can be shown.)
As by the haloalkyl alkoxyl disiloxane compound shown in above-mentioned formula (3), can exemplify 1,3-is double Double (the chloropropyl)-1,3-dimethoxy-1,3-diformazan of (chloropropyl)-1,1,3,3-tetramethoxy disiloxane, 1,3- Double (the chloropropyl)-1,1,3,3-tetraethoxy disiloxane of base-disiloxane, 1,3-, double (chloropropyl)-1 of 1,3-, Double (chlorobutyl)-1,1,3,3-tetramethoxy two silica of 3-diethoxy-1,3-dimethyl-disiloxane, 1,3- Double (the chlorobutyl)-1,3-dimethoxy-1,3-dimethyl-disiloxane of alkane, 1,3-, double (chlorobutyl)-1 of 1,3-, Double (chlorobutyl)-1,3-diethoxy-1,3-dimethyl-two silica of 1,3,3-tetraethoxy disiloxane, 1,3- Double (the bromopropyl)-1,1,3,3-tetramethoxy disiloxane of alkane, 1,3-, double (the bromopropyl)-1,3-dimethoxy of 1,3- Double (the bromopropyl)-1,1,3,3-tetraethoxy disiloxane of base-1,3-dimethyl-disiloxane, 1,3-, 1,3-are double Double (the brombutyl)-1,1,3,3-tetramethyl of (bromopropyl)-1,3-diethoxy-1,3-dimethyl-disiloxane, 1,3- Double (the brombutyl)-1,3-dimethoxy-1,3-dimethyl-disiloxane of epoxide disiloxane, 1,3-, the double (bromine of 1,3- Butyl)-1,1,3,3-tetraethoxy disiloxane, double (the brombutyl)-1,3-diethoxy-1,3-diformazan of 1,3- Double (iodine the propyl group)-1,1,3,3-tetramethoxy disiloxane of base-disiloxane, 1,3-, double (the iodine propyl group)-1 of 1,3-, Double (iodine propyl group)-1,1,3,3-tetraethoxy two silica of 3-dimethoxy-1,3-dimethyl-disiloxane, 1,3- Double (iodine the propyl group)-1,3-diethoxy-1,3-dimethyl-disiloxane of alkane, 1,3-, double (the iodine butyl)-1 of 1,3-, Double (iodine butyl)-1,3-dimethoxy-1,3-dimethyl-two silica of 1,3,3-tetramethoxy disiloxane, 1,3- Double (iodine the butyl)-1,1,3,3-tetraethoxy disiloxane of alkane, 1,3-, double (iodine the butyl)-1,3-diethoxy of 1,3- Base-1,3-dimethyl-disiloxane etc..
As by the amines shown in above-mentioned formula (4), can exemplify dimethyl amine, diethylamide, dibutylamine, Piperazine, methyl piperazine, morpholine, pyrrolidine, piperidines etc..
About by the haloalkyl alkoxyl disiloxane compound shown in formula (3) and by the amination shown in formula (4) The reaction ratio of compound, is carried out from being swift in response, the viewpoint such as the simplicity of post processing, refined easiness, rubs relative to 1 You are preferably used 4～20 moles, the amine compounds shown in formula (4) of particularly 4～8 moles by the compound shown in formula (3) Thing.
By the haloalkyl alkoxyl disiloxane compound shown in formula (3) and by the amines shown in formula (4) Although reaction be also carried out under without catalysts conditions, but sometimes can also by add catalyst improve response speed.As Catalyst used, can exemplify 4-propyl bromide, tetrabutyl ammonium bromide, tetrapropyl ammonium iodide, tetrabutylammonium iodide etc. Quaternary ammonium salt；The quaternary salts such as tetrapropyl bromination, tetrabutyl phosphonium bromide, tetrapropyl iodate, tetrabutylammonium iodide phosphine.
The usage amount of catalyst is not particularly limited, from the viewpoint of reaction facilitation effect, relative to 1 mole by leading to Compound shown in formula (3), be preferably used 0.001～1.0 mole, particularly 0.001～0.2 mole, especially 0.005～ The catalyst of 0.1 mole.
By the haloalkyl alkoxyl disiloxane compound shown in formula (3) and by the amines shown in formula (4) Although reaction be also carried out under condition of no solvent but it also may add solvent.As solvent used, penta can be exemplified The hydrocarbon system solvents such as alkane, hexane, hexamethylene, heptane, isobutyltrimethylmethane., benzene,toluene,xylene；The alcohol systems such as methanol, ethanol, isopropanol are molten Agent；The ether series solvents such as Anaesthetie Ether, oxolane, dioxane；Acetonitrile, N,N-dimethylformamide, N, N-dimethylacetamide The aprotic polar solvent such as amine, N-Methyl pyrrolidone.These solvents can be used alone, it is also possible to two or more is mixed Close.It is especially desired to use and can expect the ether series solvent of raising of response speed, aprotic polar solvent.
Reaction temperature is also not particularly limited, is 20～200 DEG C, particularly preferred 50～150 DEG C；Response time is not had yet It is particularly limited to, is 1～30 hour, particularly preferred 3～10 hours.
Embodiment
The present invention is specifically described by embodiment described below and comparative example, but the present invention is not limited by following embodiment System.
The synthesis of double (the diethyl amino propyl)-1,1,3,3-tetramethoxy disiloxane of [embodiment 1] 1,3-
Diethyl amino propyl trimethoxy is added in the flask possessing blender, return channel, Dropping funnel and thermometer Base silane 1500g (6.372 moles) and water 34.9g (1.94 moles), stirs 5 hours at 70 DEG C.Reactant liquor is distilled, obtains Obtain fraction (double (diethyl amino propyl)-1,1,3,3-tetramethoxy two silica of 1,3-of the 158 DEG C/0.2kPa of 296.3g Alkane).
To obtain fraction carried out mass spectrum,1H-NMR spectrum, IR compose mensuration.
Mass spectrum
m/z 424 363 167 86
IR composes
Spectrogram is as shown in Figure 1.
1H-NMR composes (deuterochloroform solvent)
Spectrogram is as shown in Figure 2.
Be may validate that the compound of acquisition is double (the diethyl amino propyl)-1,1,3,3-four of 1,3-by result above Methoxyl group disiloxane.
The synthesis of double (methyl piperazine base the propyl group)-1,1,3,3-tetraethoxy disiloxane of [embodiment 2] 1,3-
Chloropropyl triethoxysilane is added in the flask possessing blender, return channel, Dropping funnel and thermometer 722.6g (3.001 moles) and water 27.1g (1.51 moles), methanesulfonic acid 2.9g (0.031 mole), be stirred at room temperature 13 little Time.In reactant liquor, add 20 mass % ethanol solution 11.4g (0.0344 mole) of Sodium ethylate and stir 30 minutes.Then add Enter acetic acid 0.9g (0.02 mole) and stir 30 minutes.The reactant liquor obtained is distilled, it is thus achieved that 150 DEG C of 142.8g/ The fraction (double (the chloropropyl)-1,1,3,3-tetraethoxy disiloxane of 1,3-) of 0.4kPa.
(0.600 rubs to add methyl piperazine 60.1g in the flask possessing blender, return channel, Dropping funnel and thermometer You) and hexane 6.0g, N-Methyl pyrrolidone 6.0g, it is heated to 110 DEG C.In the reactant liquor obtained, keeping 110～120 DEG C temperature while with within 2 hours, dripping double (the chloropropyl)-1,1,3,3-tetraethoxy disiloxane 40.8g of above-mentioned 1,3- (0.100 mole), the most further stirring 5 hours.Reactant mixture is cooled to 50 DEG C, adds ethylenediamine 18.0g (0.300 mole), at the same temperature stirring 30 minutes.The ethylenediamine-hydrochloride generated is removed by separatory operation After going, add 20 mass % ethanol solution 1.2g (0.0035 mole) of Sodium ethylate in the upper layer, then with acetic acid 0.2g (0.003 Mole) carry out returning neutralization (inverse neutralization).The reactant liquor obtained is distilled, it is thus achieved that the fraction of the 219 DEG C/0.3kPa of 36.1g (double (methyl piperazine base the propyl group)-1,1,3,3-tetraethoxy disiloxane of 1,3-).
To obtain fraction carried out mass spectrum,1H-NMR spectrum, IR compose mensuration.
Mass spectrum
m/z 534 490 372 113
IR composes
Spectrogram is as shown in Figure 3.
1H-NMR composes (deuterochloroform solvent)
Spectrogram is as shown in Figure 4.
Be may validate that the compound of acquisition is double (methyl piperazine base the propyl group)-1,1,3,3-four of 1,3-by result above Ethyoxyl disiloxane.
[embodiment 3,4 and comparative example 1]
Interpolation to epoxy resin is tested
Epoxy resin (Tokyo エ Port キ シ レ ジ Application system: JER-828) 40g is added in above-described embodiment 1 of 4.0g and close 1 synthesized in the 1,3-become double (diethyl amino propyl)-1,1,3,3-tetramethoxy disiloxane, above-described embodiment 2, Double (methyl piperazine base the propyl group)-1,1,3,3-tetraethoxy disiloxane of 3-or double (aminopropyl)-1,1,3 of 1,3-, 3-tetramethoxy disiloxane, is stirred at room temperature 5 minutes.The mixture of acquisition is at room temperature stood, after 12 hours Character confirms.For the change of character, the container lean 45 degree of said mixture will be comprised, interior within being visually confirmed to be 5 seconds Tolerant whether flow.Within 5 seconds during content flowing, it is judged that for there being mobility, be judged as without mobility time unchanged.
[table 1]
May validate that by the result of table 1 the aminoalkylalkoxy disiloxane compound of the present invention can add ring to In epoxy resins.

Claims (3)

1. by the aminoalkylalkoxy disiloxane compound shown in following formula (1),
[chemical formula 1]
In formula, R1、R2For can distinguishing identical or not containing the unsubstituted or substituted 1 valency alkyl of heteroatomic carbon number 1～20 With, R1And R2Ring is formed together with the nitrogen-atoms that can bond together thus be bonded with them；R3For heteroatomic carbon number 1 can be contained ～the straight-chain of 20, branched or ring-type divalent alkyl, R4、R5For 1 valency alkyl of carbon number 1～10, n is 0 or 1.
2. described in claim 1 by the manufacture method of the aminoalkylalkoxy disiloxane compound shown in formula (1), its It is characterised by, makes to be condensed by the amino compound hydrolysis shown in following formula (2),
In formula, R1～R5And n is same as described above.
3. described in claim 1 by the manufacture method of the aminoalkylalkoxy disiloxane compound shown in formula (1), its It is characterised by, makes by the haloalkyl alkoxyl disiloxane compound shown in following formula (3) and by following formula (4) Suo Shi Amines reaction,
In formula, R3～R5And n is same as described above, X is chlorine, bromine or iodine,
In formula, R1、R2Same as described above.
CN201610507105.5A 2015-06-30 2016-06-30 Aminoalkylalkoxydisiloxane compound and method for preparing the same Pending CN106317099A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-131630 2015-06-30
JP2015131630A JP6365445B2 (en) 2015-06-30 2015-06-30 Aminoalkylalkoxydisiloxane compound and method for producing the same

Publications (1)

Publication Number Publication Date
CN106317099A true CN106317099A (en) 2017-01-11

Family

ID=57725833

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610507105.5A Pending CN106317099A (en) 2015-06-30 2016-06-30 Aminoalkylalkoxydisiloxane compound and method for preparing the same

Country Status (3)

Country Link
JP (1) JP6365445B2 (en)
KR (1) KR102341724B1 (en)
CN (1) CN106317099A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115974911A (en) * 2023-03-14 2023-04-18 北京奇点势能科技有限公司 SuFEx click chemistry aminosilane coupling agent, and preparation method and application thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102014521B1 (en) 2016-04-25 2019-10-21 주식회사 엘지화학 Modified conjugated diene polymer and preparing method thereof
KR102288852B1 (en) * 2018-05-25 2021-08-12 주식회사 엘지화학 Modified conjugated diene polymer and rubber composition comprising the same
JP2021085025A (en) * 2019-11-29 2021-06-03 株式会社ブリヂストン Rubber composition and tire
WO2024106213A1 (en) * 2022-11-17 2024-05-23 信越化学工業株式会社 Method for producing disiloxane compound

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4180642A (en) * 1977-06-29 1979-12-25 Shin-Etsu Chemical Company Room temperature curable organopolysiloxane compositions
JPH0251542A (en) * 1988-08-15 1990-02-21 Adeka Argus Chem Co Ltd Polymer material composition with improved light resistance
JPH0732547A (en) * 1993-07-16 1995-02-03 Mitsui Toatsu Chem Inc Heat resistant laminate
JPH10120690A (en) * 1996-10-23 1998-05-12 Japan Energy Corp New quaternary imidazolium salt derivative and its production
JP2002193976A (en) * 2000-12-22 2002-07-10 Shin Etsu Chem Co Ltd Production method of n-substituted-3-silylpropylamine and its derivative
RU2332422C2 (en) * 2006-05-23 2008-08-27 Ооо "Инстрой" Application of organosilicone amine as multifunctional additive for foamed polyurethane compositions
JP2009143881A (en) * 2007-12-18 2009-07-02 Shin Etsu Chem Co Ltd Method for producing alkylpiperazinoalkylsilane compound
CN101553522A (en) * 2006-10-25 2009-10-07 Jsr株式会社 Process for producing modified polymer, modified polymer obtained by the process, and rubber composition containing the same
US20110034620A1 (en) * 2009-08-07 2011-02-10 Shin-Etsu Chemical Co., Ltd. Abrasion resistant silicone coating composition, coated article, and making method

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB786452A (en) * 1954-09-10 1957-11-20 Midland Silicones Ltd Improvements in or relating to organosilicon compounds
US2814572A (en) * 1955-08-17 1957-11-26 Dow Corning Organosilicon compounds and a method for waterproofing glass and product produced thereby
US2990230A (en) * 1957-09-03 1961-06-27 Dow Corning Process of printing textiles and the composition employed therein
US4287326A (en) 1980-03-03 1981-09-01 Toray Silicone Company, Ltd. Siloxane-modified epoxy resin compositions
JPS5718758A (en) * 1980-07-08 1982-01-30 Shin Etsu Chem Co Ltd Organopolysiloxane composition curable at room temperature
JPH05295219A (en) * 1992-04-22 1993-11-09 Mitsui Toatsu Chem Inc Resin composition
DE19725501C1 (en) * 1997-06-17 1998-12-10 Huels Silicone Gmbh Alkoxy crosslinking RTVl silicone rubber mixtures
JP2003316000A (en) * 2002-04-24 2003-11-06 Toray Ind Inc Photosensitive ceramic composition
BRPI0415126A (en) * 2003-10-07 2006-11-28 Clariant Finance Bvi Ltd multiple quaternary polysiloxanes
JP4257515B2 (en) * 2003-10-10 2009-04-22 信越化学工業株式会社 Process for producing 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane
US20060269498A1 (en) * 2005-05-17 2006-11-30 Gerard Malle Hair shaping composition comprising at least one polyguanidine other than hydroxide
US20060272107A1 (en) * 2005-05-17 2006-12-07 Gerard Malle Hair relaxing composition comprising at least one non-hydroxide polyguanidine
DE102005039511A1 (en) * 2005-08-20 2007-02-22 Clariant Produkte (Deutschland) Gmbh Use of quaternary polysiloxanes in cleaning and care products
JP5076405B2 (en) * 2006-09-01 2012-11-21 東ソー株式会社 Polyurethane resin production catalyst and polyurethane resin production method using the same
JP2008111023A (en) * 2006-10-30 2008-05-15 Shin Etsu Chem Co Ltd Aqueous solution containing propylsilanol compound having tertiary amino group
JP4803381B2 (en) * 2006-12-12 2011-10-26 信越化学工業株式会社 Method for producing aminoalkylsilane compound
JP5302918B2 (en) * 2010-03-10 2013-10-02 独立行政法人科学技術振興機構 Method for producing diaminonitrile analogue
JP5900399B2 (en) * 2013-03-27 2016-04-06 信越化学工業株式会社 Bis (aminoalkyl) silane compound and method for producing the same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4180642A (en) * 1977-06-29 1979-12-25 Shin-Etsu Chemical Company Room temperature curable organopolysiloxane compositions
JPH0251542A (en) * 1988-08-15 1990-02-21 Adeka Argus Chem Co Ltd Polymer material composition with improved light resistance
JPH0732547A (en) * 1993-07-16 1995-02-03 Mitsui Toatsu Chem Inc Heat resistant laminate
JPH10120690A (en) * 1996-10-23 1998-05-12 Japan Energy Corp New quaternary imidazolium salt derivative and its production
JP2002193976A (en) * 2000-12-22 2002-07-10 Shin Etsu Chem Co Ltd Production method of n-substituted-3-silylpropylamine and its derivative
RU2332422C2 (en) * 2006-05-23 2008-08-27 Ооо "Инстрой" Application of organosilicone amine as multifunctional additive for foamed polyurethane compositions
CN101553522A (en) * 2006-10-25 2009-10-07 Jsr株式会社 Process for producing modified polymer, modified polymer obtained by the process, and rubber composition containing the same
JP2009143881A (en) * 2007-12-18 2009-07-02 Shin Etsu Chem Co Ltd Method for producing alkylpiperazinoalkylsilane compound
US20110034620A1 (en) * 2009-08-07 2011-02-10 Shin-Etsu Chemical Co., Ltd. Abrasion resistant silicone coating composition, coated article, and making method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115974911A (en) * 2023-03-14 2023-04-18 北京奇点势能科技有限公司 SuFEx click chemistry aminosilane coupling agent, and preparation method and application thereof

Also Published As

Publication number Publication date
JP2017014140A (en) 2017-01-19
KR102341724B1 (en) 2021-12-24
JP6365445B2 (en) 2018-08-01
KR20170003417A (en) 2017-01-09

Similar Documents

Publication Publication Date Title
CN106317099A (en) Aminoalkylalkoxydisiloxane compound and method for preparing the same
EP0497278A1 (en) Organopentasiloxane and method for its preparation
CN113166474A (en) Reactive siloxanes
CN107849068A (en) method for preparing polyhedral oligomeric silsesquioxane
CN108976255A (en) Novel halogenated germanide and preparation method thereof
US5364896A (en) Method for preparing silica filled organosiloxane compositions
JP5861618B2 (en) Organopolysiloxane and method for producing the same
US20080051594A1 (en) Process For Producing Organosilicon Compound
CN108728011A (en) A kind of novel bonding accelerating agent and preparation method thereof
US7402648B2 (en) Method for producing cyclic organic silicon compound and organic silicon resin having alcoholic hydroxyl group
JP5062231B2 (en) Organosilicon resin having alcoholic hydroxyl group and method for producing the same
US7365213B2 (en) Organosilicon compound, organosilicon resin having diol, and processes for producing these
EP3015471B1 (en) Novel bisalkoxysilane compound and its production method
JP2864866B2 (en) Method for producing organosilicon compound
JPS6257657B2 (en)
JP4147705B2 (en) Hydrosilyl group-containing polysilsesquioxane compound and method for producing the same
EP1196423A2 (en) PROCESS FOR PRODUCTION OF DIPHENYL-DIALKOXYSILANE, PHENYLALKYL-DIALKOXYSILANE, OCTAPHENYLCYCLOTETRASILOXANE AND i SYM /i -TETRAALKYLTETRAPHENYL-CYCLOTETRASILOXANE
JP6354721B2 (en) Organosilicon compound having diphenylethyl group and methoxysilyl group and method for producing the same
WO2012091586A1 (en) Fluorocarbofunctional silsesquioxanes containing other reactive functional groups and a method to obtain the same
JP6531656B2 (en) Process for producing nitrogen-containing organoxysilane compound
JP3124910B2 (en) Cyclotrisiloxane and method for producing the same
JP2002012597A (en) Organic silicon compound
WO2024106212A1 (en) Composition containing aminoalkyl alkoxy disiloxane compound and aminoalkyl alkoxy oligosiloxane compound, and method for producing same
JP2003064088A (en) New silazane compound and method for producing the same, and new silazane compound polymer and method for producing the same
JPH02175725A (en) Production of alkoxylated organopolysiloxane

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20170111