CN109970980A - One pack system addition type polysiloxane composition - Google Patents
One pack system addition type polysiloxane composition Download PDFInfo
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- CN109970980A CN109970980A CN201711458656.8A CN201711458656A CN109970980A CN 109970980 A CN109970980 A CN 109970980A CN 201711458656 A CN201711458656 A CN 201711458656A CN 109970980 A CN109970980 A CN 109970980A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L83/04—Polysiloxanes
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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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
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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
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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Abstract
The present invention relates to a kind of one pack system addition type polysiloxane composition, longer-term can be kept to stablize under room temperature or cryogenic conditions, but when heated can rapid curing.The invention further relates to prepare the purposes of the method for the one pack system addition type polysiloxane composition and the composition, it is especially used in the fields such as electronics, electric power, communication, automobile, high-speed railway, aerospace, medical treatment and wearable smart machine.The invention further relates to purposes of the combination of at least one heterocyclic carbene ligand/metal complex catalyst and at least one inhibitor in one pack system addition type polysiloxane composition；And a kind of Si―H addition reaction method, the combination including using at least one heterocyclic carbene ligand/metal complex catalyst and at least one inhibitor.
Description
Technical field
The present invention relates to a kind of one pack system addition type polysiloxane composition, can be kept under room temperature or cryogenic conditions compared with
It steadily in the long term, but when heated can rapid curing.The invention further relates to prepare the one pack system addition type polysiloxane
The method of composition and the purposes of the composition are especially used in electronics, electric power, communication, automobile, high-speed railway, aviation boat
It, in the fields such as medical treatment and wearable smart machine.
The invention further relates to the groups of at least one heterocyclic carbene ligand/metal complex catalyst and at least one inhibitor
Close the purposes in one pack system addition type polysiloxane composition；And a kind of Si―H addition reaction method, including use at least one
The combination of heterocyclic carbene ligand/metal complex catalyst and at least one inhibitor.
Background technique
Hydrosilylation, which is widely used in silicone industry, prepares monomer, silicon-carbon containing key polymer, organosilicon crosslinked poly-
Object is closed, to obtain various products.The transition metal such as platinum, rhodium, ruthenium, palladium, osmium and iridium are often used as catalyst for addition reaction of hydrogen and silicon.
In general, hydrosilylation catalyst using these metals compound form, such as chloroplatinic acid, chloroplatinic acid hexahydrate,
Platinous chloride etc..In addition, the Karstedt catalyst of siloxanes dissolution is also commonly used for hydrosilylation, wherein siloxanes used
It is the disiloxane containing divinyl.Generally, due to Karstedt catalyst, reaction speed is too fast at room temperature, add-on type
Silicone composition is typically prepared into two components and is stored.But in practical applications, add-on type product in many cases
It is hoped to construct so very convenient with single group form-separating packaging.In this case, one kind is developed in room temperature or cryogenic conditions
Under be able to maintain long period stable storage but show the one pack system add-on type room temperature silicone composition of reactivity at high temperature
Object is just very important.
In general, when hydrosilylation inhibitor is used to extend the storage and operation of single-component polysiloxane composition
Between.However, inhibitor could often obtain satisfied storage period relative to the molar equivalent of traditional catalyst when bigger,
Detrimental effect is crosslinked with to hydrosilylation simultaneously.
Microcapsules encapsulation platinum metal catalysts may be alternatively used for the poly- addition system of one pack system to obtain the silicon of ambient-temp-stable
Silicone compositions.Such as according to patent US 6140446A, platinum catalyst is encapsulated in the hot melt chemical combination that fusing point is 40-200 DEG C
In object, then packaged catalyst is blended to be formed with good room temperature or low-temperature stability and be heated with organopolysiloxane
The silicone composition of quick setting capabilities.However, the platinum catalyst of microencapsulation generally requires induction period to melt when in use
Change carrier, this will lead to certain lag time.Meanwhile there is also the compatibilities of siloxane systems for microcapsule coated platinum catalyst
With risk of leakage problem.
Coordination environment around pt atom has the stability of platinum catalyst and its triggering temperature of reactivity very big
It influences.Chemical structure by adjusting the ligand of platinum can obtain novel platinum catalyst, with preparation in low temperature or under room temperature
With excellent stability and at relatively high temperatures quick-setting one pack system addition type polysiloxane composition.Patent
US5728839 discloses metal/carbene complex with heterocyclic carbene ligand.These novel complex compounds can be used for insatiable hunger
With the hydrogenation or hydroformylation reaction of organic compound.In addition, patent US20060173150 is further disclosed with heterocycle
Platinum catalyst of the Cabbeen as ligand.Compared with Karstedt platinum catalyst, this novel catalyst can be used for Si―H addition reaction
The Potential feasibility to prepare crosslinked siloxane elastomer and with ambient-temp-stable storage and heated fast reaction is obtained is reacted, with
It is used to prepare one pack system addition type polysiloxane composition.Novel platinum catalyst by improving ligand structure avoids traditional platinum
Catalyst and microcapsule coated catalyst bring a series of problems.However, relying solely on the platinum containing heterocycle carbine as ligand
Catalyst can not fully meet the demand of single-component silicone composition, because storage period is still limited.
Thus always exist the needs for obtaining the one pack system addition type polysiloxane composition of excellent combination property.
Summary of the invention
It is above-mentioned to need to be satisfied through the invention.
The present invention is intended to provide can be used for the catalyst system of one pack system addition type polysiloxane composition, the catalyst system packet
Containing one or more metal complexes based on heterocycle carbine as catalyst, which has low work at ambient temperature
Property, and include a small amount of inhibitor.By the proper fit of catalyst and inhibitor, can get with more exact controllability
Catalyst system.So that the one pack system addition type polysiloxane composition can have enough in low temperature or under room temperature
Stationary phase and in a heated condition can rapid curing, realize the well balanced of storage period and cross-linking reaction.
Specifically, the purpose of the present invention is to provide a kind of one pack system addition type polysiloxane composition, include:
A, at least one polysiloxane A with alkenyl and/or alkynyl in conjunction with silicon atom；
B, at least one poly- organohydrogensiloxanes B；
C, at least one heterocyclic carbene ligand/metal complex catalyst C；
D, at least one inhibitor D.
Another object of the present invention is related to the method for being used to prepare the one pack system addition type polysiloxane composition.
A further object of the present invention is related to the purposes of the one pack system addition type polysiloxane composition, is especially used in electricity
In the fields such as son, electric power, communication, automobile, high-speed railway, aerospace, medical treatment and wearable smart machine.
Another object of the present invention is related at least one heterocyclic carbene ligand/metal complex catalyst C and at least one
Purposes of the combination of kind inhibitor D in one pack system addition type polysiloxane composition, it is especially useful in make the one pack system add-on type
Polysiloxane composition has the sufficiently stable phase in low temperature or under room temperature and in a heated condition can rapid curing.
Another object of the present invention is related to a kind of Si―H addition reaction method, including uses at least one heterocyclic carbene ligand/gold
Belong to the combination of complex compound catalyst C and at least one inhibitor D, so that corresponding polysiloxane composition can be in room temperature
Or storage of stable and long period under low temperature, while the rapid curing when temperature is higher.
A, the polysiloxane A with alkenyl and/or alkynyl in conjunction with silicon atom
The polysiloxanes basis composition reacted for that can pass through Si―H addition reaction has the alkenyl in conjunction with silicon atom
And/or the polysiloxane of alkynyl and poly- organohydrogensiloxanes are the basis for constituting silicon composition.In the present invention
In, polysiloxanes basis composition is not particularly limited, as long as it can be formed by curing corresponding organosilicon material.
Polysiloxanes basis composition be it is cured based on Si―H addition reaction, i.e., by having in system and silicon atom knot
The alkenyl of conjunction and/or the polysiloxane of alkynyl and poly- organohydrogensiloxanes are crosslinked solid under platinum metal catalysts effect
Change.
For having the polysiloxane A of alkenyl and/or alkynyl in conjunction with silicon atom, the alkenyl and/or alkynes
Base can be in any position in the polysiloxane backbone, such as in the end of strand or centre or both ends and intermediate.
Preferably, the polysiloxane A with alkenyl and/or alkynyl in conjunction with silicon atom includes:
(i) siloxy units of formula (I-1)
R0 aZbSiO[4-(a+b)]/2 (I-1)
Wherein
R0Indicate C2-12, preferably C2-6Alkenyl or alkynyl, most preferably vinyl or allyl,
Z can indicate the univalence hydrocarbyl with 1 to 30, preferably 1 to 12 carbon atom identical or differently, preferred to select
From C1-8Alkyl, including the alkyl optionally replaced by least one halogen atom, and further preferably selected from aryl, particularly
C6-20Aryl,
A is 1 or 2, and b is that the summation of 0,1 or 2 and a+b is 1,2 or 3,
Optionally,
(ii) other siloxy units of formula (I-2)
Wherein
Z has meaning as described above and c is 0,1,2 or 3.
In a preferred embodiment, Z can be selected from methyl, ethyl, propyl, 3,3,3- trifluoropropyl groups, benzene
Base, xylyl and tolyl etc..Preferably, the group Z of at least 60mol% (or in quantitative terms) is methyl.
Described there is the polysiloxane A of alkenyl and/or alkynyl in conjunction with silicon atom can have 50mPa.s extremely
The viscosity of 2,000,000mPa.s viscosity, preferably 200mPa.s to 1,000,000mPa.s.The polysiloxane A can also
To be the bigger glue of viscosity.In this application, what all viscositys were directed to is Dynamic Viscosity numerical value and can be for example with
The mode known uses Brookfield apparatus measures at 20 DEG C.It is not suitable for if viscosity is very big with Brookfield instrument
Words are then measured using such as needle penetration or other methods.
Polysiloxane A with alkenyl and/or alkynyl in conjunction with silicon atom can be only by the unit shape of formula (I-1)
At or can also additionally include formula (I-2) unit.The alkenyl having in conjunction with silicon atom and/or the poly- of alkynyl have
Organic siloxane A is straight chain, branching or cricoid.Under the premise of not destroying the object of the invention, it can also contain in strand
Network-like structure, it is preferred that the network-like structure is in the poly-organosilicon with alkenyl and/or alkynyl in conjunction with silicon atom
Weight ratio in the molecule of oxygen alkane A is no more than 10%, more preferably no more than 5%.
The example of the siloxy units of formula (I-1) is vinyidimethylsiloxy groups, vinyl phenylmethyl
Siloxy, vinyl methyl siloxy and vinyl silane oxygroup unit.
The example of the siloxy units of formula (I-2) is SiO4/2Unit, dimethyl silane oxygroup, aminomethyl phenyl first
Siloxy, diphenyl silicon oxygroup, methyl silicane oxygroup and phenylsilane oxygroup.
The example of the described polysiloxane A with alkenyl and/or alkynyl in conjunction with silicon atom include straight chain or
Cricoid compound, such as dimethyl polysiloxane with dimethylvinylsilyl end group, with trimethyl silyl
(methyl ethylene) (dimethyl) polysiloxane copolymer of cardinal extremity the base, (first with dimethylvinylsilyl end group
Base vinyl) (dimethyl) polysiloxane copolymer and cricoid methylvinyl-polysiloxane.
B, poly- organohydrogensiloxanesB
In polysiloxanes basis composition of the invention, poly- organohydrogensiloxanes B must have at least two to be connected to
Hydrogen atom on identical or different silicon atom, with the polysiloxane A with alkenyl and/or alkynyl in conjunction with silicon atom
Carry out cross-linking reaction.Therefore, as poly- organohydrogensiloxanes B, it is bonded at least two that at least one per molecule can be used
At least two per molecules can be used at least in the hydrogen containing siloxane of hydrogen atom on identical or different silicon atom
The hydrogen containing siloxane of one hydrogen atom being connected on identical or different silicon atom.
In component B according to the present invention, SiH group can any position in polysiloxane backbone, such as point
The end or centre of subchain or both ends and centre.
The poly- organohydrogensiloxanes B with SiH group can be crosslinked with component A to react, i.e., by making in component B
SiH group in component A alkenyl and/or alkynyl react and form solidfied material.Preferably as component B, using at least one
The each molecule of kind has the poly- organohydrogensiloxanes of two, three or more SiH group.
In a preferred embodiment, the poly- organohydrogensiloxanes B includes
(i) siloxy units of formula (II-1):
HdR1 eSiO[4-(d+e)]/2 (II-1)
Wherein
R1Univalence hydrocarbyl can be indicated identical or differently, be preferably selected from C1-8Alkyl, including optionally by least one
The alkyl that a halogen atom replaces, and further preferably it is selected from aryl, particularly C6-20Aryl,
D is 1 or 2, and e is that the summation of 0,1 or 2 and d+e is 1,2 or 3,
Optionally,
(ii) other units of at least one formula (II-2)
R2 fSiO(4-f)/2 (II-2)
Wherein
R2With as above for R1The meaning and f is 0,1,2 or 3.
In a kind of preferred embodiment, R2Methyl, ethyl, propyl, 3,3,3- trifluoro propyl, benzene can be selected from
Base, xylyl and tolyl etc..
The Dynamic Viscosity of the component B is at least 1mPa.s and preferably 3 between 1000mPa.s, more preferable 5-
300mPa.s。
The poly- organohydrogensiloxanes B can be formed only by the unit of formula (II-1) or or additionally be included formula (II-
2) unit.The poly- organohydrogensiloxanes B can have straight chain, branching or cricoid structure.Do not destroying the object of the invention
Under the premise of, network-like structure can also be contained in strand, it is preferred that the network-like structure is in the poly- organohydrogensilicon
Weight ratio in oxygen alkane B is no more than 10%, more preferably no more than 5%.
The example of formula (II-1) unit is H (CH3)2SiO1/2,HCH3SiO2/2With H (C6H5)SiO2/2。
The example of formula (II-2) unit then can be identical as example those of is provided above with respect to formula (I-2) unit.
The example of available poly- organohydrogensiloxanes B includes straight chain or cricoid compound, such as has hydrogenation dimethyl methyl
The dimethyl polysiloxane of silylation end group has (dimethyl) (hydrogen methyl) poly- silicon oxygen with trimethylsilyl end groups
The copolymer of alkane unit, with hydrogenation dimetylsilyl end group with (dimethyl) (hydrogen methyl) polysiloxane unit
Copolymer, the hydrogenating methyl polysiloxanes with trimethylsilyl end groups and cricoid hydrogenating methyl polysiloxanes.
In one embodiment, which can be comprising hydrogenation dimetylsilyl end group
The mixture of dimethyl polysiloxane and the organopolysiloxane comprising at least three hydrosilyls.
(C) heterocyclic carbene ligand/metal complex catalyst
In one pack system addition type polysiloxane composition of the invention, at least one heterocyclic carbene ligand/metal is used
Complex compound catalyst.The catalyst can generate all very high selective catalysis activity on qualitative and quantitative in reaction medium, and
With temperature sensitivity.
Under the action of the catalyst, at least one poly-organosilicon with alkenyl and/or alkynyl in conjunction with silicon atom
Oxygen alkane A and at least one poly- organohydrogensiloxanes B is crosslinked by Si―H addition reaction.By being matched with inhibitor (D), thus
Corresponding polysiloxane composition is stablized under room temperature or low temperature and is stored for a long time, for example, up to one month or
One month or more, preferably three months or three months or more or even six months or six months or more, at the same it is fast when temperature is higher
Speed solidification.
The catalyst C includes the compound of at least one formula (III):
Wherein, M, which is represented, is selected from Handbook of Chemistry and Physics the 65th edition, discloses in 1984-1985
The periodic table of elements the 8th race's metal metal, such as palladium, platinum or the nickel of 0 oxidation state, preferably M represent the platinum of 0 oxidation state；
LγThe Cabbeen of representative formula (III-1):
Wherein:
A and B independently represents C or N, and when A represents N, then only T3Or T5One of them is nonsensical, when B is represented
When N, then only T4Or T6One of them is nonsensical；
T3、T4、T5And T6Independently represent hydrogen atom；Alkyl；The naphthenic base optionally replaced by alkyl or alkoxy；Appoint
The aryl that selection of land is replaced by alkyl or alkoxy；Alkenyl；Alkynyl；Or in which aryl moiety is optionally taken by alkyl or alkoxy
The aralkyl in generation；Or
T1、T2、T3、T4、T5Or T6Naphthenic base, aryl or heterocycle can be formed together with the A and B for representing carbon atom.
T1And T2Independently represent alkyl；Optionally by alkyl-substituted alkyl；Perfluoroalkyl or optionally by perfluoroalkyl
Substituted alkyl；The naphthenic base optionally replaced by alkyl or alkoxy；The aryl optionally replaced by alkyl or alkoxy；Chain
Alkenyl；Alkynyl；Or in which the aralkyl that aryl moiety is optionally replaced by alkyl or alkoxy；Or
T1And T2Independently represent the univalent perssad of following formula (III-1.1):
V1-V2 (III-1.1)
Wherein:
V1 is divalent hydrocarbon group, preferably alkylidene,
V2 is the univalent perssad selected from following substituent group:
Alkoxy ,-OR3, wherein R3Corresponding to hydrogen, alkyl or aryl
Amine, preferably N (R3)2, wherein R3Corresponding to hydrogen, alkyl or aryl, or
T1And T2Independently represent the univalent perssad of following formula (III-1.2):
W1-ω-W2 (III-1.2)
Wherein:
W1For divalent hydrocarbon group, preferably optionally substituted linear chain or branched chain C1-C10Alkylidene.
ω is represented:
-R4C=CR4-
Wherein R4Corresponding to H or alkyl or-C ≡ C-
W2For the univalent perssad selected from following substituent group:
R5=alkyl, H；
Si- alkyl or Si- alkoxy, preferably Si- (R6)3, wherein R6=alkyl；
Alcohol, preferably-C (R7)2OH, wherein R7=H or alkyl；
Ketone, preferably
Wherein R8=alkyl；
Carboxyl, preferably
Wherein R9=alkyl；
Amide, preferably
Wherein R10=H, alkyl；
Acyl group, preferably
Wherein R11=alkyl；
Or substituent group T1、T2、T3、T4、T5And T6It can be formed in couples when on two adjacent atoms in formula (III-1)
Saturated or unsaturated hydro carbons chain.
Preferably, in the Cabbeen of formula (III-1):
T3Or T5One of those and T4Or T6One of those represents hydrogen atom or is formed together phenyl；And/or
T1And T2It may be the same or different, represent (C1-C8) alkyl or (C3-C8) naphthenic base, be preferably selected from: methyl, n-propyl,
N-pentyl, neopentyl (- CH2-C(CH3)3), cyclopenta, cyclohexyl, adamantyl, allyl (- CH2- CH=CH2), first is for alkene
Propyl (- CH2-C(CH3)=CH2), propargyl, high-propargyl (- (CH2)2- C ≡ CH) or
-(CH2)γ=1 to 3-C≡C-C(CH3)3
Or-(CH2)γ=1 to 3-C≡C-Si(CH3)3
Or-(CH2)γ=1 to 4Amine (such as N (CH3)2)
Or-(CH2)γ=1 to 4Alkoxy (such as O (CH3)2),
Or optionally substituted aryl is represented, such as by one or more C1-C3Alkyl, one or more halohydrocarbyls
Such as CF3, one or more alkoxies such as CH3Hydro carbons group such as CH of the O or one or more comprising one or more ketone units3CO-
Replace, wherein the preferred phenyl of the aryl, naphthalene, anthryl and phenanthryl；
A and B represent carbon atom.
According to ligand L in a kind of version, with catalyst CγThe Cabbeen of corresponding formula (III-1) can contain at least two
Condensed core, i.e. T1、T2、T3、T4、T5Or T6In be located on two adjacent cyclic atoms at least two substituent groups be formed together it is full
And/or unsaturated hydro carbons chain, preferably comprise 3 to 6 carbon atoms.Wording " saturated or unsaturated hydro carbons chain " means to contain
There are one or more olefinic double bond types or the unsaturated linear chain or branched chain hydro carbons chain of three bond type of acetylene series.
When Cabbeen (III-1) is containing condensed core, correspond to one of following formula, wherein alk represents saturated or unsaturated
Hydro carbons chain:
Wherein A, B, T1、T2、T3、T4、T5、T6With definitions as described above.
Alternatively, LγThe Cabbeen of representative formula (III-2):
Wherein:
A and B independently represent C, and when A and B independently represents N, formula (III-2) is nonsensical；
T1And T2It is defined as described in formula (III-1)；
T7And T8Independently represent alkyl；The naphthenic base optionally replaced by alkyl or alkoxy；Optionally by alkyl or alkane
The aryl that oxygroup replaces；Alkenyl；Alkynyl；Or in which the aralkyl that aryl moiety is optionally replaced by alkyl or alkoxy；Or
Person is the group that nitrogen, oxygen, sulphur, phosphorus etc. can form double bond with carbon.
T7Or T8Naphthenic base, aryl or heterocycle can be formed together with the A and B for representing carbon atom.
Preferably, in the Cabbeen of formula (III-2): T7Or T8With the T in the Cabbeen of preferred formula (III-1)3、T4、T5Or T6
Definition having the same.T simultaneously7Or T8In at least two substituent groups that are located on two adjacent cyclic atoms be formed together saturation
Or unsaturated hydro carbons chain, preferably comprise 3 to 6 carbon atoms.Wording " saturated or unsaturated hydro carbons chain " means to contain
One or more olefinic double bond types or the unsaturated linear chain or branched chain hydro carbons chain of three bond type of acetylene series.
When Cabbeen (III-2) is containing condensed core, correspond to one of following formula, wherein alk represents saturated or unsaturated
Hydro carbons chain:
Wherein A, B, T1、T2、T7、T8With definitions as described above；
Alternatively, LγThe Cabbeen of representative formula (III-3):
Wherein,
A independently represents C, and B independently represents C or N, and when A independently represents N, formula (III-3) is nonsensical, when B is only
When on the spot representing N, then only T4Or T6One of them is nonsensical；Wherein A and B interchanging positions, it is equally applicable；
T1, T2, T4, T6And T7It is defined as described above.
In the Cabbeen of preferred formula (III-3): T4, T6Or T7With the T in the Cabbeen of preferred formula (III-1)3、T4、T5Or
T6Definition having the same.T simultaneously4, T6Or T7In at least two substituent groups that are located on two adjacent cyclic atoms be formed together
Saturated or unsaturated hydro carbons chain, preferably comprises 3 to 6 carbon atoms.Wording " saturated or unsaturated hydro carbons chain " means possibility
Contain one or more olefinic double bond types or the unsaturated linear chain or branched chain hydro carbons chain of three bond type of acetylene series.
When Cabbeen (III-3) is containing condensed core, correspond to one of following formula, wherein alk represents saturated or unsaturated
Hydro carbons chain:
Wherein A, B, T1、T2、T4、T6、T7With definitions as described above.
In formula (III), LαAnd LβIt for ligand, may be the same or different, be independently represented each other:
In formula (IV-1) and (IV-2): Z1、Z2、Z3、Z4、Z5、Z6It is independently represented each other: a. hydrogen, b. halogen, c. cyanogen
Base, the saturated or unsaturated electrophilic hydro carbons group of d., preferably adjacent with double or triple bonds, the Z at two ortho positions e.1-6It can be together
Form the Cabbeen L advantageously with formula (III)γElectrophilic ring that is different and optionally including hetero atom (preferably O, N or S)；Or
(IV-1) substituent group Z in1And Z2It is formed together the monovalence chain comprising at least one electrophilic residue preferably adjacent with three key
Alkenyl；Or Z in (IV-2)3To Z6It is formed in couples comprising at least one electrophilic residue preferably adjacent with the double bond
Monovalence alkenyl；
Or ligand LαAnd LβIt is formed together ligand Lδ, wherein as previously mentioned, LαAnd LβIt may be the same or different and preferably select
From formula (IV-2), to obtain the ligand L of lower formula (V)δ:
Wherein:
Y1And Y2Independently represent CRaRbOr SiRcRd；
X represents O, NReOr CRfRg；
R13、R14、R16And R17It may be the same or different, selected from hydrogen atom, alkyl and optionally by alkyl-substituted aryl；
R12、R15、Ra、Rb、RcAnd RdIndependently selected from hydrogen atom；Alkyl；Acyl group；Optionally by alkyl-substituted aryl；Appoint
Selection of land is by alkyl-substituted naphthenic base；Wherein aryl moiety is optionally by alkyl-substituted aralkyl；
ReSelected from hydrogen atom；Alkyl；Optionally by alkyl-substituted aryl；Optionally by alkyl-substituted naphthenic base；With
Wherein aryl moiety is optionally by alkyl-substituted aralkyl；Or
Work as Y1And Y2Independently represent SiRcRdWhen, two connected R of silicon atoms different from twocBase is formed together following formula
Chain:
Wherein n is integer of 1 to 3；X is as defined above；R and R ' may be the same or different, using above for ReIt provides
In all senses, it will be understood that when n is 2 or 3, the only one silicon atom of the chain can be taken by one or two alkenyl or alkynyl
Generation；Or
Y1And Y2Independently represent SiRcRdWhen, two Rs connected from different silicon atomscBase is formed together saturated hydrocarbons chain,
The two RcBase and the silicon atom and X are formed together 6- to 10- member ring；Or
Work as Y1And Y2Independently represent CRaRbWhen, two Rs connected from different carbon atomsaBase is formed together saturated hydrocarbons chain,
The two RaBase and the carbon atom for carrying them and X are formed together 6- to 10- member ring；With
RfAnd RgIndependently represent hydrogen atom；Alkyl；Acyl group；Optionally by alkyl-substituted aryl；Optionally taken by alkyl
The naphthenic base in generation；Wherein aryl moiety is optionally by alkyl-substituted aralkyl；Halogen atom；Alkenyl；Alkynyl；Or SiG1G2G3
Base, wherein G1、G2And G3It independently is alkyl；Alkoxy；The aryl optionally replaced by alkyl or alkoxy；Or in which aryl
The aralkyl that part is optionally replaced by alkyl or alkoxy.
Belong to the ligand L of the catalyst C of the formula (III) in the present compositionαAnd LβCan independently represent is had at least
The group Z of one electrophilic unit1To Z6The alkynyl of substituted formula (IV-1) or the alkenyl of formula (IV-2), the electrophilic unit
To LαAnd Lβπ unsaturation be it is active, promote ligand in conjunction with the metal M of complex compound.
Electrophilic residue in formula (IV-1) and formula (IV-2) is advantageously selected from:
Wherein:
R18、R19、R20、R21And R22For substituted or unsubstituted alkyl, alkenyl, alkynyl or trialkylsilkl, n '
Between 1 and 50.
The group Z that can be mentioned that1To Z6Example include: selected from-CN ,-COOCH3、-COOCH2CH3、-CONC12H25That
A bit, and in substituent group Z1And Z2Ring Cy1 and Z are formed together with three keys in (IV-1) in couples3To Z6It (is with or without in couples
(IV-2) double bond in) form ring Cy2 in the case where, these rings Cy1 and Cy2 independently and are preferably selected from following ring:
LαAnd LβIt is formed together the ligand L of formula (V)δWhen, the ligand more preferably wherein Y1And Y2Represent CRaRbOr equal generation
Table SiRcRdType, so that the ligand has formula (V-1) or formula (V-2):
Two of them Ra, two Rb, two RcWith two RdIt is mutually the same, R12=R15；R13=R17；R14=R16, and this
A little groups and group X are as defined above.
According to a kind of version, two R in formula (V-2)cIt is formed together:
(a) following chain
Wherein n is integer of 1 to 3；X is as defined above；R and R ' may be the same or different, using above for RdIt provides
In all senses, it will be understood that when n is 2 or 3, the only one silicon atom of the chain can be taken by one or two alkenyl or alkynyl
Generation；Or
(b) saturated hydrocarbons chain, so that two substituent Rsc6- is formed together extremely with two silicon atoms and X for carrying them
10- member ring, preferably 6- are to 8- member ring.
As two R in formula (V-2)cWhen forming chain (a), preferably n is 1 or 2 (more preferable n is 1), in R=RdIn the case where,
It is preferred that two R of two silicon atom institute bandsdBase phase is same.In the case, RdIt is preferred that representing alkyl, such as methyl；More preferably these
R ' representative-CR in compound15=CR16R17And R16=R14；R13=R17；R15=R12。
In this case, it is preferable to X represents O in formula (V-2), then ligand LδThere is following formula:
Among these compounds, preferably two RdIt is identical, advantageously represent alkyl, such as methyl.
It is preferred that n " is 0-2, more preferable n "=0, and R=Rd, it will be understood that when n " is 2, the chain O- (SiRR '-O)n?
Only one silicon atom can be by one or two alkenyl or alkynyl substituted；More preferable R '=- CR15=CR16R17And R16=R14；
R13=R17；R15=R12。
Two RcWhen being formed together chain (b) with two silicon atoms and X base, preferably two RcBase forms 8- member ring.In this situation
Under, preferably two RdIt is identical, then ligand LδWith following formula:
Wherein T represents alkyl, and i is the integer between 0 and 5, and T is located at the one or more of the annular atom 1,2,3,4 and 5 of above formula
On a position.
Similarly, as Y in formula (V-1)1And Y2Represent CRaRbWhen, two Rs connected from different carbon atomsaBase can shape together
At saturated hydrocarbons chain (c), so that two RaBase and the carbon for carrying them and X are formed together 6- to 10- member ring.It is preferred that being formed by
Ring is 8- member ring, in the case ligand LδWith following formula:
Wherein T represents alkyl, and i is the integer between 0 and 5, and T is located at the one or more of the annular atom 1,2,3,4 and 5 of above formula
On a position.
Work as RfAnd/or RgRepresent SiG1G2G3When, preferably RfAnd/or RgFor trialkylsilkl, such as wherein G1=G2=
G3The SiG of=alkyl1G2G3。
Constitute metal complex, that is, catalyst C ligand L of present composition a partδGroup be made up of,
Wherein:
X=O；Y1And Y2Independently represent SiRcRd；Or
X=NRe；Y1And Y2Independently represent CRaRb；Or
X=NRe；Y1And Y2Independently represent SiRcRd；Or
X=CRfRg；Y1And Y2Independently represent CRaRb；Or
X=CRfRg；Y1And Y2Independently represent SiRcRd。
In these ligand Ls of formula (V)δIn, preferably wherein:
When X represents O, Y1And Y2Independently represent SiRcRd；Or
When X represents NReWhen, Y1And Y2Independently represent CRaRb；Or
When X represents CRfRg, Y1And Y2Independently represent CRaRb。
In practice, the ligand L of formula (V)δMiddle X represents O and Y1And Y2Independently represent SiRcRd。
For example, the diene ligand L of formula (V)δIt is symmetrical, that is to say, that R13=R17；R14=R16；R12=R15And two
Group Y1And Y2Mutual exactly the same or Y1=CRaRbAnd Y2=CRaRbOr Y1=SiRcRdAnd Y2=SiRcRd。
It should be mentioned that for the catalyst C in composition of the present invention, the metal complex of particularly preferably lower formula (VI)
Object:
Wherein: T1And T2It is identical and as defined above；T3And T4As defined above；RcAnd RdAs defined above.
It is particularly preferred that as follows as heterocyclic carbene ligand/structure of metal complex of catalyst in the present invention:
Wherein iPr is isopropyl.
Within the scope of the invention, " the independently representing " being previously mentioned means that signified substituent group is identical or different.For example, formula
(V) ligand LδMiddle R13、R14、R16And R17For hydrogen atom.R12And R15Preferred meaning especially hydrogen atom；Alkyl；Optionally
By alkyl-substituted aryl；Optionally by alkyl-substituted naphthenic base.In these preferred meanings, R12And R15Represent
Hydrogen atom；(C3-C8) naphthenic base or (C1-C8) alkyl is particularly advantageous.For example, the diolefins ligand L of formula (V)δBe it is symmetrical,
That is R13=R17；R14=R16；R12=R15And two group Y1And Y2Strictly mutually the same or Y1=CRaRbAnd Y2=
CRaRb(two of them RaIt is formed together Symmetric Chain) or Y1=SiRcRdAnd Y2=SiRcRd(two of them RcIt is formed together pair
Claim chain).
" alkyl " mentioned in above-mentioned statement indicates the linear chain or branched chain hydro carbons chain of saturation, be optionally substituted (such as by
One or more alkyl replace), preferably there is 1 to 10 carbon atom, such as 1 to 8 carbon atom, more preferable 1 to 7 carbon original
Son.
The example of alkyl especially methyl, ethyl, isopropyl, n-propyl, tert-butyl, normal-butyl, isobutyl group, n-pentyl,
Isopentyl and 1,1- dimethyl propyl.The moieties of alkoxy are as defined above.
" naphthenic base " being previously mentioned means monocycle or polycyclic, preferably monocycle or bicyclic saturated hydrocarbons group, preferably containing 3 to
10, more preferable 3 to 8 carbon atoms.Wording " polycyclic saturated hydrocarbon class group " mean comprising by σ be keyed together and/or
The group of condensed two or more ring nucleus in pairs.The example of polycyclic naphthene base is adamantane and norbornane.Monocycle cycloalkanes
The example of base is cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl and cyclooctyl.
" perfluoroalkyl " being previously mentioned indicates the alkyl comprising at least one perfluoroalkyl, preferably has following formula :-(CH2)p-
CqF2q+1
Wherein p represents 0,1,2,3 or 4；Q is integer of 1 to 10；CqF2q+1For linear chain or branched chain.The preference of the group
Son is :-(CH2)2-(CF2)5-CF3With-(CF2)7-CF3。
" aryl " that is previously mentioned indicates monocycle containing 6 to 18 carbon atoms or polycyclic, preferably monocycle or bicyclic aromatic hydrocarbons
Group.It should be understood that term " multiring aromatic hydrocarbon group " within the scope of the present invention means the group containing two or more aromatic cores,
Together with these aromatic cores condensed (unilateral condensed or ortho position-is condensed with peri-position -), i.e., at least two pairs of shared carbon.
The aromatic hydrocarbons group (" aryl ") is optionally substituted, such as by one or more C1-C3Alkyl, one or more
A halohydrocarbyl (such as CF3), one or more alkoxy (such as CH3O) or one or more includes one or more ketone units
Hydro carbons group (such as CH3CO-) replace.
The example for the aryl that can be mentioned that includes phenyl, naphthalene, anthryl and phenanthryl.
" aralkyl " being previously mentioned indicates the alkyl as defined above replaced on its hydro carbons chain by one or more aryl,
The aryl is as defined above.The example of these aralkyl is benzyl and trityl.
" acyl group " being previously mentioned means R3- CO- base, wherein R3Represent alkyl as defined above；Or Ar-CO- base, wherein Ar
Aryl or aralkyl as defined above are represented, wherein aryl and alkyl are as defined above, and wherein aryl moiety is optionally taken
Generation, such as replaced by alkyl.
" alkenyl " being previously mentioned mean it is linear chain or branched chain, substituted or unsubstituted, containing at least one olefinic double bond,
The unsaturated hydro carbons chain of only one more preferable double bond.The alkenyl preferably comprises 2 to 8, more preferable 2 to 6 carbon atoms.
This hydro carbons chain optionally includes at least one hetero atom such as O, N or S.
The preferred example of alkenyl is allyl and high allyl (homoallyl).
According to the present invention, " alkynyl " being previously mentioned mean it is linear chain or branched chain, substituted or unsubstituted, contain at least one
The unsaturated hydro carbons chain of three key of acetylene series, more preferably only one three key.The alkynyl preferably comprise 2 to 8, it is 2 to 6 more preferable
Carbon atom.The example that can be mentioned that includes acetenyl and propinyl.This hydro carbons chain optionally include at least one hetero atom such as O, N or
S。
Wording " nonsensical " means that mentioned substituent group is not present.Such as in formula (III-1), nitrogen-atoms three
Valence, therefore when A or B represent N, the nitrogen-atoms can not contain additional substituent group.
Within the scope of the invention, the catalyst C is used in the compositions of the present invention with catalytically effective amount.Generally,
The dosage of the catalyst C accounts for the 0.1-500ppm of the weight of polysiloxane composition with the poidometer of the metal in catalyst,
It is preferred that 0.1-100ppm, more preferable 0.25-50ppm.
D, inhibitor (D)
The present invention proposes the inhibitor cooperated with heterocyclic carbene ligand/metal complex as catalyst, especially
It is alkynyl or alkyne inhibitor, double bond containing maleate and silanization maleic acid, more vinyl polysiloxanes etc., to obtain
The comprehensive performance of optimization suitable for Si―H addition reaction system balances long-term storage at room temperature and quick elevated cure speed.
The inhibitor (D) is advantageously selected from:
Polysiloxane is advantageously polysiloxane that is cricoid, being replaced by least one alkenyl, especially
Preferably tetramethyl-ethylene base tetrasiloxane, example may is that tetramethyl divinyl siloxanes, multi-vinyl silicone oil, four
Methyl tetravinyl cyclotetrasiloxane.
Unsaturated amides,
Malaysia dialkylaminobenzoic acid, alkenyl or alkynyl ester, particularly preferably diallyl maleate,
Alkynol class,
Acetylenedicarboxylic acid alkyl, alkenyl or alkynyl ester,
And the combination of the above inhibitor.
Preferably, the inhibitor is alkyne inhibitor.Preferably, the alkyne inhibitor has following formula:
Rx-(Ry)C(OH)-C≡C-[C(OH)(Rw)]m-Rz
In formula:
Rx、RzFor linear or branched alkyl group or phenyl；
Ry、RwFor H or linear or branched alkyl group or phenyl；
RxAnd RyOr RwAnd RzCan respectively and positioned at the position α of three key carbon atom formed ring；
Rx、Ry、RwAnd RzIn contained the total number of carbon atoms be at least 5, preferably 9 to 20.
Wherein m=0 or 1.
The alkynol is preferably selected from boiling point greater than those of 100 DEG C, and the example that can be mentioned that includes: 1- acetenyl -1- hexamethylene
Alcohol, 3- methyl-1-dodecyne-3- alcohol, 3,7,11- trimethyl-1- dodecyne-3- alcohol, 1,1- diphenyl-2- propine-1- alcohol, 3-
Ethyl -6- ethyl -1- n-heptylacetylene -3- alcohol,-ten five alkynes -3- alcohol of 3- methyl-1,3- butyne-2-alcohol, 1- pentyne -3- alcohol, 1- hexin -
3- alcohol, 1- heptyne-3- alcohol, 5- methyl-1-hexin-3- alcohol, 3,5- dimethyl-1- hexin-3- alcohol, 1- acetenyl-1- cyclopentanol,
1- acetenyl-1- suberol, 3- ethyl-1- hexin-3- alcohol, 3- ethyl-1- heptyne-3- alcohol, 3- isobutyl group-5- methyl-1-oneself
Alkynes-3- alcohol, 3,4,4- trimethyl-1- pentyne-3- alcohol, 3- ethyl-5- methyl-1-heptyne-3- alcohol, 4- ethyl-1- octyne-3-
Alcohol, 3,7,11- trimethyl-1- dodecyne-3- alcohol, 1- acetenyl-1- Lotka-Volterra circle system, 3- methyl-1-butine-3- alcohol, 3- methyl-1-
Pentyne-3- alcohol, 3- methyl-1-hexin-3- alcohol, 3- methyl-1-heptyne-3- alcohol, 3- methyl-1-octyne-3- alcohol, 3- methyl-1-
Nonyl-3- alcohol, 3- methyl-1-decine-3- alcohol, 3- ethyl-1- pentyne-3- alcohol, 2,4,7,9- tetramethyl-5- decine-4,7- two
Alcohol, 3- phenyl -2- propine -1- alcohol.The pure and mild ethynylcyclohexanol of particularly preferred 2,4,7,9- tetramethyl -5- decine -4,7- two.
The molar ratio between metal in inhibitor and catalyst can be 10-600, preferably 10-400.
For example, the molar ratio between metal in inhibitor and metallic catalyst is for example when inhibitor is alkynol class
40-600, preferably 50-400, further preferably 70-200；When inhibitor is alkyl maleates, in inhibitor and metallic catalyst
Metal between molar ratio be 10-150, preferably 10-100, more preferable 10-50.
Other ingredients (E)
In one pack system addition type polysiloxane composition of the invention, also optionally include it is one or more it is other at
Point.The premise that these optional members are added is that the type for these ingredients being added and dosage will not influence the combination of polysiloxanes basis
Storage stability, operating time, the curing rate of object, mechanical performance etc..
For example, the one pack system addition type polysiloxane composition may include other non-reacted polysiloxane, such as
Non-reacted dimethyl silicone polymer.
The one pack system addition type polysiloxane composition may include other silicone resins, Polyorganosilsesquioande, have
Machine silicon composition powder etc..
The one pack system addition type polysiloxane composition also may include additive, be preferably but not limited to: antistatic agent, radiation
Screener, free radical inhibitors, tack-modifier, flame-retardant additive, surfactant, storage stability modifier, ozone drop
Solve inhibitor, light stabilizer, viscosity builder, plasticizer, thixotropic agent, antioxidant, pigment and heat stabilizer etc..
One pack system addition type polysiloxane composition of the invention can also include filler, be preferably but not limited to: precipitating two
Silica, fumed silica, diatomite, talcum powder, barium sulfate, white lime, calcium carbonate, aluminium oxide, iron oxide, zinc oxide,
Titanium oxide, cerium oxide, aluminium powder, iron powder, nickel powder, nickel packet carbon dust, copper powder, silver powder, bronze, graphite, carbon black, carbon nanotube, graphite
Alkene etc..
If necessary, by adjusting the different proportion of the above ingredient (such as additive or filler), and/or pass through control addition
The ratio of silicon hydrogen and alkenyl or alkynyl in type system, it is hereby achieved that the organosilicon solidfied material of different hardness.In general, it is above-mentioned this
It is no more than 90% weight, preferably more than 80% weight that the amount of a little optional members (such as additive or filler), which is based on formula total amount,
Amount.
The hydrosilylation can be carried out in a solvent or be carried out in the case where solvent is not present.As a kind of variation
Form, one of described reagent can play solvent action: the compound for example containing olefinic double bond and/or containing three key of acetylene series.
Applicable solvent is solvent that can be miscible with the compound containing Si-H unit.In the condition of hydrosilylation
Under, the catalytic complexes should be dissolved in reaction medium.It can be used for the example especially aliphatic hydrocarbon (such as penta of the solvent of Si―H addition reaction
Alkane, hexane, heptane, five methylheptane or petroleum distillate)；Aromatic hydrocarbons (for example, benzene, toluene or dimethylbenzene such as ortho-xylene, to diformazan
Benzene and meta-xylene)；The aliphatic series or aromatic hydrocarbon (such as tetrachloro-ethylene) of halogenation；Or ether (such as tetrahydrofuran or twoAlkane).
For the content of various composition of the present invention, unless otherwise indicated, otherwise those skilled in the art can use and meet
The conventional amount used of the art, and the dosage is accounted for target application institute+requirement content.
Generally, within the scope of the invention, there is the polysiloxane of the alkenyl and/or alkynyl in conjunction with silicon atom
The ratio of A and poly- organohydrogensiloxanes B make silicon hydrogen (Si-H) in B component in component A in conjunction with silicon atom alkenyl and/
Or the molar ratio of alkynyl is 0.5-10, preferably 0.7-6, more preferable 0.8-5.
About the preparation of the present composition, any mode well known by persons skilled in the art can be used to carry out.Usually
Ground using component A, B, C, D and optional one or more other components (such as additive or filler) and mixes them.It is described
Hybrid manipulation is completely in the limit of power of those skilled in the art.
The polysiloxane A and B, inhibitor D and other components such as additive or filler etc. are those skilled in the art
Commodity obtained by member.
Specific embodiment
Embodiment
The invention will be further described with reference to embodiments.But the present invention is not limited to the following embodiments.In addition,
Percent data and share ratio in present specification are by weight, unless expressly stated otherwise,.
The raw material used
Performance evaluation
According to the present invention, after obtained one pack system addition type polysiloxane composition, method is to each as described below
A product is evaluated, and the results are shown in table 2.
Storage stability evaluation: configured one pack system addition type polysiloxane composition is real in 45 DEG C of progress agings
Test, and to before aging and after aging viscosity and mechanical performance etc. be compared.
Viscosity: the concentration of uncured one pack system addition type polysiloxane composition, test temperature are measured according to ASTM D445
It is 23 DEG C, specific test condition is shown in Table 2 and table 3.
Needle penetration: the hardness of solidfied material is measured according to ISO2137.Condition of cure: according to different sample situations at 120 DEG C
Curing time is selected, 2 and table 3 are specifically shown in Table.
DSC test: DSC manufacturer used is TA Instruments-Waters, model Q20.Sample is obtained by DSC
The initial temperature and peak temperature at exothermic heat of reaction peak in solidification process, and initial sample and aged samples are compared, to obtain
Obtain the assessment of storage stability.
Embodiment 1 (Ex1)
As shown in table 1,0.01 parts by weight are added in the mixture of 24.82 parts by weight A-1 and 74.34 parts by weight E-1
Hydrosilylation inhibitor D-1 adds 0.84 parts by weight hydrogen-containing siloxane B-1 after mixing, is further sufficiently mixed.It presses
C-1 catalyst solvent is prepared according to toluene and C-1 mass ratio are 6:1, prepared polysiloxanes group is added in C-1 toluene solvant
It closes and is uniformly mixed in object, wherein platinum content is 0.5ppm in total polysiloxane mixture in catalyst.Uniformly mixed list
Component addition type polysiloxane composition solidifies at 120 DEG C.Take a part of sample after 45 DEG C of progress agings simultaneously, comparison is old
Change the variation of front and back viscosity and needle penetration.
Embodiment 2-9 (Ex2-Ex9)
Embodiment 2-9 is carried out as described in Example 1, in addition to using different raw material dosage and preparation as shown in Table 1
Condition.Wherein the ratio of inhibitor and platinum is molar ratio.
Comparative example 1-2 (C-Ex1-C-Ex2)
Comparative example 1-2 is carried out as described in Example 1, in addition to using different raw material dosages and system as shown in table 1
Standby condition.
The inhibitor used in embodiment and comparative example is as follows:
Table 1
Table 2
Table 3
According to above-mentioned test method, to cured one pack system additive poly obtained in embodiment 1-9 and comparative example 1-2
The performance of silicone composition is evaluated, and its result is listed in respectively in table 2 and table 3.As can be seen from the table, lead to
The cooperation of used catalyst of the present invention Yu inhibitor D-1 to D-5 is crossed, the present composition shows good storage and performance is steady
It is qualitative, especially as shown in embodiment 1,2,7 and 9.
By being compared with comparative example 1 and 2 it can be found that the cooperation of used catalyst and inhibitor through the invention,
Need less inhibitor only to obtain excellent storage and stability, and traditional platinum catalyst generally requires phase
Metal molar in catalyst is likely to realize than more inhibitor.Meanwhile using identical inhibitor and inhibitor
When identical as catalyst ratio, with more stable performance when the present composition stores at room temperature.This can implemented
See in example 1,7 and comparative example 2.It follows that in the presence of metallic catalyst containing carbenes according to the present invention,
The introducing of certain inhibitor can obtain stable one pack system addition type polysiloxane composition.It is according to the present invention to match containing Cabbeen
Body metallic catalyst with inhibitor is suitable can get good stability when engaged, be conducive to store for a long time and guarantee phase
Answer the stabilization of performance.
Claims (15)
1. one pack system addition type polysiloxane composition, includes:
A, at least one polysiloxane A with alkenyl and/or alkynyl in conjunction with silicon atom；
B, at least one poly- organohydrogensiloxanes B；
C, at least one heterocyclic carbene ligand/metal complex catalyst C；
D, at least one inhibitor D,
Wherein the catalyst C includes the compound of at least one formula (III):
Wherein, M, which is represented, is selected from Handbook of Chemistry and Physics, and the 65th edition, disclosed in 1984-1985
The metal of 8th race's metal of the periodic table of elements, such as palladium, platinum or the nickel of 0 oxidation state, preferably M represent the platinum of 0 oxidation state；
LγThe Cabbeen of representative formula (III-1):
Wherein:
A and B independently represents C or N, and when A represents N, then only T3Or T5One of them is nonsensical, when B represents N,
Then only T4Or T6One of them is nonsensical；
T3、T4、T5And T6Independently represent hydrogen atom；Alkyl；The naphthenic base optionally replaced by alkyl or alkoxy；Optionally by
The aryl that alkyl or alkoxy replace；Alkenyl；Alkynyl；Or in which the virtue that aryl moiety is optionally replaced by alkyl or alkoxy
Alkyl；Or
T1、T2、T3、T4、T5Or T6Naphthenic base, aryl or heterocycle can be formed together with the A and B for representing carbon atom；
T1And T2Independently represent alkyl；Optionally by alkyl-substituted alkyl；Perfluoroalkyl is optionally replaced by perfluoroalkyl
Alkyl；The naphthenic base optionally replaced by alkyl or alkoxy；The aryl optionally replaced by alkyl or alkoxy；Alkene
Base；Alkynyl；Or in which the aralkyl that aryl moiety is optionally replaced by alkyl or alkoxy；Or
T1And T2Independently represent the univalent perssad of following formula (III-1.1):
V1-V2 (III-1.1)
Wherein:
V1 is divalent hydrocarbon group, preferably alkylidene,
V2 is the univalent perssad selected from following substituent group:
Alkoxy ,-OR3, wherein R3Corresponding to hydrogen, alkyl or aryl
Amine, preferably N (R3)2, wherein R3Corresponding to hydrogen, alkyl or aryl, or
T1And T2Independently represent the univalent perssad of following formula (III-1.2):
W1-ω-W2 (III-1.2)
Wherein:
W1For divalent hydrocarbon group, preferably optionally substituted linear chain or branched chain C1-C10Alkylidene；
ω is represented:
-R4C=CR4-
Wherein R4Corresponding to H or alkyl or-C ≡ C-
W2For the univalent perssad selected from following substituent group:
R5=alkyl, H；
Si- alkyl or Si- alkoxy, preferably Si- (R6)3, wherein R6=alkyl；
Alcohol, preferably-C (R7)2OH, wherein R7=H or alkyl；
Ketone, preferably
Wherein R8=alkyl；
Carboxyl, preferably
Wherein R9=alkyl；
Amide, preferably
Wherein R10=H, alkyl；
Acyl group, preferably
Wherein R11=alkyl；
Or substituent group T1、T2、T3、T4、T5And T6Saturation can be formed in couples when on two adjacent atoms in formula (III-1)
Or unsaturated hydro carbons chain；
LαAnd LβIt for ligand, may be the same or different, be independently represented each other:
In formula (IV-1) and (IV-2): Z1、Z2、Z3、Z4、Z5、Z6It is independently represented each other: a. hydrogen, b. halogen, c. cyano, d.
Saturated or unsaturated electrophilic hydro carbons group, preferably adjacent with double or triple bonds, the Z at two ortho positions e.1-6It can be formed together
The Cabbeen L on sharp ground and formula (III)γDifference and the optionally heteroatomic electrophilic ring comprising being preferably selected from O, N or S；Or
(IV-1) substituent group Z in1And Z2It is formed together the monovalence chain comprising at least one electrophilic residue preferably adjacent with three key
Alkenyl；Or Z in (IV-2)3To Z6It is formed in couples comprising at least one electrophilic residue preferably adjacent with the double bond
Monovalence alkenyl；
Or ligand LαAnd LβIt is formed together ligand Lδ, wherein as previously mentioned, LαAnd LβIt may be the same or different and be preferably selected from formula
(IV-2), to obtain the ligand L of lower formula (V)δ:
Wherein:
Y1And Y2Independently represent CRaRbOr SiRcRd；
X represents O, NReOr CRfRg；
R13、R14、R16And R17It may be the same or different, selected from hydrogen atom, alkyl and optionally by alkyl-substituted aryl；
R12、R15、Ra、Rb、RcAnd RdIndependently selected from hydrogen atom；Alkyl；Acyl group；Optionally by alkyl-substituted aryl；Optionally
By alkyl-substituted naphthenic base；Wherein aryl moiety is optionally by alkyl-substituted aralkyl；
ReSelected from hydrogen atom；Alkyl；Optionally by alkyl-substituted aryl；Optionally by alkyl-substituted naphthenic base；It is wherein fragrant
Base portion point is optionally by alkyl-substituted aralkyl；And
RfAnd RgIndependently represent hydrogen atom；Alkyl；Acyl group；Optionally by alkyl-substituted aryl；It is optionally alkyl-substituted
Naphthenic base；Wherein aryl moiety is optionally by alkyl-substituted aralkyl；Halogen atom；Alkenyl；Alkynyl；Or SiG1G2G3Base,
Middle G1、G2And G3It independently is alkyl；Alkoxy；The aryl optionally replaced by alkyl or alkoxy；Or in which aryl moiety is appointed
The aralkyl that selection of land is replaced by alkyl or alkoxy.
2. one pack system addition type polysiloxane composition according to claim 1, wherein in the Cabbeen of formula (III-1):
T3Or T5One of those and T4Or T6One of those represents hydrogen atom or is formed together phenyl；
And/or
T1And T2It may be the same or different, represent (C1-C8) alkyl or (C3-C8) naphthenic base, it is preferably selected from: methyl, n-propyl, positive penta
Base, neopentyl (- CH2-C(CH3)3), cyclopenta, cyclohexyl, adamantyl, allyl (- CH2- CH=CH2), methylallyl
(-CH2-C(CH3)=CH2), propargyl, high-propargyl (- (CH2)2- C ≡ CH) or
-(CH2)γ=1 to 3-C≡C-C(CH3)3
Or-(CH2)γ=1 to 3-C≡C-Si(CH3)3
Or-(CH2)γ=1 to 4Amine (such as N (CH3)2)
Or-(CH2)γ=1 to 4Alkoxy (such as O (CH3)2),
Or optionally substituted aryl is represented, such as by one or more C1-C3Alkyl, one or more halohydrocarbyls are such as
CF3, one or more alkoxies such as CH3Hydro carbons group such as CH of the O or one or more comprising one or more ketone units3CO- takes
Generation, wherein the aryl is preferably selected from phenyl, naphthalene, anthryl and phenanthryl；
And/or
A and B represent carbon atom.
3. according to the one pack system addition type polysiloxane composition of any one of the claims, wherein LαAnd LβIt is formed together formula
(V) ligand Lδ, the ligand preferably wherein Y1And Y2Represent CRaRbOr represent SiRcRdType, so that the ligand has
There are formula (V-1) or formula (V-2):
Two of them Ra, two Rb, two RcWith two RdIt is mutually the same, R12=R15；R13=R17；R14=R16, and these bases
Group and group X are as defined above.
4. one pack system addition type polysiloxane composition according to claim 3, wherein in formula (V-2), two RcShape together
At:
(a) following chain
Wherein n is integer of 1 to 3；X is as defined above；R and R ' may be the same or different, using above for RdWhat is provided is any
Meaning, it will be understood that when n is 2 or 3, the only one silicon atom of the chain can be by one or two alkenyl or alkynyl substituted；Or
(b) saturated hydrocarbons chain, so that two substituent Rsc6- to 10- member is formed together with two silicon atoms and X for carrying them
Ring, preferably 6- are to 8- member ring；
As two R in formula (V-2)cWhen forming chain (a), preferably n is 1 or 2, and more preferable n is 1, in R=RdIn the case where, preferably two
Two R of a silicon atom institute banddBase phase is same；In the case, RdIt is preferred that alkyl is represented, such as methyl, these more preferable compounds
Middle R ' representative-CR15=CR16R17And R16=R14；R13=R17；R15=R12。
5. one pack system addition type polysiloxane composition according to claim 3, wherein X represents O, then ligand in formula (V-2)
LδWith following formula:
Two of them RdIt is identical, advantageously represent alkyl, such as methyl；
N " is 0-2, more preferable n "=0, and R=Rd, it will be understood that when n " is 2, the chain O- (SiRR '-O)nOnly one silicon
Atom can be by one or two alkenyl or alkynyl substituted；More preferable R '=- CR15=CR16R17And R16=R14；R13=R17；
R15=R12。
6. according to the one pack system addition type polysiloxane composition of any one of the claims, wherein in ligand LδIn,
X=O；Y1And Y2Independently represent SiRcRd；Or
X=NRe；Y1And Y2Independently represent CRaRb；Or
X=NRe；Y1And Y2Independently represent SiRcRd；Or
X=CRfRg；Y1And Y2Independently represent CRaRb；Or
X=CRfRg；Y1And Y2Independently represent SiRcRd；
Preferably, in the ligand L of formula (V)δIn:
When X represents O, Y1And Y2Independently represent SiRcRd；Or
When X represents NReWhen, Y1And Y2Independently represent CRaRb；Or
When X represents CRfRg, Y1And Y2Independently represent CRaRb；
It is highly preferred that in the ligand L of formula (V)δIn, X represents O and Y1And Y2Independently represent SiRcRd；
For example, the diene ligand L of formula (V)δIt is symmetrical, that is to say, that R13=R17；R14=R16；R12=R15And two groups
Y1And Y2Mutual exactly the same or Y1=CRaRbAnd Y2=CRaRbOr Y1=SiRcRdAnd Y2=SiRcRd。
7. wherein catalyst C is selected from following formula according to the one pack system addition type polysiloxane composition of any one of the claims
(VI) metal complex:
Wherein: T1And T2It is identical and as defined above；T3And T4As defined above；RcAnd RdAs defined above.
8. wherein catalyst C has following formula according to the one pack system addition type polysiloxane composition of any one of the claims:
Wherein iPr is isopropyl.
9. according to the one pack system addition type polysiloxane composition of any one of the claims, wherein the inhibitor D is selected from:
Polysiloxane is advantageously polysiloxane that is cricoid, being replaced by least one alkenyl, particularly preferably
Be tetramethyl-ethylene base tetrasiloxane, such as tetramethyl divinyl siloxanes, multi-vinyl silicone oil, tetramethyl tetravinyl
Cyclotetrasiloxane；
Unsaturated amides,
Malaysia dialkylaminobenzoic acid, alkenyl or alkynyl ester, particularly preferably diallyl maleate,
Alkynol class,
Acetylenedicarboxylic acid alkyl, alkenyl or alkynyl ester,
And the combination of the above inhibitor.
10. according to the one pack system addition type polysiloxane composition of any one of the claims, wherein inhibitor D and catalyst
The molar ratio between metal in C is 10-600, preferably 10-400,
Preferably, the molar ratio for example 40- between metal when inhibitor is alkynol class, in inhibitor and metallic catalyst
600, preferably 50-400, further preferably 70-200；Gold when inhibitor is alkyl maleates, in inhibitor and metallic catalyst
Molar ratio between category is 10-150, preferably 10-100, more preferable 10-50.
11. the inhibitor D is under according to the one pack system addition type polysiloxane composition of any one of the claims
The alkyne inhibitor of formula:
Rx-(Ry)C(OH)-C≡C-[C(OH)(Rw)]m-Rz
In formula:
Rx、RzFor linear or branched alkyl group or phenyl；
Ry、RwFor H or linear or branched alkyl group or phenyl；
RxAnd RyOr RwAnd RzCan respectively and positioned at the position α of three key carbon atom formed ring；
Rx、Ry、RwAnd RzIn contained the total number of carbon atoms be at least 5, preferably 9 to 20；
Wherein m=0 or 1；
Preferably, the alkyne inhibitor is that boiling point is greater than those of 100 DEG C, is more preferably selected from: 1- acetenyl -1- hexamethylene
Alcohol, 3- methyl-1-dodecyne-3- alcohol, 3,7,11- trimethyl-1- dodecyne-3- alcohol, 1,1- diphenyl-2- propine-1- alcohol, 3-
Ethyl -6- ethyl -1- n-heptylacetylene -3- alcohol,-ten five alkynes -3- alcohol of 3- methyl-1,3- butyne-2-alcohol, 1- pentyne -3- alcohol, 1- hexin -
3- alcohol, 1- heptyne-3- alcohol, 5- methyl-1-hexin-3- alcohol, 3,5- dimethyl-1- hexin-3- alcohol, 1- acetenyl-1- cyclopentanol,
1- acetenyl-1- suberol, 3- ethyl-1- hexin-3- alcohol, 3- ethyl-1- heptyne-3- alcohol, 3- isobutyl group-5- methyl-1-oneself
Alkynes-3- alcohol, 3,4,4- trimethyl-1- pentyne-3- alcohol, 3- ethyl-5- methyl-1-heptyne-3- alcohol, 4- ethyl-1- octyne-3-
Alcohol, 3,7,11- trimethyl-1- dodecyne-3- alcohol, 1- acetenyl-1- Lotka-Volterra circle system, 3- methyl-1-butine-3- alcohol, 3- methyl-1-
Pentyne-3- alcohol, 3- methyl-1-hexin-3- alcohol, 3- methyl-1-heptyne-3- alcohol, 3- methyl-1-octyne-3- alcohol, 3- methyl-1-
Nonyl-3- alcohol, 3- methyl-1-decine-3- alcohol, 3- ethyl-1- pentyne-3- alcohol, 2,4,7,9- tetramethyl-5- decine-4,7- two
Alcohol, 3- phenyl -2- propine -1- alcohol；Particularly preferably it is selected from the pure and mild acetenyl hexamethylene of 2,4,7,9- tetramethyl -5- decine -4,7- two
Alcohol.
12. the method for being used to prepare any one of -11 one pack system addition type polysiloxane composition according to claim 1, the party
Method is implemented by mixing the various components of the composition.
13. any one of -11 one pack system addition type polysiloxane composition is in electronics, electric power, communication, vapour according to claim 1
Purposes in vehicle, high-speed railway, aerospace, medical treatment and wearable smart machine field.
14. the combination of at least one heterocyclic carbene ligand/metal complex catalyst C and at least one inhibitor D is in one pack system
Purposes in addition type polysiloxane composition, wherein the catalyst C and the inhibitor D are respectively as claim 1-11 appoints
It is limited in one.
15. a kind of Si―H addition reaction method, including use at least one heterocyclic carbene ligand/metal complex catalyst C at least
A kind of combination of inhibitor D, wherein the catalyst C and the inhibitor D in any one of claim 1-11 respectively as limited.
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| CN201711458656.8A CN109970980A (en) | 2017-12-28 | 2017-12-28 | One pack system addition type polysiloxane composition |
| PCT/CN2018/124278 WO2019129131A1 (en) | 2017-12-28 | 2018-12-27 | Single-component addition-type polysiloxane composition |
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Cited By (5)
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| CN111116863A (en) * | 2019-12-31 | 2020-05-08 | 广州核心新材料科技有限公司 | Polyurethane modified organic silicon defoaming agent, preparation method and application |
| CN111748099A (en) * | 2020-07-08 | 2020-10-09 | 上海麦豪新材料科技有限公司 | Preparation method of polyether organic silicon copolymer |
| CN112940258A (en) * | 2021-04-02 | 2021-06-11 | 浙江清华柔性电子技术研究院 | Reactive inhibitor and preparation method thereof, silicone rubber composition, silicone rubber and preparation method thereof |
| CN113024816A (en) * | 2021-03-30 | 2021-06-25 | 中国日用化学研究院有限公司 | Comb-type aminosiloxane-allyl polydimethylsiloxane co-modified organic silicon and preparation method thereof |
| CN113583264A (en) * | 2021-07-09 | 2021-11-02 | 镇江高美新材料有限公司 | Cross-linking vulcanization method of silicone rubber |
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