CN109485672A - Organic titanic compound, moisture-curable composition and formed body - Google Patents
Organic titanic compound, moisture-curable composition and formed body Download PDFInfo
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- CN109485672A CN109485672A CN201811053348.1A CN201811053348A CN109485672A CN 109485672 A CN109485672 A CN 109485672A CN 201811053348 A CN201811053348 A CN 201811053348A CN 109485672 A CN109485672 A CN 109485672A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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Abstract
The present invention relates to organic titanic compound, moisture-curable composition and formed bodys.Present invention offer has the curability same with existing organic titanic compound and has cooperated the curability of the moisture-curable composition of the organic titanic compound good and then given the novel organotitanium compound of the high elastic solid (Hookean body) object of the transparency when the moisture-curable composition of unmated filler solidifies；And contain the organic titanic compound as moisture-curables compositions such as curing catalysts, the normal temperature cured organic polysiloxane compositions for solidifying and giving elastomer；Formed body obtained from solidifying the composition etc..Organic titanic compound contains the hydrolization group that at least one is indicated by following structural formula (1) in the molecule.In formula, E is the alkylidene of carbon atom number 1~4, and R is the alkyl of carbon atom number 1~4.-O-E-Si(R)3 (1)。
Description
Technical field
The present invention relates to novel organotitanium compound, use the organic titanic compound as the moisture-curable group of catalyst
Formed body obtained from closing object and solidifying the composition etc..
Background technique
The organosiloxane group of elastic solid (Hookean body) object is cured as by condensation reaction if with the contact with moisture in air
Object is closed to be well-known.Such composition is typically via will have reactive terminal base (generally silanol group) two
The silane crosslinker of organopolysiloxane and diorganopolysiloxanecompositions such as alkoxy silane, acetoxylsilane, oximido silicon
Alkane or amino silane are obtained by mixing.These materials solidify if being exposed in atmospheric water at room temperature, form elasticity
Solids.Wherein, especially release the organosiloxane composition of alcohol and cured type with no offensive odour, no
Corrosion metal class is characterized, and is suitable for the sealing in elec-tric-electronic equipment etc., bonding, is used in coating.
As such typical example, disclose comprising hydroxy-end capped organopolysiloxane, alkoxy silane and organic
The moisture-curable composition of titanium compound blocks organopolysiloxane, alkoxy silane comprising alkoxysilyl and has
The moisture-curable composition of machine titanium compound (alkoxytitanium), comprising with containing silicon ethylidene alkoxysilyl block
The organopolysiloxane of straight-chain, alkoxy silane and organic titanic compound (alkoxytitanium) moisture-curable composition,
And include hydroxy-end capped organopolysiloxane or alkoxy end-capped organopolysiloxane and alkoxy-α-silyl ester chemical combination
Moisture-curable composition (the Patent Documents 1 to 4: Japanese Patent Publication 39-27643 bulletin, Japanese Unexamined Patent Application 55-43119 of object
Number bulletin, Japanese Patent Publication 7-39547 bulletin, Japanese Unexamined Patent Publication 7-331076 bulletin).
As shown in above-mentioned typical example, it is known to make use of organic titanic compound uses organic as catalyst
When titanium compound makes composition, in the case where especially requiring the transparency to elastic solid (Hookean body) object when solidifying, in solidification midway
Organic titanic compound hydrolyzes and becomes titanium oxide, and organic titanic compound reacts with methoxy silane and generates white in the composition
Sediment, thus the problem of producing the transparency reduction of elastic solid (Hookean body) object made of the composition solidifies.It is asked to solve this
Topic, has carried out various researchs, for the moisture-curable composition for having cooperated existing organic titanic compound, in any feelings
All be difficult to inhibit under condition to generate white depositions in solidification midway organic titanic compound, used organic titanic compound as urging
In the moisture-curable composition of agent, the method for obtaining the elastic solid (Hookean body) object with high transparency is still unknown.
In turn, in organic titanic compound, when using titanium chelate, due to becoming solid under cryogenic in the type
Body, therefore when manufacturing the moisture-curable composition, it needs in advance to heat the titanium chelate used and melt, also produce manufacture
On problem.
As described above, being wished in the case where having used catalyst of the organic titanic compound as moisture-curable composition
Hope there is following organic titanic compound: the elastic solid (Hookean body) object tool that moisture-curable composition when without filler obtains when solidifying
There is a high transparency, and there is the curability same with the organic titanic compound that used in the past.In turn, expecting that exploitation is following has
Machine titanium compound: when having selected certain titanium chelate as organic titanic compound, solid will not be become under low-temperature condition
State is handled in manufacture and is easy.
Further more, as with the associated prior art of the present invention, following documents are enumerated together with above-mentioned document.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Publication 39-27643 bulletin
Patent document 2: Japanese Unexamined Patent Application 55-43119 bulletin
Patent document 3: Japanese Patent Publication 7-39547 bulletin
Patent document 4: Japanese Unexamined Patent Publication 7-331076 bulletin
Patent document 5: Japanese Unexamined Patent Application Publication 2012-511607 bulletin
Summary of the invention
Subject to be solved by the invention
The present invention is completed in view of above-mentioned actual conditions, and it is an object of the present invention to provide having same with existing organic titanic compound
Curability and cooperated the curability of the moisture-curable composition of the organic titanic compound good and then unmated
The moisture-curable composition of filler (filler) gives the novel organotitanium of the high elastic solid (Hookean body) object of the transparency when solidifying
Close object；And contain the organic titanic compound as curing catalysts, solidification and the room temp solidified organic poly- of elastomer is provided
The moisture-curables composition such as silicone composition；Formed body obtained from solidifying the composition etc..
Means for solving the problems
The present inventor is conscientiously studied to achieve the goals above, as a result, it has been found that: by using containing in the molecule
Organic titanic compound the urging as moisture-curable composition for the hydrolization group that at least one is indicated by following structural formula (1)
Agent to have the curability same with the organic titanic compound that used in the past, and has used above-mentioned organic titanic compound
The elastic solid (Hookean body) object that is obtained when solidifying of the moisture-curable organopolysiloxane composition without filler there is high transparency,
Complete the present invention.
-O-E-Si(R)3 (1)
(in formula, E is the alkylidene of carbon atom number 1~4, and R is the alkyl of carbon atom number 1~4.)
Therefore, the present invention provides following organic titanic compounds, the moisture-curable composition comprising the compound and incites somebody to action
Formed body obtained from the composition solidification etc..
[1] organic titanic compound contains the hydrolization group that at least one is indicated by following structural formula (1) in the molecule.
-O-E-Si(R)3 (1)
(in formula, E is the alkylidene of carbon atom number 1~4, and R is the alkyl of carbon atom number 1~4.)
[2] organic titanic compound described in [1] is indicated by any of the following general formula (2), (3), (4) or (5).
Ti[OR1]x1[OR2]y1 (2)
Ti[C6H9O3]x2[OR2]y2 (3)
Ti[C5H7O2]x2[OR2]y2 (4)
Ti[C8H17O2]x2[OR2]y2 (5)
[in formula, R1For 1 valency alkyl of carbon atom number 1~6.R2For by the following general formula (6)
-E-Si(R)3 (6)
(in formula, E is the alkylidene of carbon atom number 1~4, and R is the alkyl of carbon atom number 1~4.) indicate trialkyl first silicon
Alkyl replaces alkyl.X1 is average value 0~3, and y1 is average value 1~4, and x1+y1 is 4.
X2 is average value 1~3, and y2 is average value 1~3, and x2+y2 is 4.]
[3] organic titanic compound described in [1] or [2], is used for the curing catalysts of moisture-curable composition.
[4] moisture-curable composition contains organic titanic compound described in [3], elasticity is given with moisture-curable
Body.
[5] moisture-curable composition described in [4], contain has 2 or more the hydroxyls in conjunction with silicon in the molecule
Or the high molecular material and organic oxysilane curing agent of alkoxy.
[6] moisture-curable composition described in [5], wherein in the molecule with 2 or more hydroxyls in conjunction with silicon or
The high molecular material of alkoxy is organopolysiloxane in the molecule with 2 or more the hydroxyls or alkoxy in conjunction with silicon.
[7] moisture-curable composition described in [5] or [6], also contains filler.
[8] electrical and electronic parts, the solidfied material with composition described in any one of [4]~[7].
[9] Building Encapsulant, it includes the solidfied materials of the composition described in any one of [4]~[7].
[10] automobile oil sealing, it includes the solidfied materials of the composition described in any one of [4]~[7].
If used above-mentioned organic titanic compound as the catalyst of moisture-curable composition, have with it is existing
The same curability of organic titanic compound, and cooperated the curability of the moisture-curable composition of the organic titanic compound can
Become good.
In turn, it mentions and has used above-mentioned organic titanic compound, there is 2 or more the hydroxyls or alkane in conjunction with silicon in the molecule
The normal temperature cured organic polysiloxane group without filler of the organopolysiloxane of oxygroup and organic oxysilane curing agent
The moisture-curables compositions such as object are closed, since the hydrolization group of novel organotitanium compound is using the similar knot of organopolysiloxane
Structure, therefore improved with the compatibility of silicone ingredients, the high elastic solid (Hookean body) object of the transparency can be obtained.Such moisture-curable
The elastic solid (Hookean body) object of composition is since optical characteristics is excellent, suitable for electrical and electronic parts etc..
In addition, by containing filler in the moisture-curable composition for having used above-mentioned organic titanic compound, thus right
Moisture-curable composition under uncured state can carry out the adjustment of viscosity adjustment, mobility.For making moisture-curable
For the elastic solid (Hookean body) object that composition obtains when solidifying, due to can be improved mechanical property, chemical-resistant, it is suitable as
Oil sealing of sealant, automobile for building etc. uses.
The effect of invention
Organic titanic compound of the invention can become the moisture with the curability same with existing organic titanic compound
The catalyst of curing composition, and then for comprising organic titanic compound of the invention, in the molecule with 2 or more and silicon
In conjunction with hydroxyl or alkoxy organopolysiloxane and organic oxysilane curing agent, unmated filler moisture-curable
For composition, the high elastic solid (Hookean body) object of the transparency can be become when being solidified.
Specific embodiment
Organic titanic compound of the invention be contain by the molecule containing at least one it is similar with organopolysiloxane
The hydrolization group of structure, i.e. by following structural formula (1) indicate hydrolization group, so as to become have with it is existing organic
The novel organotitanium compound of the catalyst of the moisture-curable composition of the same curability of titanium compound.
-O-E-Si(R)3 (1)
(in formula, E is the alkylidene of carbon atom number 1~4, and R is the alkyl of carbon atom number 1~4.)
That is, novel organotitanium compound of the invention is following organic titanic compound, which is characterized in that contain in the molecule
There is at least one trialkylsilkl as the hydrolization group indicated by structure above (1).
As above-mentioned organic titanic compound, it is able to use the alkoxide of the titanium indicated by the following general formula (2), by the following general formula
(3) titanium chelate using ethyl acetoacetate as ligand that indicates, by the following general formula (4) indicate using acetylacetone,2,4-pentanedione as matching
The titanium chelate of body, the titanium chelate using ethohexadiol as ligand indicated by the following general formula (5).
Ti[OR1]x1[OR2]y1 (2)
Ti[C6H9O3]x2[OR2]y2 (3)
Ti[C5H7O2]x2[OR2]y2 (4)
Ti[C8H17O2]x2[OR2]y2 (5)
[in formula, R1For 1 valency alkyl of carbon atom number 1~6.R2For by the following general formula (6)
-E-Si(R)3 (6)
(in formula, E, R are as described above.)
The trialkylsilkl of expression replaces alkyl.X1 is average value 0~3, and y1 is average value 1~4, and x1+y1
It is 4.X2 is average value 1~3, and y2 is average value 1~3, and x2+y2 is 4.]
These novel organotitanium compounds be for the purpose of being used using the curing catalysts as moisture-curable composition and
Exploitation.Moisture-curable composition comprising these novel organotitanium compounds is solidified well using moisture, forms elasticity
Body.The moisture-curable composition is generally possible to by making containing in the molecule with 2 or more the hydroxyls or alkane in conjunction with silicon
It is obtained in the mixture of the high molecular material of oxygroup and organic oxysilane curing agent containing above-mentioned organic titanic compound.Energy
Enough moisture-curable compositions obtained in this way are solidified well using the moisture in air, in the moisture-curable for being free of filler
In the case where organopolysiloxane composition, the elastic solid (Hookean body) object with high transparency can be obtained, optical characteristics is excellent, therefore
Suitable for electrical and electronic parts.In addition, in the case where containing filler in above-mentioned moisture-curable composition, when uncured
Viscosity adjustment, the adjustment of mobility are possibly realized, in addition, the elastic solid (Hookean body) object obtained when solidifying moisture-curable composition
In, can be improved mechanical property, chemical-resistant, therefore be suitable as sealant for building, the oil sealing etc. of automobile uses.
The present invention is explained in detail below.
[novel organotitanium compound]
Organic titanic compound of the invention is to indicate water-disintegrable by following structural formula (1) containing at least one in the molecule
The organic titanic compound of group.
-O-E-Si(R)3 (1)
(in formula, E is the alkylidene of carbon atom number 1~4, and R is the alkyl of carbon atom number 1~4.)
Wherein, in structure above (1), E is the alkylidene of carbon atom number 1~4, it is highly preferred that for methylene, sub- second
The alkylidene that base, propylidene (trimethylene, methyl ethylidene) etc. are selected from carbon atom number 1~3, each E can it is identical can also
It is different.
In addition, R is the alkyl of carbon atom number 1~4, such as methyl, ethyl, propyl, isopropyl, butyl, different can be enumerated
The alkyl such as butyl, sec-butyl, tert-butyl, more preferably methyl, ethyl, propyl, isopropyl etc. are selected from carbon atom number 1~3
Alkyl, each R can it is identical can also be different.
Organic titanic compound of the invention passes through the hydrolization group for containing indicated by structure above (1) in the molecule,
In the case where the catalyst as the moisture-curable organopolysiloxane composition without filler uses, the organic titanium is utilized
Trialkylsilkl in the hydrolization group of compound, the dispersibility in the organopolysiloxane as host agent improve,
It can obtain the elastic solid (Hookean body) object with high transparency.
As the concrete example of the hydrolization group indicated by structure above (1), trimethyl silyl first can be enumerated
Oxygroup, triethylsilyl methoxyl group, tripropylsilyl ylmethoxy, tributylsilyl methoxyl group, trimethyl first
Silane base oxethyl, triethylsilyl ethyoxyl, tripropylsilyl base oxethyl, tributylsilyl ethyoxyl,
Trimethyl silyl propoxyl group, triethylsilyl propoxyl group, tripropylsilyl base propoxyl group, tributylsilyl
Propoxyl group, trimethyl silyl butoxy, triethylsilyl butoxy, tripropylsilyl base butoxy, tributyl
Silicyl butoxy, triisopropylsilyl methoxyl group, triisopropylsilyl ethyoxyl, triisopropylsilyl
Propoxyl group, triisopropylsilyl butoxy, three (tert-butyl) silicyl methoxyl groups, three (tert-butyl) silicyl second
Oxygroup, three (tert-butyl) silicyl propoxyl group, three (tert-butyl) silicyl butoxy etc..In these, particularly preferred E is
Methylene, ethylidene, the structural formula (1) that R is methyl, ethyl, i.e. trimethyl silyl methoxyl group, triethylsilyl first
Oxygroup, trimethylsilylethoxy), triethylsilyl ethyoxyl.
As the organic titanic compound of hydrolization group for containing at least one in the molecule and being indicated by structure above (1),
The organic titanic compound shown in any one as the following general formula (2), (3), (4) or (5) can be enumerated.
Ti[OR1]x1[OR2]y1 (2)
Ti[C6H9O3]x2[OR2]y2 (3)
Ti[C5H7O2]x2[OR2]y2 (4)
Ti[C8H17O2]x2[OR2]y2 (5)
[in formula, R1For 1 valency alkyl of carbon atom number 1~6.R2For by the following general formula (6)
-E-Si(R)3 (6)
(in formula, E, R are as described above.)
The trialkylsilkl of expression replaces alkyl.X1 is average value 0~3, and y1 is average value 1~4, and x1+y1
It is 4.X2 is average value 1~3, and y2 is average value 1~3, and x2+y2 is 4.]
Wherein, in above-mentioned general formula (2), R1First can be enumerated as 1 valency alkyl for 1 valency alkyl of carbon atom number 1~6
The alkyl such as base, ethyl, propyl, isopropyl, butyl, isobutyl group, sec-butyl, tert-butyl, amyl, hexyl, the naphthenic base such as cyclohexyl,
Aryl such as phenyl etc., in these, particularly preferably isopropyl or methyl, ethyl, propyl, carbon atom number 1~4 as butyl
The linear aliphatic hydrocarbon groups (straight-chain alkyl) of 1 valence.
In above-mentioned general formula (2)~(5), R2Trialkylsilkl to be indicated by the following general formula (6) replaces alkyl.
-E-Si(R)3 (6)
(in formula, E, R are same as described above, can illustrate group similar to the above.)
Organic titanic compound shown in above-mentioned is by containing trialkylsilkl containing what is indicated by general formula (6) in the molecule
Hydrolization group, will by above-mentioned general formula (2), (3), (4) or (5) indicate organic titanic compound as be free of filler it is wet
The catalyst of curing type organopolysiloxane composition in use, using the trialkylsilkl in hydrolization group,
Dispersibility in organopolysiloxane improves, and can obtain the elastic solid (Hookean body) object with high transparency.
The concrete example for replacing alkyl as the trialkylsilkl indicated by above-mentioned general formula (6), can enumerate trimethyl
Silyl methyl, triethylsilylmethyl, tripropylsilyl ylmethyl, tributylsilyl methyl, trimethyl
Silyl ether, triethylsilyl ethyl, tripropylsilyl base ethyl, tributylsilyl ethyl, trimethyl
Silylpropyl, triethylsilyl propyl, tripropylsilyl base propyl, tributylsilyl propyl, trimethyl
Silicyl butyl, triethylsilyl butyl, tripropylsilyl base butyl, tributylsilyl butyl, three isopropyls
Base silyl methyl, triisopropylsilyl ethyl, triisopropylsilyl propyl, triisopropylsilyl fourth
Base, three (tert-butyl) silyl methyls, three (tert-butyl) silyl ethers, three (tert-butyl) silylpropyls, three
(tert-butyl) silicyl butyl etc..In these, particularly preferred E is methylene, ethylidene, the general formula that R is methyl, ethyl
(6), i.e. trimethylsilyl methyl, triethylsilylmethyl, trimethylsilyethyl, triethylsilyl
Ethyl.
In above-mentioned general formula (2), x1 is average value 0~3, and y1 is average value 1~4, and x1+y1 is 4.Wherein, with regard to x1 and
Y1 it is preferred value for, x1 be average value 0~2, y1 be average value 2~4 in the range of, that is, be used as R2By general formula (6)
The hydrolization group containing trialkylsilkl indicated is more, as the moisture-curable organopolysiloxane group for being free of filler
In the case where the curing catalysts use for closing object, the more available elastic solid (Hookean body) object with high transparency.
In addition, x2 is average value 1~3, and y2 is average value 1~3, and x2+y2 is in above-mentioned general formula (3), (4) and (5)
4.Wherein, for the preferred value of x2 and y2, x2 can be average value 1~2, and y2 can be in the range of average value 2~3.Its
Reason is as described above.
In the organic titanic compound indicated by general formula (2), (3), (4) or (5), urged by the organic titanium that general formula (2) indicate
Agent is the alkoxide of titanium, in addition, the organotitanium indicated by general formula (3) is with ethyl acetoacetate [C6H9O3(that is, CH3C
(=O) CHC (=O) OC2H5)] be ligand titanium chelate, by general formula (4) indicate organotitanium be with acetylacetone,2,4-pentanedione
[C5H7O2(that is, CH3C (=O) CHC (=O) CH3)] for the titanium chelate of ligand, the organotitanium by general formula (5) expression is
With ethohexadiol [C8H17O2(that is, HO (CH2)8It O is)] titanium chelate of ligand.These organic titanic compounds can a kind individually make
With the different organic titanic compound of more than two kinds of structure can also be applied in combination.In addition their partial hydrolystate also becomes pair
As.
[manufacturing method of novel organotitanium compound]
The organic titanic compound indicated by general formula (2) can be by the alcohol of titanium tetrachloride and the skeleton with structural formula (1)
Reaction and obtain.
Wherein, the alcohol as the skeleton with structural formula (1) can enumerate the alcohol indicated by following formula (7).
H-O-E-Si(R)3 (7)
(in formula, E, R are same as described above, can illustrate group same as described above.)
For titanium tetrachloride is with the reaction ratio of the alcohol of the skeleton with structural formula (1), rub relative to titanium tetrachloride 1
You, simultaneously by the alcohol by formula (7) expression of 1 mole of the addition above and 10 moles of amounts below skeleton with structural formula (1)
Make its reaction, so as to obtain the organotitanium indicated by general formula (2).Further more, in the skeleton with structural formula (1)
In the remaining situation of alcohol indicated by formula (7), preferably the alcohol of remainder is removed under reduced pressure.
Above-mentioned reaction condition is had no and is specified, for reaction temperature, preferably at 0~100 DEG C, more preferably 10
It is reacted in~80 DEG C of temperature range.But in the case where reaction is violent, need the temperature not solidified in reaction solution
Under reacted, in addition, reacting very slow in the alcohol of titanium tetrachloride and the skeleton with structural formula (1) indicated by formula (7)
It, then can be as long as the boiling point temperature below for the alcohol of the skeleton with structural formula (1) indicated by formula (7) in the case where slow
It is reacted at a temperature of more than above-mentioned temperature range.In reaction due to titanium tetrachloride and reaction product using moisture water
Solution, it is therefore desirable to carry out reaction under conditions of having blocked moisture.Therefore, it is necessary to hinder moisture using means such as nitrogen sealings
It is reacted under disconnected atmosphere.
For the reaction time also without specifying, to titanium tetrachloride and there can be knot using means such as gas chromatographic analysis
The carry out situation of the reaction solution following response for the alcohol of the skeleton of structure formula (1) indicated by formula (7), side confirmation have structural formula (1)
Skeleton by formula (7) indicate alcohol reduce side determines react end time.At this point, if titanium tetrachloride with have structure
The reaction time for the alcohol of the skeleton of formula (1) indicated by formula (7) is too short, sometimes titanium tetrachloride and the skeleton with structural formula (1)
By formula (7) indicate alcohol reaction product yield reduce.If in addition, opposite titanium tetrachloride with there is structural formula (1)
Skeleton by formula (7) indicate alcohol reaction time it is too long, then moisture be mixed into the probability in reactor increase, therefore react life
A possibility that hydrolyzing, oligomeric object increase at object, the unfavorable situations such as viscosity rising occur increases.
In addition, the organic titanic compound indicated by general formula (2) can also by the alkoxide of the titaniums such as tetraisopropoxy titanium with have
The ester exchange reaction of the alcohol of the skeleton of structural formula (1) and obtain.Using the alkoxide of titanium and the ester exchange reaction of comparable alcohol
In generation, since reaction is reversible, it is therefore desirable to synthesize object in the alcohol that the alkoxide removed by titanium generates.There are various
The process removed, commonly known following method: the at a temperature of progress more than the boiling point of the alcohol of the alkoxide generation by titanium is anti-
It answers or under vacuum removes the alcohol generated by the alkoxide of titanium.
Wherein, it as the alkoxide of titanium, can enumerate by Ti [OR1]4(in formula, R1It is same as described above) indicate titanium alkoxide.
In addition, the alcohol as the skeleton with structural formula (1), can enumerate the alcohol indicated by above-mentioned formula (7).
For the alkoxide of titanium is with the reaction ratio of the alcohol of the skeleton with structural formula (1), the alkoxide 1 relative to titanium rubs
You, simultaneously by the alcohol by formula (7) expression of 1 mole of the addition above and 10 moles of amounts below skeleton with structural formula (1)
Make its reaction, so as to obtain the organotitanium indicated by general formula (2).Further more, in the skeleton with structural formula (1)
In the remaining situation of alcohol indicated by formula (7), preferably the alcohol of remainder is removed under reduced pressure.
The reaction condition of above-mentioned ester exchange reaction is had no and is specified, for reaction temperature, preferably 40~120
DEG C, ester exchange reaction is more preferably carried out in 60~100 DEG C of temperature range.This is because the alkoxide of titanium with have structural formula
(1) alcohol of skeleton indicated by formula (7) reacts, and needs to remove the alcohol generated by the alkoxide of titanium.Wherein, the alkoxide of titanium with
In the slowly situation of reaction for the alcohol of skeleton with structural formula (1) indicated by formula (7), as long as having structural formula
(1) boiling point of the alcohol of skeleton temperature below, then can more than above-mentioned temperature range at a temperature of reacted.In reaction by
It is hydrolyzed in the alkoxide and reaction product of titanium using moisture, it is therefore desirable to carry out reaction under conditions of having blocked moisture.
Therefore, it is necessary to will react under atmosphere that moisture blocks using means such as nitrogen sealings.
For the reaction time also without specifying, to the alkoxide of titanium and there can be knot using means such as gas chromatographic analysis
The carry out situation of the reaction solution following response for the alcohol of the skeleton of structure formula (1) indicated by formula (7), side confirmation have structural formula (1)
Skeleton by formula (7) indicate alcohol reduce side determines react end time.At this point, if the alkoxide of titanium with have structure
The ester exchange reaction time of the alcohol of the skeleton of formula (1) is too short, and the alkoxide of titanium is with the skeleton with structural formula (1) by formula sometimes
(7) yield of the reaction product of the alcohol indicated is reduced.If in addition, the alkoxide of opposite titanium and the skeleton with structural formula (1)
The alcohol indicated by formula (7) reaction time it is too long, then moisture is mixed into the increase of the probability in reactor, therefore reaction product water
A possibility that solution, oligomeric object increase, and the unfavorable situations such as viscosity rising occur increases.
By general formula (3), (4) or (5) indicate organic titanic compound can by make it is above-mentioned synthesize by general formula (2) indicate
The alkoxide of titanium and the compound for becoming ligand (are then ethyl acetoacetate [C if it is general formula (3)6H10O3(that is, CH3C (=O)
CH2C (=O) OC2H5)], it is then acetylacetone,2,4-pentanedione [C if it is general formula (4)5H8O2(that is, CH3C (=O) CH2C (=O) CH3)], such as
Fruit is general formula (5), then is ethohexadiol [C8H18O2(that is, HO (CH2)8OH)]) reaction obtains.If ligand with by general formula (2) table
The alcohol reactant salt of the titanium shown, the then alcohol for being incorporated into the alkoxide of titanium are detached from.Even if the alcohol that not will be disengaged from removes, quality will not be made to drop
It is low, but since the purity of organic titanic compound reduces, more preferably the alcohol of generation is removed using the removal step of above-mentioned record
It goes.
Wherein, the alkoxide of the titanium just indicated by general formula (2) reacts ratio with ethyl acetoacetate, acetylacetone,2,4-pentanedione or ethohexadiol
For example, relative to 1 mole of alkoxide of the titanium indicated by general formula (2), need to add the acetoacetate second of 3 moles of amounts below
Ester, acetylacetone,2,4-pentanedione or ethohexadiol make its reaction.Wherein, if it exceeds 3 moles come add ethyl acetoacetate, acetylacetone,2,4-pentanedione or
Ethohexadiol, then ethyl acetoacetate, acetylacetone,2,4-pentanedione or ethohexadiol are remaining, therefore less desirable.
The reaction condition of alkoxide and ethyl acetoacetate, acetylacetone,2,4-pentanedione or ethohexadiol to the titanium indicated by general formula (2) is simultaneously
Without specifying, for reaction temperature, preferably 10~140 DEG C, more preferably carried out in 20~120 DEG C of temperature range it is anti-
It answers.Wherein, very slow in the alkoxide of the titanium indicated by general formula (2) and reacting for ethyl acetoacetate, acetylacetone,2,4-pentanedione or ethohexadiol
It, then can temperature more than above-mentioned temperature range as long as become the boiling point temperature below of the compound of ligand in the case where slow
It is reacted under degree.In reaction, since the alkoxide of titanium and reaction product that are indicated by general formula (2) are hydrolyzed using moisture, because
This needs carries out reaction under conditions of having blocked moisture.Therefore, it is necessary to use the means such as nitrogen sealing to block moisture
It is reacted under atmosphere.
For the reaction time also without specifying, if using means such as gas chromatographic analysis to being indicated by general formula (2)
The carry out situation of the reaction solution following response of the alkoxide and ethyl acetoacetate, acetylacetone,2,4-pentanedione or ethohexadiol of titanium, due to as anti-
Answer the alcohol in conjunction with the alkoxide with titanium of by-product to increase, and become ligand compound reduce, therefore can by any one
The peak area substantially unconverted time is set as the end time of reaction.At this point, if by general formula (2) indicate titanium alkoxide with
The reaction time of ethyl acetoacetate, acetylacetone,2,4-pentanedione or ethohexadiol is too short, the alkoxide and acetyl of the titanium indicated sometimes by general formula (2)
The yield of the reaction product of ethyl acetate, acetylacetone,2,4-pentanedione or ethohexadiol is reduced.If in addition, on the contrary by general formula (2) expression
The alkoxide of titanium and the reaction time of ethyl acetoacetate, acetylacetone,2,4-pentanedione or ethohexadiol are too long, then moisture is mixed into general in reactor
A possibility that rate increases, therefore reaction product hydrolyzes, and oligomeric object increases, and the unfavorable situations such as viscosity rising occur increases.
[the utilization method of novel organotitanium compound]
Above-mentioned novel organotitanium compound can be modified etc. with using on the way on various coating, surface, especially as
In the case where the curing catalysts use of moisture-curable composition, its feature can be played.The reason is that have with it is previous
The same curability of the organic titanic compound used, and the moisture-curable organopolysiloxane composition when being free of filler
In, using the trialkylsilkl in hydrolization group, the dispersibility in organopolysiloxane is improved, therefore energy when solidification
Access the elastic solid (Hookean body) object with high transparency.In turn, selected as the organic titanic compound used in the past certain
In the case where titanium chelate, due to becoming solid state under low-temperature condition, it is difficult to handle in manufacture, but of the invention
Organic titanic compound is also able to maintain that liquid due to containing trialkylsilkl in hydrolization group at low temperature
As a result character becomes and handles easy organic titanium chemical combination while keeping the curability same with existing organic titanic compound
Object.
[application of the novel organotitanium compound in moisture-curable composition]
Organic titanic compound of the invention is as the moisture by solidify giving elastomer character using moisture
The curing catalysts of curing composition use.The moisture-curable composition can have 2 or more and silicon knot in the molecule
The hydroxyl (silanol group) of conjunction or silicyl (such as trialkoxysilyl, dialkoxyalkyl first containing alkoxy
Silylation, alkoxydialkylsilyl etc.) high molecular material, preferably in the molecule have 2 or more in conjunction with silicon
Hydroxyl (silanol group) or silicyl (such as trialkoxysilyl, dialkoxyalkyl monosilane containing alkoxy
Base, alkoxydialkylsilyl etc.) organopolysiloxane (especially with above-mentioned silanol group or contain the first of alkoxy
Silylation is by the straight-chain diorganopolysiloxanecompositions of two end-capped of strand) in the mixture of organic oxysilane curing agent
Use organic titanic compound of the invention.
As the high molecular material in the molecule with 2 or more the hydroxyls or alkoxy in conjunction with silicon, preferably in molecule
In there is 2 or more the hydroxyls (silanol group) in conjunction with silicon or the silicyl containing alkoxy (such as tri-alkoxy first silicon
Alkyl, dialkoxyalkyl silicyl, alkoxydialkylsilyl etc.) organopolysiloxane, especially as not
In the case where moisture-curable composition use containing filler, from above-mentioned organic titanic compound dispersibility aspect,
It is preferable to use have 2 or more the hydroxyls (silanol group) in conjunction with silicon or the silicyl (example containing alkoxy in the molecule
Such as trialkoxysilyl, dialkoxyalkyl silicyl, alkoxydialkylsilyl) organopolysiloxane
(silicyl especially with above-mentioned silanol group or containing alkoxy is organic poly- by the straight-chain two of two end-capped of strand
Siloxanes).
As the organopolysiloxane, such as the organopolysiloxane indicated by the following general formula (8)~(12) can be illustrated.
[changing 1]
(in formula, R3For the saturated hydrocarbyl of unsubstituted or substituted 1 valence of carbon atom number 1~10, a is 10 or more, preferably 20
~2,000, more preferable 30~1,200 integer.)
[changing 2]
(in formula, a is as described above.R4For methyl or ethyl, preferably methyl.R5For the unsubstituted of carbon atom number 1~10 or take
1 valency alkyl in generation.Y is the alkylidene of oxygen atom or carbon atom number 1~5, and N independently is 0 or 1 integer.)
[changing 3]
(in formula, R4、R5, a, Y, N it is as described above.Z is the alkenyl of methyl or carbon atom number 2~5.)
[changing 4]
[in formula, R4、R5, a, Y, N it is as described above.In addition, the integer that b is 1 or more, preferably 1~10.In addition, R6For under
State general formula
[changing 5]
(in formula, R4、R5, Y, N it is as described above.)
The group containing hydrolization group indicated.]
[changing 6]
(in formula, R4、R5、R6, a, b, Y, Z, N it is as described above.)
In above-mentioned formula (8), R3Saturated hydrocarbyl for unsubstituted or substituted 1 valence of carbon atom number 1~10 specifically can
Enumerate the alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, amyl, neopentyl, hexyl, octyl, ring
Naphthenic base such as hexyl etc., these groups hydrogen atom part or all by the halogen atoms such as fluorine, bromine, chlorine, cyano etc. replace
Made of group such as chloromethyl, chloropropyl, bromoethyl, trifluoro propyl, cyano ethyl etc., preferably methyl, ethyl, phenyl.
In above-mentioned formula (9)~(12), R5It specifically can for unsubstituted or substituted 1 valency alkyl of carbon atom number 1~10
Enumerate the alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, amyl, neopentyl, hexyl, octyl, ring
The aryl such as the alkenyls such as the naphthenic base such as hexyl, vinyl, allyl, acrylic, phenyl, tolyl, xylyl, naphthalene, benzyl,
Aralkyl such as phenylethyl, phenyl propyl etc., these groups hydrogen atom part or all by the halogens such as fluorine, bromine, chlorine original
Group such as chloromethyl, chloropropyl, bromoethyl, trifluoro propyl, cyano ethyl made of son, cyano etc. replace etc., preferably first
Base, ethyl, phenyl.
Y is the alkylidene of oxygen atom or carbon atom number 1~5, as alkylidene, can enumerate methylene, ethylidene, Asia third
Base (trimethylene, methyl ethylidene), butylidene (tetramethylene, methyl propylene) etc., as Y, preferably oxygen atom, methylene
Base, ethylidene, propylidene.
Z can enumerate vinyl, allyl, acrylic, fourth as alkenyl for the alkenyl of methyl or carbon atom number 2~5
Alkenyl, pentenyl etc., as Z, preferably methyl, vinyl.
High molecular material with 2 or more the hydroxyls in conjunction with silicon or the silicyl containing alkoxy in the molecule
(silicyl especially with above-mentioned silanol group or containing alkoxy is organic poly- by the straight-chain two of two end-capped of strand
Siloxanes) 23 DEG C at viscosity be preferably 50~200,000mPas, particularly preferably 100~50,000mPas.If
Viscosity is too low, needs a large amount of time or keeping quality to reduce sometimes up to solidification, if excessively high, coating, out gassing sometimes
It reduces, workability is deteriorated.It should be noted that viscosity can use rotary viscosity design determining.
As organic oxysilane curing agent used in moisture-curable composition, can illustrate by the following general formula
(13) organic oxysilane such as indicate, alkoxy silane.Wherein, for organic oxysilane curing agent, general formula (13)
Organic oxysilane partly partial hydrolysis condensate made of hydrolytic condensation (that is, having at least two, preferably 3 in the molecule
The organosiloxane oligomers of the above remaining hydrolization group) also become object.
R7 4-nSi(OR8)n (13)
(in formula, R7For the alkyl, vinyl or halogen-substituted alkyl of carbon atom number 1~6, R8For the alkane of carbon atom number 1~4
Base, alkenyl or alkoxyalkyl.In addition, the integer that n is 2~4.)
Used organic oxysilane curing agent (above-mentioned organic oxysilane or part thereof hydrolytic condensate) make it is wet
Curing type composition plays a role when solidifying as crosslinking agent.
The R of above-mentioned general formula (13)7Replace alkane for the alkyl, vinyl or halogen of identical or different carbon atom number 1~6
Base, specifically, can illustrate methyl, ethyl, propyl, butyl, amyl, hexyl, vinyl, chloromethyl, chloropropyl, bromoethyl,
Trifluoro propyl etc., wherein particularly preferred methyl.In addition, R8For the alkyl, alkenyl or alkoxyalkyl of carbon atom number 1~4, specifically
Ground can illustrate methyl, ethyl, propyl, butyl, acrylic, methoxy, methoxy ethyl, ethoxyl methyl, ethyoxyl
Ethyl etc., preferably methyl or ethyl, more preferably methyl.The integer that n is 2~4, preferably 3 or 4, particularly preferred 3.
As the concrete example of above-mentioned organic oxysilane curing agent, silester, silicic acid propyl ester, methyl trimethoxy oxygen can be illustrated
Base silane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, (the methoxyl group second of methyl three
Oxygroup) silane, vinyl three (methoxy ethoxy) silane, three isopropenoxysilane of methyl etc. and their partial hydrolysis
Condensation product etc..Wherein, methyltrimethoxysilane, vinyltrimethoxysilane are particularly preferably used.
The silicon oxygen that organic oxysilane curing agent can be above-mentioned organic oxysilane, is condensed to yield by its partial hydrolysis
Alkane it is any, as long as the siloxanes in silicon atom have 2 or more, particularly 3 or more alkoxies, straight-chain, divide
Branch shape, ring-type, they are not limited to a kind, two or more can be used.
For the usage amount of organic oxysilane curing agent, relative in the molecule with 2 or more in conjunction with silicon
100 mass parts of high molecular material of hydroxyl (silanol group) or the silicyl containing alkoxy, preferably 0.1~30 mass parts,
Particularly preferred 0.5~10 mass parts.If the usage amount of organic oxysilane curing agent is very few, the composition obtained sometimes through when
Ground thickening or solidification, if excessively, sometimes up to solidify needs a large amount of time or solidifies the machinery of obtained solidfied material
Characteristic is deteriorated.
In above-mentioned moisture-curable composition, relative in the molecule with 2 or more the hydroxyl (silanols in conjunction with silicon
Base) or the silicyl containing alkoxy 100 mass parts of high molecular material, the use level of organic titanic compound of the invention is excellent
Select 0.1~30 mass parts, more preferable 0.5~15 mass parts, particularly preferred 1~5 mass parts.If the cooperation of organic titanic compound
Measure very few, curability timely changes or uncured in the worst case sometimes, if excessively, deep curability drops sometimes
Low or surface cure is too fast and fails to obtain the moisture-curable composition of target.
The hydroxyl (silanol group) with 2 or more in conjunction with silicon or contain alkoxy in the molecule shown in above-mentioned
The moisture of organic titanic compound has been used in the mixture of the organopolysiloxane of silicyl and organic oxysilane curing agent
Curing type organopolysiloxane composition is similar using organopolysiloxane due to the hydrolization group of novel organotitanium compound
Structure, therefore improved with the compatibility of silicone ingredients, about the moisture-curable organopolysiloxane composition for being free of filler
Object can obtain the high elastic solid (Hookean body) object of the transparency.The elastic solid (Hookean body) object of such moisture-curable composition is due to optics spy
Property it is excellent, therefore suitable for electrical and electronic parts etc..
In addition, filler can be contained as needed in above-mentioned moisture-curable composition, it, can be to not solid by containing filler
Moisture-curable composition under change state carries out the adjustment of the adjustment of viscosity, mobility.It is solid for making the moisture containing filler
For the elastic solid (Hookean body) object that change type composition obtains when solidifying, since mechanical property, chemical-resistant can be made to improve, energy
Enough it is suitable as sealant for building, the oil sealing of automobile uses.
Used filler is able to use well known filler.Such as fumed silica, wet type titanium dioxide can be enumerated
Silicon, settleability silica, diatomite, powdered whiting, gel calcium carbonate, titanium oxide, carbon black, talcum, aluminium hydroxide, oxidation
Aluminium, magnesia, zinc carbonate, zinc oxide etc. can be used alone, and can also be used in mixed way two or more.Wherein preferred heavy carbonic acid
Calcium, gel calcium carbonate, fumed silica, settleability silica, aluminium hydroxide, aluminium oxide, zinc carbonate, zinc oxide make
With.In addition, surface treatment for these fillers and being not limited.As surface treating agent when being surface-treated, can illustrate
Dichlorodimethylsilane, chlorine trimethyl silane, dimethyl polysiloxane, octamethylcy-clotetrasiloxane, hexamethyldisilazane this
Organo-silicon compound, fatty acid, resin acid, sulfonic acid, paraffin class of sample etc..
For usage amount when cooperating filler, relative in the molecule with 2 or more the hydroxyl (silane in conjunction with silicon
Alcohol radical) or the silicyl containing alkoxy 100 mass parts of high molecular material, preferably 0.1~500 mass parts, particularly preferably
0.5~200 mass parts.
Any ingredient can be cooperated in above-mentioned moisture-curable composition.As any ingredient, such as can enumerate
Out as the plasticizer of the end unreacted polymer for adjusting rubber physical property, the pigment for coloring, dyestuff, for assigning
It gives electric conductivity, the metal powder of thermal diffusivity, squeeze out the viscosity modifier of workability, ultraviolet absorbing agent, mould inhibitor, resistance to for improving
Various other additives can also be added in hot enhancer, fire retardant etc..
Moisture-curable composition of the invention can by by above-mentioned each ingredient, and then be added thereto above-mentioned various add
The specified amount of agent is added equably to be obtained by mixing in dry atmosphere.In addition, moisture-curable composition of the invention by
It places and solidifies under room temperature (23 DEG C ± 10 DEG C), forming method, condition of cure etc. can be used to be consistent with the type of composition
Well known method, condition.
The moisture-curable composition of the invention obtained in this way is promptly solidified at room temperature using the moisture in air,
It forms heat resistance, weatherability, low-temperature characteristics, the rubber elastomer excellent in adhesion of various substrates, particularly metal consolidated
Compound.In addition, moisture-curable composition of the invention especially storage stability, curability was excellent, such as at 12 months
After storage, if be exposed in air, also promptly solidify, gives solidfied material as described above with excellent physical property.Especially
It is not release toxicity or corrosive gas in solidification, the rust of looking unfamiliar that applied the composition will not be made.Particularly, should
Moisture-curable organopolysiloxane composition is in the case where unmated filler, since the transparency is excellent, in addition to can
Other than electrical and electronic parts coating material, insulating materials, bonding agent, the sealing for various substrates can be used as
Agent, smears, coating agent, mold release treating agent, and be widely used as fibre finish, specifically, can illustrate has
The electrical and electronic parts of the solidfied material of moisture-curable composition of the invention, solidfied material comprising the composition it is for building close
Seal agent, automobile oil sealing of solidfied material comprising the composition etc..Wherein, so-called transparent, it is intended that: positioned at object opposite side,
The permeability of light that internal object can clearly be had an X-rayed and see and rely on wavelength does not have to reduce significantly.
Embodiment
The present invention is specifically described below by way of synthetic example, embodiment and comparative example, but following embodiments is determined
Do not limit the present invention.It should be noted that viscosity is the measured value obtained using rotational viscometer at 23 DEG C, " part " in embodiment
" % " respectively indicates " mass parts " and " quality % ".In addition, having for the tenor of organic titanic compound by what is obtained
The firing of machine titanium compound, measures its mass change, is found out according to following formula.
Tenor (%)=100 × 0.5994 × { ((quality after firing)-(container mass))
/ ((quality before being burnt into)-(container mass)) }
[synthetic example 1]
Sealed with dry nitrogen, have thermometer, ester trap, cooling tube, dropping funel 300ml four-hole boiling flask in
It is packed into tetraisopropyl titanate 28.4g (0.1 mole), instills trimethylsilylmethanol 41.7g (0.4 mole) while stirring.
Then, it ventilates as dry nitrogen, has carried out reaction 8 hours.Ester trap is flowed back into using gas chromatographic analysis
Interior transparency liquid, as a result confirmation makes most isopropyl alcohol reflux.Then, four-hole boiling flask is made to become vacuum condition, using 60
1 hour condition removes remaining alcohol contained in system at DEG C.Transparent liquid is remained in flask, has obtained about 41g
Organic titanic compound (1) (R in general formula (2)1=isopropyl, R2=trimethyl silyl substituent methyl, x1=0, y1=4
Organic titanic compound) (yield: about 89.1%).The tenor of obtained organic titanic compound (1) be 11.1% (theoretical value:
10.4%).
[synthetic example 2]
Sealed with dry nitrogen, have thermometer, ester trap, cooling tube, dropping funel 300ml four-hole boiling flask in
It is packed into tetraisopropyl titanate 28.4g (0.1 mole), instills Trimethylsilylethanol 47.3g (0.4 mole) while stirring.
Then, it ventilates as dry nitrogen, has carried out reaction 8 hours.Ester trap is flowed back into using gas chromatographic analysis
Interior transparency liquid, as a result confirmation makes most isopropyl alcohol reflux.Then, four-hole boiling flask is made to become vacuum condition, using 60
1 hour condition removes remaining alcohol contained in system at DEG C.Transparent liquid is remained in flask, has obtained about 45g
Organic titanic compound (2) (R in general formula (2)1=isopropyl, R2=trimethyl silyl replaces ethyl, x1=0, y1=4
Organic titanic compound) (yield: about 87.3%).The tenor of obtained organic titanic compound (2) be 10.1% (theoretical value:
9.3%).
[synthetic example 3]
Sealed with dry nitrogen, have thermometer, dropping funel 100ml four-hole boiling flask in be packed into synthetic example 1
Obtained in organic titanic compound (1) 23g (about 0.05 mole), while stirring instill ethyl acetoacetate 13.2g (0.1 rubs
You).Then, after so that reaction has been carried out 8 hours at 60 DEG C, four-hole boiling flask is made to become vacuum condition, using 3 hours at 60 DEG C
Condition removes remaining alcohol contained in system.The transparent liquid of brown is remained in flask, has obtained the organic titanium of about 21g
Compound (3) (R in general formula (3)2The organic titanic compound of=trimethyl silyl substituent methyl, x2=2, y2=2) it (receives
Rate: about 81.7%).The tenor of obtained organic titanic compound (3) is 9.5% (theoretical value: 9.3%).
[synthetic example 4]
Sealed with dry nitrogen, have thermometer, dropping funel 100ml four-hole boiling flask in be packed into synthetic example 2
Obtained in organic titanic compound (2) 27.8g (about 0.05 mole), while stirring instill ethyl acetoacetate 13.2g (0.1 rubs
You).Then, after so that reaction has been carried out 8 hours at 60 DEG C, four-hole boiling flask is made to become vacuum condition, using 3 hours at 60 DEG C
Condition removes remaining alcohol contained in system.The liquid that yellow transparent is remained in flask, has obtained the organic titanium of about 23g
Compound (4) (R in general formula (3)2=trimethyl silyl replaces the organic titanic compound of ethyl, x2=2, y2=2) it (receives
Rate: about 84.9%).The tenor of obtained organic titanic compound (4) is 9.0% (theoretical value: 8.8%).
Use organic titanic compound obtained in above-mentioned synthetic example 1~4 and as the tetraisopropyl titanate compared, two
Bis- (ethyl acetoacetate) titaniums of isopropoxy, have carried out evaluation below.Their result is shown in Table 1.
A. water-disintegrable evaluation:
The exposure under 23 DEG C/50%RH environment by organic titanic compound, to the character visual confirmation after 24 hours.
B. low temperature Character Evaluation:
Organic titanic compound is filled in closed container, the exposure under -0 DEG C of environment, visual confirmation is after 24 hours
Character.
[table 1]
By the result of above-mentioned table 1 it is found that the above-mentioned organic titanic compound synthesized is all solid by water-disintegrable evaluation test
Change, therefore there is the hydrolysis property same with the existing organic titanic compound used as compared with.In addition, being commented in low temperature character
In valence, bis- (ethyl acetoacetate) titaniums of existing titanium chelate, i.e. diisopropoxy are solid, and the titanium chelate, i.e. synthesized
Organic titanic compound obtained in above-mentioned synthetic example (1)~(4) are liquid under room temperature (23 DEG C ± 10 DEG C).Thus may be used
Know, also causes character to change unlike bis- (ethyl acetoacetate) titaniums of diisopropoxy under equal low temperature environment in winter, because
This processing is easy.
[embodiment 1]
The straight-chain dimethyl that trimethoxysilyl blocks in two end of strand of viscosity 1,000mPas is poly-
5.0 parts and (1) 3.0 part of organic titanic compound of methyltrimethoxysilane are added in 100 parts of siloxanes, are mixed under moisture blocking
Until becoming uniformly, to prepare composition (1).
[embodiment 2]
The straight-chain dimethyl that trimethoxysilyl blocks in two end of strand of viscosity 1,000mPas is poly-
5.0 parts and (2) 3.0 parts of organic titanic compound of methyltrimethoxysilane are added in 100 parts of siloxanes, are mixed under moisture blocking
Until becoming uniformly, to prepare composition (2).
[embodiment 3]
The straight-chain dimethyl that trimethoxysilyl blocks in two end of strand of viscosity 1,000mPas is poly-
5.0 parts and (3) 3.0 parts of organic titanic compound of methyltrimethoxysilane are added in 100 parts of siloxanes, are mixed under moisture blocking
Until becoming uniformly, to prepare composition (3).
[embodiment 4]
The straight-chain dimethyl that trimethoxysilyl blocks in two end of strand of viscosity 1,000mPas is poly-
5.0 parts and (4) 3.0 parts of organic titanic compound of methyltrimethoxysilane are added in 100 parts of siloxanes, are mixed under moisture blocking
Until becoming uniformly, to prepare composition (4).
[comparative example 1]
In embodiment 1, other than replacing organic titanic compound (1) and having used 3.0 parts of tetraisopropyl titanate, together
It carries out to sample, prepares composition (5).
[comparative example 2]
In embodiment 1, other than replacing organic titanic compound (1) and having used 3.0 parts of butyl titanate, equally
Ground carries out, and prepares composition (6).
[comparative example 3]
In embodiment 1, in addition to replace organic titanic compound (1) and used 3.0 parts of (tert-butyl) ester of metatitanic acid four with
Outside, it is carried out similarly, prepares composition (7).
[comparative example 4]
In embodiment 3,3.0 parts of bis- (the acetyl second of diisopropoxy have been used in addition to replacement organic titanic compound (3)
Acetoacetic ester) other than titanium, it is carried out similarly, is prepared for composition (8).
[comparative example 5]
In embodiment 3, used 3.0 parts of two octyloxies bis- (ethohexadiol) in addition to replacing organic titanic compound (3)
It other than titanium, is carried out similarly, is prepared for composition (9).
[comparative example 6]
In embodiment 3,3.0 parts of bis- (the acetyl second of diisopropoxy have been used in addition to replacement organic titanic compound (3)
Acetoacetic ester) other than titanium, it is carried out similarly, is prepared for composition (10).
Tack-free time, the solidification of composition obtained in above-described embodiment, comparative example are measured using method shown in following
The hardness and the transparency of object are simultaneously evaluated.
[test method]
For the composition prepared in above-described embodiment, comparative example, determines and disappear according to method specified in JIS A5758
Viscous time (drying time of finger-touching).
In addition, by the composition prepared in above-described embodiment, comparative example be cast to thickness about 2mm it is framed in, 23 DEG C,
It is maintained 7 days under 50%RH, has obtained the sheet rubber of 2mm thickness.Using obtained sheet rubber, rubber is determined according to JIS K6249
Hardness.It should be noted that hardness is measured using the Durometer A hardometer of JIS K6249.
In addition, using (strain) Hitachi Ha イ テ Network サ イ エ Application ス system to be divided for the transparency of obtained sheet rubber
Photometer U-3310 measures the light transmittance of 500nm (A) and 800nm (B), its difference is determined as " conjunction for the situation within ± 5%
Lattice ".
The result of Examples 1 to 4 and comparative example 1~6 is shown in Table 2 below.
[table 2]
[evaluation]
It knows that the composition of Examples 1 to 4 meets important document of the invention, there is good curability, and composition is solid
The hardness of solidfied material made of change is also high, becomes good elastomer.In addition, the difference of the light transmittance due to 800nm to 500nm
It also is 1~3% or so, it may thus be appreciated that the transparency is very high.
And the composition of comparative example 1~6 is using existing organic titanic compound as the catalyst of moisture-curable composition
It uses.The composition of comparative example 1~4 is to have used the alkoxide of existing titanium as the example of catalyst, although indicating curability
Tack-free time it is rapid, but the water-disintegrable height of the alkoxide of titanium, compound variation after hydrolysis is is difficult in organopolysiloxane
The substance of dissolution, therefore the result is that the difference of the light transmittance of 800nm to 500nm becomes 5% or more, the transparency is poor.In addition, comparative example
5,6 composition is to use existing titanium chelate as the example of catalyst, even if the compound using them, after hydrolysis
Variation is is difficult to the substance dissolved in organopolysiloxane, therefore the difference of the light transmittance of 800nm to 500nm becomes 5% or more, knot
Fruit is that the transparency is poor.Effectiveness of the invention is able to confirm that by above-mentioned result.
Industrial availability
Organic titanic compound of the invention has the curability same with existing organic titanic compound, and has cooperated this
The curability of the moisture-curable composition of organic titanic compound is good, and then by unmated filler with organopolysiloxane
When solidifying for the moisture-curable composition of host agent, the high elastic solid (Hookean body) object of the transparency can be become.Therefore, it is hopeful electrical
It is applied in electronic component etc., and then also it can be expected that being used as Building Encapsulant, automobile oil sealing.
Claims (10)
1. organic titanic compound contains the hydrolization group that at least one is indicated by following structural formula (1) in the molecule:
-O-E-Si(R)3 (1)
In formula, E is the alkylidene of carbon atom number 1~4, and R is the alkyl of carbon atom number 1~4.
2. organic titanic compound according to claim 1, by any of the following general formula (2), (3), (4) or (5)
It indicates:
Ti[OR1]x1[OR2]y1 (2)
Ti[C6H9O3]x2[OR2]y2 (3)
Ti[C5H7O2]x2[OR2]y2 (4)
Ti[C8H17O2]x2[OR2]y2 (5)
In formula, R1For 1 valency alkyl of carbon atom number 1~6, R2Trialkylsilkl to be indicated by the following general formula (6) replaces alkane
Base, x1 are average value 0~3, and y1 is average value 1~4, and it is average value 1~3 that x1+y1, which is 4, x2, and y2 is average value 1~3,
And x2+y2 is 4,
-E-Si(R)3 (6)
In formula, E is the alkylidene of carbon atom number 1~4, and R is the alkyl of carbon atom number 1~4.
3. organic titanic compound according to claim 1 or 2 is used for the curing catalysts of moisture-curable composition.
4. moisture-curable composition provides elasticity with moisture-curable containing organic titanic compound as claimed in claim 3
Body.
5. moisture-curable composition according to claim 4 contains in the molecule with 2 or more in conjunction with silicon
The high molecular material and organic oxysilane curing agent of hydroxyl or alkoxy.
6. moisture-curable composition according to claim 5, wherein in the molecule with 2 or more in conjunction with silicon
The high molecular material of hydroxyl or alkoxy is organic poly- silicon in the molecule with 2 or more the hydroxyls or alkoxy in conjunction with silicon
Oxygen alkane.
7. moisture-curable composition according to claim 5 or 6, also contains filler.
8. electrical and electronic parts, the solidfied material with composition described in any one of the claims 4~7.
9. Building Encapsulant, it includes the solidfied materials of the composition described in any one of the claims 4~7.
10. automobile oil sealing, it includes the solidfied materials of the composition described in any one of the claims 4~7.
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| JP2017-174189 | 2017-09-11 | ||
| JP2017174189A JP6816681B2 (en) | 2017-09-11 | 2017-09-11 | Curing catalyst, moisture-curable room temperature curable organopolysiloxane composition and molded article |
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| CN109485672B CN109485672B (en) | 2023-09-26 |
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| JP (1) | JP6816681B2 (en) |
| CN (1) | CN109485672B (en) |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5984948A (en) * | 1982-07-30 | 1984-05-16 | ロ−ヌ−プ−ラン・スペシヤリトウ・シミク | One component organopolysiloxane composition |
| US6197896B1 (en) * | 1999-07-12 | 2001-03-06 | International Business Machines Corporation | Graft polymers and use thereof |
| JP2002371185A (en) * | 2001-06-06 | 2002-12-26 | Dow Corning Corp | Silicone composition and cured silicone product |
| JP2003160587A (en) * | 2001-11-28 | 2003-06-03 | Nitto Kasei Co Ltd | Titanium compound, curing catalyst comprising the same and moisture curing organopolysiloxane composition containing curing catalyst |
| JP2003165916A (en) * | 2001-11-28 | 2003-06-10 | Nitto Kasei Co Ltd | Curing catalyst for organic polymer, and moisture-curing organic polymer composition containing the same |
| JP2005213487A (en) * | 2004-02-02 | 2005-08-11 | Ge Toshiba Silicones Co Ltd | Room temperature-curing polyorganosiloxane composition |
| JP2005247923A (en) * | 2004-03-02 | 2005-09-15 | Ge Toshiba Silicones Co Ltd | Curable polymer composition and method for preparing curable polymer composition |
| CN106795182A (en) * | 2014-09-04 | 2017-05-31 | 信越化学工业株式会社 | New organic titanic compound, the manufacture method of the organic titanic compound and room temperature-curable resin composition |
-
2017
- 2017-09-11 JP JP2017174189A patent/JP6816681B2/en active Active
-
2018
- 2018-07-24 TW TW107125424A patent/TWI791562B/en active
- 2018-09-11 CN CN201811053348.1A patent/CN109485672B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5984948A (en) * | 1982-07-30 | 1984-05-16 | ロ−ヌ−プ−ラン・スペシヤリトウ・シミク | One component organopolysiloxane composition |
| US6197896B1 (en) * | 1999-07-12 | 2001-03-06 | International Business Machines Corporation | Graft polymers and use thereof |
| JP2002371185A (en) * | 2001-06-06 | 2002-12-26 | Dow Corning Corp | Silicone composition and cured silicone product |
| JP2003160587A (en) * | 2001-11-28 | 2003-06-03 | Nitto Kasei Co Ltd | Titanium compound, curing catalyst comprising the same and moisture curing organopolysiloxane composition containing curing catalyst |
| JP2003165916A (en) * | 2001-11-28 | 2003-06-10 | Nitto Kasei Co Ltd | Curing catalyst for organic polymer, and moisture-curing organic polymer composition containing the same |
| JP2005213487A (en) * | 2004-02-02 | 2005-08-11 | Ge Toshiba Silicones Co Ltd | Room temperature-curing polyorganosiloxane composition |
| JP2005247923A (en) * | 2004-03-02 | 2005-09-15 | Ge Toshiba Silicones Co Ltd | Curable polymer composition and method for preparing curable polymer composition |
| CN106795182A (en) * | 2014-09-04 | 2017-05-31 | 信越化学工业株式会社 | New organic titanic compound, the manufacture method of the organic titanic compound and room temperature-curable resin composition |
Non-Patent Citations (1)
| Title |
|---|
| BY JOHN JEFFERY 等: "Metallocene Derivatives of Early Transition Metals. Part 4.1 Chemistry of the Complexes [M(η-C5H5)2RR"][M=Ti,Zr,or Hf;R=CH2M"Me3(M"=C,Si,Ge,or Sn) or CH(SiMe3)2; R"=Cl or alkyl] and the X-Ray Structures of [Zr(η-C5H5)2(CH2M"Me3)2] (M"=C or Si)", 《JOURNAL OF THE CHEMICAL SOCIETY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201920216A (en) | 2019-06-01 |
| TWI791562B (en) | 2023-02-11 |
| CN109485672B (en) | 2023-09-26 |
| JP2019048784A (en) | 2019-03-28 |
| JP6816681B2 (en) | 2021-01-20 |
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