CN102516314A - N-heterocyclic carbene complex catalyst and preparation and application thereof - Google Patents

N-heterocyclic carbene complex catalyst and preparation and application thereof Download PDF

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CN102516314A
CN102516314A CN201110405370XA CN201110405370A CN102516314A CN 102516314 A CN102516314 A CN 102516314A CN 201110405370X A CN201110405370X A CN 201110405370XA CN 201110405370 A CN201110405370 A CN 201110405370A CN 102516314 A CN102516314 A CN 102516314A
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catalyst
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朱晓飚
胡建红
郑群亮
杨雄发
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ZHEJIANG Z-LIGHT OPTOELECTRONICS Co Ltd
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ZHEJIANG Z-LIGHT OPTOELECTRONICS Co Ltd
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Abstract

The invention relates to an N-heterocyclic carbene complex catalyst and preparation and an application thereof. The structure of the catalyst is shown as a formula (I). LED (Light-Emitting Diode) encapsulating silica gel can be cured and molded by adding an N-heterocyclic carbine ligand into a catalyst, forming a complex silicon-hydrogen addition catalyst under a certain reaction condition, adding the catalyst into the LED encapsulating silica gel, stirring uniformly, defoaming in vacuum and curing at a set temperature for a certain period of time. Compared with the conventional silicon-hydrogen addition catalyst, the N-heterocyclic carbene complex catalyst has the beneficial effects that: the coordination and activation of metal atoms are facilitated, the activity of the catalyst is raised under the actions of a stereo-hindrance effect and an electronic effect formed by N-heterocyclic carbine, the resistance of the catalyst to organic tin, organic amine and the like is enhanced, and devitalization is avoided.

Description

A kind of N-heterocyclic carbine platinum complex catalyst and preparation thereof and application
(1) technical field
The present invention relates to the curing of a kind of LED encapsulation silica gel and use catalyzer---N-heterocyclic carbine platinum complex and preparation method thereof and application.
(2) background technology
Addition reaction of silicon with hydrogen is to utilize hydrogen containing siloxane and vinyl ZGK 5 under catalyst action, carries out addition reaction.Addition reaction of silicon with hydrogen is since nineteen forty-seven is found, the organosilicon worker is devoted to the research of effective catalyst always.What at first, use was maximum is platinum complexs such as Platinic chloride or Platinic chloride sylvite.Nineteen fifty-seven Speier adopts Virahol to handle Platinic chloride and forms H 2PtCl 6/ i-PrOH catalystsystem makes the hydrosilation ability of platinum be greatly improved.Afterwards, this catalyzer was used the ZGK 5 (divinyl tetramethyl disiloxane) that contains ethylene linkage and substituted as Karstedt catalyzer catalyst ligand, more highly active.
Improving activity of such catalysts, suppress the generation of side reaction, is investigator and worker's major issue that must solve, very crucial of research and preparation catalyst for addition reaction of hydrogen and silicon, also is a challenge greatly.People add various types of parts usually to reach optionally purpose of raising catalyst activity and special outcome in catalyzer.For example, interpolation contains the P part, contains the N part, contains S part etc., obtains certain effect to special reaction.
LED encapsulation silica gel is through the addition reaction of silicon with hydrogen curing molding.LED encapsulation silica gel is solidified, and catalyst levels is few, activity is adjustable, is significant.
(3) summary of the invention
The problem that the present invention need solve provides a kind of efficient, active controlled, and organotin, organic amine etc. is difficult for inactivation, is suitable for LED encapsulation silica gel solidified N-heterocyclic carbine platinum complex catalyst preparation method and application thereof.
A kind of N-heterocyclic carbine platinum complex, structure is suc as formula shown in (I):
Figure BDA0000117496510000021
In the formula (I), R 1=R 2=H or tBu (C (CH 3) 3), X=F, Cl, Br or I, R 3=H, Me, Et, nPr, iPr, nBu, tBu or Ph.
The invention still further relates to the method for the described N-heterocyclic carbine platinum complex of preparation; Said method comprises: adding metal platinum precursor compound and the aza ring carbene precursor of structure shown in (II) in the solvent; 30～80 ℃ were reacted 1～20 hour; Reaction finishes the back except that desolvating, and vacuum-drying obtains said N-heterocyclic carbine platinum complex;
Figure BDA0000117496510000022
In the formula (II), R 1=R 2=H or tBu (C (CH 3) 3), X=F, Cl, Br or I, R 3=H, Me, Et, nPr, iPr, nBu, tBu or Ph;
R 1=R 2During=H, aza ring carbene precursor is one of following:
[2-(O)C 6H 2CH＝NCH 2CH 2(C-{NCHCHNH})]X，
[2-(O)C 6H 2CH＝NCH 2CH 2(C-{NCHCHNMe})]X，
[2-(O)C 6H 2CH＝NCH 2CH 2(C-{NCHCHNEt})]X，
[2-(O)C 6H 2CH＝NCH 2CH 2(C-{NCHCHN nPr})]X，
[2-(O)C 6H 2CH＝NCH 2CH 2(C-{NCHCHN iPr})]X
[2-(O)C 6H 2CH＝NCH 2CH 2(C-{NCHCHN tBu})]X，
[2-(O)C 6H 2CH＝NCH 2CH 2(C-{NCHCHN nBu})]X，
[2-(O)C 6H 2CH＝NCH 2CH 2(C-{NCHCHN nPh})]X；
R 1=R 2= tDuring Bu, aza ring carbene precursor is one of following:
[3，5- tBu 2-2-(O)C 6H 2CH＝NCH 2CH 2(C-{NCHCHNH})]X，
[3，5- tBu 2-2-(O)C 6H 2CH＝NCH 2CH 2(C-{NCHCHNMe})]X，
[3，5- tBu 2-2-(O)C 6H 2CH＝NCH 2CH 2(C-{NCHCHNEt})]X，
[3，5- tBu 2-2-(O)C 6H 2CH＝NCH 2CH 2(C-{NCHCHN nPr})]X，
[3，5- tBu 2-2-(O)C 6H 2CH＝NCH 2CH 2(C-{NCHCHN iPr})]X
[3，5- tBu 2-2-(O)C 6H 2CH＝NCH 2CH 2(C-{NCHCHN tBu})]X，
[3，5- tBu 2-2-(O)C 6H 2CH＝NCH 2CH 2(C-{NCHCHN nBu})]X，
[3，5- tBu 2-2-(O)C 6H 2CH＝NCH 2CH 2(C-{NCHCHN nPh})]X。
Said metal platinum precursor compound is one of following: Platinic chloride, potassium platinichloride, potassium chloroplatinite;
Said metal platinum precursor compound and aza ring carbene precursor molar feed ratio are 1: 10～100;
Said solvent is one of following or wherein two or more mixture: water, THF, acetone, ether, sherwood oil, toluene, YLENE, methyl alcohol, ethanol, Virahol, the trimethyl carbinol, ETHYLE ACETATE, methyl aceto acetate.
Preparation aza ring carbene precursor compound is according to following flow process: formula (III) and formula (IV) compound are according to 1: 1 mol ratio of material; In absolute ethyl alcohol (absolute ethyl alcohol quality be raw materials quality with); 60 ℃ are stirred down, reaction 1h, and recrystallization is three times then; Vacuum-drying 24h under the room temperature obtains the aza ring carbene precursor compound:
Figure BDA0000117496510000041
Preferably, said metal platinum precursor compound is a Platinic chloride, and said solvent is one of following or wherein two or more mixture: water, THF, acetone, ethanol.
The invention still further relates to described N-heterocyclic carbine platinum complex as the application of catalyzer in LED packaging adhesive film curing reaction.Said LED packaging adhesive film is preferably the A/B glue that containing hydrogen silicone oil and vinyl base polymer etc. are formed.
Preferably, said curing reaction carries out under 25～200 ℃ (preferred 25～150 ℃), and reaction times 0.5～48h more preferably carries out 2～24h) under 25～150 ℃.
The present invention forms solvay-type silicon hydrogen addition catalyst through in catalyzer, adding nitrogen heterocycle carbine ligand under certain reaction conditions; Catalyzer is joined in the LED encapsulation silica gel, stir, after vacuum defoamation, under design temperature, solidify certain hour, can make LED encapsulation silica gel curing molding.
Beneficial effect of the present invention is mainly reflected in: N-heterocyclic carbine platinum complex catalyst of the present invention is than traditional silicon hydrogen addition catalyst; Help the coordination and the activation of atoms metal; Formed space steric effect of N-heterocyclic carbine and electronic effect; Help improving activity of such catalysts, help improving the resistibility of catalyzer, be difficult for inactivation organotin, organic amine etc.
(4) description of drawings
Fig. 1 is the HMR spectrogram of embodiment 1 N-heterocyclic carbine platinum complex catalyst.
(5) embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1:
(1) part [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNMe})] Br preparation:
In the 250ml there-necked flask, add 12.2g (0.1mol) salicylic aldehyde, 20.5g (0.1mol) H 2NCH 2CH 2(C-{NCHCHNMe})] Br and 32.7g absolute ethyl alcohol, 60 ℃ are stirred down, reaction 1h, recrystallization is three times then, and vacuum-drying 24h under the room temperature obtains 28.6g part [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNMe})] Br.
Figure BDA0000117496510000051
(2) Me 2ViSiO (MePhSiO) 121.6(Me 2SiO) 15.5(MeViSiO) 4SiViMe 2Preparation:
With 165.4g methyl-phenyl hybrid ring siloxane (([C 6H 5CH 3SiO] nN is 3～10)), 11.5g octamethylcyclotetrasiloxane, 3.44g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, 1.86g vinyl double-seal head (tetramethyl divinyl disiloxane) and 9.0g TMAH alkali glue joins in the 250ml there-necked flask; 100 ℃ are reacted 2h down; Through 170 ℃/-0.96MPa handles 3h, acquisition 144.5g Me 2ViSiO (MePhSiO) 121.6(Me 2SiO) 15.5(MeViSiO) 4SiViMe 2
(3) Me 2HSiO (MePhSiO) 121.6(Me 2SiO) 15.5(MeHSiO) 4.9SiHMe 2Preparation:
With 165.4g methyl-phenyl hybrid ring siloxane, 11.5g octamethylcyclotetrasiloxane, 3.04g tetramethyl-tetrahydrochysene cyclotetrasiloxane, the hydrogeneous double-seal head of 1.34g (tetramethyl-dihydro sily oxide); 9.0g the vitriol oil (98%; W/w) join in the 250ml there-necked flask, 60 ℃ of following reaction 2h leave standstill, separating funnel separatory after washing is to neutral; Through 170 ℃/-0.96MPa handles 3h, acquisition 128.8gMe 2HSiO (MePhSiO) 121.6(Me 2SiO) 15.5(MeHSiO) 4.9SiHMe 2
(4) N-heterocyclic carbine platinum complex catalyst preparation:
In 250ml single port bottle, add 0.614g [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNMe})] Br, the 0.51g Platinic chloride, the 80ml THF stirs 3h down at 60 ℃, and heating under vacuum is removed THF, and the gained solid is placed 60 ℃ of dried overnight in the vacuum drying oven, and obtaining part is [2-(O) C 6H 2CH=NCH 2CH 2(C-{NCHCHNMe})] the catalyzer 1.02g of Br, yield 90.8%, its HMR spectrogram be referring to Fig. 1, gained catalyzer n (L)/n (Pt)=2: 1.
(5) LED packaging adhesive film preparation:
Getting the A component is Me 2ViSiO (MePhSiO) 121.6(MePhSiO) 15.5(MeViSiO) 4SiViMe 2, the B component is Me 2HSiO (MePhSiO) 121.6(Me 2SiO) 15.5(MeHSiO) 4.9SiHMe 2A and the B component of LED encapsulation silica gel respectively get 10g, add the middle gained platinum complex catalyst of 0.010g (about 6ppm) (1), after mixing, obtain LED and encapsulate silica gel, its refractive index 1.54 is 8h at 25 ℃ of following operable times.Through vacuum defoamation 15min, in 120 ℃ of curing 2h, cured article hardness is 30shore A, records transmittance 99.8% with ultraviolet spectrophotometer.
Embodiment 2:
(1) part [2-(OH) C 6H 2CH=N CH 2CH 2(C-{NCHCHNH})] Cl preparation:
In the 250ml there-necked flask, add 12.2g (0.1mol) salicylic aldehyde, 14.7g (0.1mol) H 2N CH 2CH 2(C-{NCHCHNH})] Cl and 26.9g absolute ethyl alcohol, 60 ℃ are stirred down, reaction 1h, recrystallization is three times then, and vacuum-drying 24h under the room temperature obtains 24.0g part [2-(OH) C 6H 2CH=N CH 2CH 2(C-{NCHCHNH})] Cl.
Figure BDA0000117496510000061
(2) silica gel Me 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 2Preparation:
100.0g octamethylcyclotetrasiloxane, 3.44g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, 1.86g vinyl double-seal head and 5.0g TMAH alkali glue are joined in the 250ml there-necked flask; 100 ℃ are reacted 2h down; Through 170 ℃/-0.96MPa handles 3h, acquisition 82.5g Me 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 2
(3) Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 2Preparation:
With 101.5g octamethylcyclotetrasiloxane, 3.04g tetramethyl-tetrahydrochysene cyclotetrasiloxane, the hydrogeneous double-seal head of 1.34g; 5.0g acidic cation-exchange resin (LD605) joins in the 250ml there-necked flask, 65 ℃ are reacted 4h down, filter; Through 170 ℃/-0.96MPa handles 3h, acquisition 85.8.8g Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 2
(4) N-heterocyclic carbine platinum complex catalyst preparation:
In 250ml single port bottle, add 0.497g [2-(OH) C 6H 2CH=N CH 2CH 2(C-{NCHCHNH})] Cl, the 0.51g Platinic chloride, 100ml water stirs 10h down at 60 ℃, and heating under vacuum dewaters, and the gained solid is placed 60 ℃ of dried overnight in the vacuum drying oven, and obtaining part is [2-(O) C 6H 2CH=NCH 2CH 2(C-{NCHCHNH})] the catalyzer 0.959g of Cl, yield 95.2%, gained catalyzer n (L)/n (Pt)=2: 1.
(5) LED packaging adhesive film preparation:
Getting the A component is Me 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 2, the B component is Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 2A and the B component of LED encapsulation silica gel respectively get 10g, add the middle gained platinum complex catalyst of 0.021g (about 8ppm) (1), after mixing, obtain LED and encapsulate silica gel, its refractive index 1.41 is 12h at 25 ℃ of following operable times.Through vacuum defoamation 15min, in 60 ℃ of curing 4h, cured article hardness is 25shore A, records transmittance 99.5% with ultraviolet spectrophotometer.
Embodiment 3:
(1) part [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNEt})] I preparation:
In the 250ml there-necked flask, add 12.2g (0.1mol) salicylic aldehyde, 26.6g (0.1mol) H 2NCH 2CH 2(C-{NCHCHNEt})] I and 38.8g absolute ethyl alcohol, 60 ℃ are stirred down, reaction 1h, recrystallization is three times then, and vacuum-drying 24h under the room temperature obtains 32.1g part part [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNEt})] I.
(2) Me 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 2Preparation: 100g octamethylcyclotetrasiloxane, 3.44g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, 1.86g vinyl double-seal head and 9.0g TMAH alkali glue are joined in the 250ml there-necked flask; 100 ℃ are reacted 2h down; Through 170 ℃/-0.96MPa handles 3h, acquisition 91.5g Me 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 2
(3) Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 13.7SiHMe 2Preparation:
With 101.5g octamethylcyclotetrasiloxane, 8.2g tetramethyl-tetrahydrochysene cyclotetrasiloxane, the hydrogeneous double-seal head of 1.34g; 5.0g acidic cation-exchange resin (LD605) joins in the 250ml there-necked flask; 60 ℃ are reacted 2h down; Leave standstill, separating funnel separatory after washing is to neutral, through 170 ℃/-0.96MPa handles 3h, acquisition 128.8g Me 2HSiO (MePhSiO) 121.6(Me 2SiO) 15.5(MeHSiO) 4.9SiHMe 2
(4) N-heterocyclic carbine platinum complex catalyst preparation:
In 250ml single port bottle, add 0.184g [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNEt})] I, the 0.26g Platinic chloride, 100ml acetone stirs 8h down at 30 ℃, and heating under vacuum is removed acetone, and the gained solid is placed 60 ℃ of dried overnight in the vacuum drying oven, and getting part is [2-(O) C 6H 2CH=NCH 2CH 2(C-{NCHCHNEt})] the catalyzer 0.428g of I, yield 96.5%, gained catalyzer n (L)/n (Pt)=2: 1.
(5) LED packaging adhesive film preparation:
Get Me by 10g 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 2The A component of forming is by 10.0g Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 13.7SiHMe 2In the silica gel of the B component of forming, add gained platinum catalyst among the 0.045g (about 12ppm) (1), after mixing, obtain LED encapsulation silica gel, its refractive index 1.41 is 24h at 25 ℃ of following operable times.Through vacuum defoamation 15min, under 150 ℃, solidify 3h, cured article hardness is 60shore A, tensile strength 3.2MPa records transmittance 99.2% with ultraviolet spectrophotometer.
Embodiment 4:
(1) part [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN nPr})] F preparation:
In the 250ml there-necked flask, add 12.2g (0.1mol) salicylic aldehyde, 15.8g (0.1mol) H 2NCH 2CH 2(C-{NCHCHN nPr})] F and 28g absolute ethyl alcohol, 60 ℃ are stirred down, reaction 1h, recrystallization is three times then, and vacuum-drying 24h under the room temperature obtains 19.6g part [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN nPr})] F.
Figure BDA0000117496510000091
(2) Me 2ViSiO (MePhSiO) 121.6(MePhSiO) 15.5(MeViSiO) 4SiViMe 2Preparation is with embodiment 1.
(3) Me 2HSiO (MePhSiO) 121.6(Me 2SiO) 15.5(MeHSiO) 4.9SiHMe 2Preparation is with embodiment 1.
(4) N-heterocyclic carbine platinum complex catalyst preparation:
In 250ml single port bottle, add 0.548g [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN nPr})] F, the 0.51g Platinic chloride, 100ml ethanol stirs 1h down at 80 ℃, and heating under vacuum is removed ethanol, and the gained solid is placed 60 ℃ of dried overnight in the vacuum drying oven, and getting part is [2-(O) C 6H 2CH=NCH 2CH 2(C-{NCHCHN nPr})] the catalyzer 0.942g of F, yield 94.2%, gained catalyzer n (L)/n (Pt)=2: 1.
(5) LED packaging adhesive film preparation:
Get Me by 10g 2ViSiO (MePhSiO) 121.6(MePhSiO) 15.5(MeViSiO) 4SiViMe 2The A component of forming is by 10g Me 2HSiO (MePhSiO) 121.6(Me2SiO) 15.5(MeHSiO) 4.9In the silica gel of the B component that SiHMe forms, add gained platinum catalyst among the 0.045g (about 12ppm) (1), after mixing, obtain LED encapsulation silica gel, its refractive index 1.54 is 14h at 25 ℃ of following operable times.Through vacuum defoamation 15min, in 25 ℃ of curing 24h, cured article hardness is 65shore A, and tensile strength 3.5MPa records transmittance 99.6% with ultraviolet spectrophotometer.
Embodiment 5:
(1) part [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN iPr})] Br preparation:
In the 250ml there-necked flask, add 12.2g (0.1mol) salicylic aldehyde, 20.5g (0.1mol) H 2NCH 2CH 2(C-{NCHCHNMe})] Br and 32.7g absolute ethyl alcohol, 60 ℃ are stirred down, reaction 1h, in-10 ℃ of following recrystallizations three times, vacuum-drying 24h under the room temperature obtains 28.6g part [2-(OH) C then 6H 2CH=NCH 2CH 2(C-{NCHCHNMe})] Br.
(2) Me 2ViSiO (MePhSiO) 96(Me 2SiO) 41(MeViSiO) 4SiViMe 2Preparation:
130.5g methyl-phenyl hybrid ring siloxane, 30.3g octamethylcyclotetrasiloxane, 3.44g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, 1.86g vinyl double-seal head and 9.0g TMAH alkali glue are joined in the 250ml there-necked flask; 100 ℃ are reacted 2h down; Through 170 ℃/-0.96MPa handles 3h, acquisition 128.5g Me 2ViSiO (MePhSiO) 96(Me 2SiO) 41(MeViSiO) 4SiViMe 2
(3) Me 2HSiO (MePhSiO) 96(Me 2SiO) 41(MeHSiO) 4.9SiHMe 2Preparation
With 130.5g methyl-phenyl hybrid ring siloxane, 30.3g octamethylcyclotetrasiloxane, 3.04g tetramethyl-tetrahydrochysene cyclotetrasiloxane, the hydrogeneous double-seal head of 1.34g; 9.0g the vitriol oil (98%) joins in the 250ml there-necked flask; 60 ℃ are reacted 2h down; Leave standstill, separating funnel separatory after washing is to neutral, through 170 ℃/-0.96MPa handles 3h, acquisition 118.5g Me 2HSiO (MePhSiO) 96(Me 2SiO) 41(MeHSiO) 4.9SiHMe 2
(4) N-heterocyclic carbine platinum complex catalyst preparation:
In 250ml single port bottle, add 0.67g [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN iPr})] Br, the 0.51g Platinic chloride, 100ml toluene stirs 10h down at 80 ℃, and heating under vacuum is removed toluene, and the gained solid is placed 60 ℃ of dried overnight in the vacuum drying oven, and getting part is [2-(O) C 6H 2CH=NCH 2CH 2(C-{NCHCHN iPr})] the catalyzer 0.9735g of Br, yield 82.5%, gained catalyzer n (L)/n (Pt)=2: 1.
(4) LED packaging adhesive film preparation:
Get Me by 10g 2ViSiO (MePhSiO) 96(Me 2SiO) 41(MeViSiO) 4SiViMe 2The A component of forming is by 11.8g Me 2HSiO (MePhSiO) 96(Me 2SiO) 41(MeHSiO) 4.9SiHMe 2In the silica gel of the B component of forming, add gained platinum catalyst among the 0.045g (about 12ppm) (1), after mixing, obtain LED encapsulation silica gel, its refractive index 1.52 is 6h at 25 ℃ of following operable times.Through vacuum defoamation 15min, in 100 ℃ of curing 4h, cured article hardness is 80shore A, and tensile strength 2.4MPa records transmittance 98.5% with ultraviolet spectrophotometer.
Embodiment 6:
(1) part [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN tBu})] Br preparation:
In the 250ml there-necked flask, add 12.2g (0.1mol) salicylic aldehyde, 24.9g (0.1mol) H 2NCH 2CH 2(C-{NCHCHN tBu})] Br and 37.1g absolute ethyl alcohol, 60 ℃ are stirred down, reaction 1h, recrystallization is three times then, and vacuum-drying 24h under the room temperature obtains 29.8g part [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNMe})] Br.
(2) Me 2ViSiO (MePhSiO) 82(Me 2SiO) 55(MeViSiO) 4SiViMe 2Preparation:
111.5g methyl-phenyl hybrid ring siloxane, 40.7g octamethylcyclotetrasiloxane, 3.44g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, 1.86g vinyl double-seal head and 9.0g TMAH alkali glue are joined in the 250ml there-necked flask; 100 ℃ are reacted 2h down; Through 170 ℃/-0.96MPa handles 3h, acquisition 144.5g Me 2ViSiO (MePhSiO) 82(Me 2SiO) 55(MeViSiO) 4SiViMe 2
(3) Me 2HSiO (MePhSiO) 82(MePhSiO) 55(MeHSiO) 4.9SiHMe 2Preparation
With 165.4g methyl-phenyl hybrid ring siloxane, 11.5g octamethylcyclotetrasiloxane, 3.04g tetramethyl-tetrahydrochysene cyclotetrasiloxane, the hydrogeneous double-seal head of 1.34g; 9.0g acidic cation-exchange resin (LD605) joins in the 250ml there-necked flask; 60 ℃ are reacted 2h down; Leave standstill, separating funnel separatory after washing is to neutral, through 170 ℃/-0.96MPa handles 3h, acquisition 146.8g Me 2HSiO (MePhSiO) 82(MePhSiO) 55(MeHSiO) 4.9SiHMe 2
(4) N-heterocyclic carbine platinum complex catalyst preparation:
In 250ml single port bottle, add 0.698g [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN tBu})] Br, the 0.51g Platinic chloride, the 80ml Virahol stirs 7h down at 80 ℃, and heating under vacuum is removed Virahol, and the gained solid is placed 60 ℃ of dried overnight in the vacuum drying oven, and getting part is [2-(O) C 6H 2CH=NCH 2CH 2(C-{NCHCHN tBu})] the catalyzer 1.186g of Br, yield 98.2%, gained catalyzer n (L)/n (Pt)=2: 1.
(5) LED packaging adhesive film preparation:
Get Me by 10g 2ViSiO (MePhSiO) 82(MePhSiO) 55(MeViSiO) 4SiViMe 2The A component of forming is by 10g Me 2HSiO (MePhSiO) 82(MePhSiO) 55(MeHSiO) 4.9SiHMe 2In the silica gel of the B component of forming, add gained platinum catalyst among the 0.045g (about 12ppm) (1), after mixing, obtain LED encapsulation silica gel, its refractive index 1.50 is 6h at 25 ℃ of following operable times.Through vacuum defoamation 15min, in 150 ℃ of curing 4h, cured article hardness is 78shore A, and tensile strength 2.8MPa records transmittance 99.5% with ultraviolet spectrophotometer.
Embodiment 7:
(1) part [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN nBu})] Br preparation:
In the 250ml there-necked flask, add 12.2g (0.1mol) salicylic aldehyde, 20.5g (0.1mol) H 2NCH 2CH 2(C-{NCHCHNMe})] Br and 32.7g absolute ethyl alcohol, 60 ℃ are stirred down, reaction 1h, recrystallization is three times then, and vacuum-drying 24h under the room temperature obtains 29.5g part [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNMe})] Br.
(2) Me 2ViSiO (MePhSiO) 82(Me 2SiO) 55(MeViSiO) 4SiViMe 2Preparation is with embodiment 6.
(3) Me 2HSiO (MePhSiO) 82(Me 2SiO) 55(MeHSiO) 4.9SiHMe 2Preparation is with embodiment 6.
(4) N-heterocyclic carbine platinum complex catalyst preparation:
In 250ml single port bottle, add 0.698g [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN nBu})] Br, the 0.51g Platinic chloride, 50ml ETHYLE ACETATE stirs 15h down at 40 ℃, and heating under vacuum is removed ETHYLE ACETATE, and the gained solid is placed 60 ℃ of dried overnight in the vacuum drying oven, and getting part is [2-(O) C 6H 2CH=NCH 2CH 2(C-{NCHCHN nBu})] the catalyzer 1.155g of Br, yield 95.6%, gained catalyzer n (L)/n (Pt)=2: 1.
(5) LED packaging adhesive film preparation:
Get Me by 10g 2ViSiO (MePhSiO) 82(Me 2SiO) 55(MeViSiO) 4SiViMe 2The A component of forming is by 10g Me 2HSiO (MePhSiO) 82(Me 2SiO) 55(MeHSiO) 4.9In the silica gel of the B component that SiHMe forms, add gained platinum catalyst among the 0.045g (about 12ppm) (1), after mixing, obtain LED encapsulation silica gel, its refractive index 1.50 is 4h at 25 ℃ of following operable times.Through vacuum defoamation 15min, in 150 ℃ of curing 2h, cured article hardness is 78shore A, and tensile strength 2.8MPa records transmittance 99.8% with ultraviolet spectrophotometer.
Embodiment 8:
(1) part [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN nPh})] Br preparation:
In the 250ml there-necked flask, add 12.2g (0.1mol) salicylic aldehyde, 25.3g (0.1mol) H 2NCH 2CH 2(C-{NCHCHN Ph})] Br and 37.5g absolute ethyl alcohol, 60 ℃ are stirred down, reaction 1h, recrystallization is three times then, and vacuum-drying 24h under the room temperature obtains 31.9g part [2-[2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN nPh})] Br.
(2) Me 2ViSiO (MePhSiO) 82(Me 2SiO) 55(MeViSiO) 4SiViMe 2Preparation is with embodiment 6.
(3) Me 2HSiO (MePhSiO) 82(Me 2SiO) 55(MeHSiO) 4.9SiHMe 2Preparation is with embodiment 6.
(4) N-heterocyclic carbine platinum complex catalyst preparation:
In 250ml single port bottle, add 0.738g [2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN Ph})] Br, the 0.51g Platinic chloride, the 50ml methyl aceto acetate stirs 20h down at 50 ℃, and heating under vacuum is removed methyl aceto acetate, and the gained solid is placed 60 ℃ of dried overnight in the vacuum drying oven, and getting part is [2-(O) C 6H 2CH=NCH 2CH 2(C-{NCHCHN nPh})] the catalyzer 1.198g of Br, yield 96.0%, gained catalyzer n (L)/n (Pt)=2: 1.
(5) LED packaging adhesive film preparation:
Get Me by 10g 2ViSiO (MePhSiO) 82(Me 2SiO) 55(MeViSiO) 4SiViMe 2The A component of forming is by 10g Me 2HSiO (MePhSiO) 82(MePhSiO) 55(MeHSiO) 4.9In the silica gel of the B component that SiHMe forms, add gained platinum catalyst among the 0.045g (about 12ppm) (1), after mixing, obtain LED encapsulation silica gel, its refractive index 1.50 is 3h at 25 ℃ of following operable times.Through vacuum defoamation 15min, in 150 ℃ of curing 2h, cured article hardness is 78shore A, and tensile strength 2.8MPa records transmittance 99.8% with ultraviolet spectrophotometer.
Embodiment 9:
(1) part [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNH})] Cl preparation:
In the 250ml there-necked flask, add 23.6g (0.1mol) 3,5-di-tert-butyl salicylaldehyde, 13.3g (0.1mol) H 2NCH 2CH 2(C-{NCHCHNH})] Cl and 36.9g absolute ethyl alcohol, 60 ℃ are stirred down, reaction 1h, recrystallization is three times then, vacuum-drying 24h under the room temperature, acquisition 33.5g part [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNH})] Cl.
(2) Me 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 2Preparation
183.7g methyl-phenyl hybrid ring siloxane, 3.44g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, 1.86g vinyl double-seal head and 9.0g TMAH alkali glue are joined in the 250ml there-necked flask; 100 ℃ are reacted 2h down; Through 170 ℃/-0.96MPa handles 3h, acquisition 162.5g Me 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 2
(3) Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 2Preparation:
With 183.7g methyl-phenyl hybrid ring siloxane, 3.04g tetramethyl-tetrahydrochysene cyclotetrasiloxane, the hydrogeneous double-seal head of 1.34g; 9.0g the vitriol oil (98%) joins in the 250ml there-necked flask; 60 ℃ are reacted 2h down; Leave standstill, separating funnel separatory after washing is to neutral, through 170 ℃/-0.96MPa handles 3h, acquisition 148.9g Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 2
(4) N-heterocyclic carbine platinum complex catalyst preparation:
In 250ml single port bottle, and adding 0.721g [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNH})] Cl, the 0.51g Platinic chloride, 100ml water stirs down 10h at 60 ℃, heating under vacuum dewaters, and the gained solid is placed 60 ℃ of dried overnight in the vacuum drying oven, obtain part for [3,5- tBu 2-2-(O) C 6H 2CH=NCH 2CH 2(C-{NCHCHNH})] the catalyzer 1.065g of Cl, yield 86.5%, gained catalyzer n (L)/n (Pt)=2: 1.
(4) LED packaging adhesive film preparation:
Getting the A component is Me 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 2, the B component is Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 2A and the B component of LED encapsulation silica gel respectively get 10g, add the middle gained platinum complex catalyst of 0.021g (about 8ppm) (1), after mixing, obtain LED and encapsulate silica gel, its refractive index 1.41 is 12h at 25 ℃ of following operable times.Through vacuum defoamation 15min, in 60 ℃ of curing 4h, cured article hardness is 25shore A, records transmittance 99.5% with ultraviolet spectrophotometer.
Embodiment 10:
(1) part [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNMe})] Br preparation:
In the 250ml there-necked flask, add 23.6g (0.1mol) 3,5-di-tert-butyl salicylaldehyde, 20.5g (0.1mol) H 2NCH 2CH 2(C-{NCHCHNMe})] Br and 44.1g absolute ethyl alcohol, 60 ℃ are stirred down, reaction 1h, recrystallization is three times then, vacuum-drying 24h under the room temperature, acquisition 39.5g part [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNMe})] Br.
(2) Me 2ViSiO (MePhSiO) 121.6(MePhSiO) 15.5(MeViSiO) 4SiViMe 2Preparation is with embodiment 1
(3) Me 2HSiO (MePhSiO) 121.6(Me 2SiO) 15.5(MeHSiO) 4.9SiHMe 2Preparation Me 2ViSiO (MePhSiO) 121.6(MePhSiO) 15.5(MeViSiO) 4SiViMe 2Preparation is with embodiment 1
(4) N-heterocyclic carbine platinum complex catalyst preparation:
In 250ml single port bottle, and adding 0.838g [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNMe})] Br, the 0.51g Platinic chloride, the 50ml THF stirs down 3h at 60 ℃, heating under vacuum is removed THF, and the gained solid is placed 60 ℃ of dried overnight in the vacuum drying oven, obtain part for [3,5- tBu 2-2-(O) C 6H 2CH=NCH 2CH 2(C-{NCHCHNMe})] the catalyzer 1.166g of Br, yield 86.5%, gained catalyzer n (L)/n (Pt)=2: 1.
(5) LED packaging adhesive film preparation:
Getting the A component is Me 2ViSiO (MePhSiO) 121.6(MePhSiO) 15.5(MeViSiO) 4SiViMe 2, the B component is Me 2HSiO (MePhSiO) 121.6(Me 2SiO) 15.5(MeHSiO) 4.9SiHMe 2A and the B component of LED encapsulation silica gel respectively get 10g, add the middle gained platinum complex catalyst of 0.010g (about 6ppm) (1), after mixing, obtain LED and encapsulate silica gel, its refractive index 1.54 is 8h at 25 ℃ of following operable times.Through vacuum defoamation 15min, in 120 ℃ of curing 2h, cured article hardness is 30shore A, records transmittance 99.8% with ultraviolet spectrophotometer.
Embodiment 11:
(1) part [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNEt})] I preparation:
In the 250ml there-necked flask, add 23.6g (0.1mol) 3,5-di-tert-butyl salicylaldehyde, 26.6g (0.1mol) H 2NCH 2CH 2(C-{NCHCHNEt})] I and 50.2g absolute ethyl alcohol, 60 ℃ are stirred down, reaction 1h, recrystallization is three times then, vacuum-drying 24h under the room temperature, acquisition 44.3g part [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNEt})] I.
(2) Me 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 2Preparation is with embodiment 9.
(3) Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 2Preparation is with embodiment 9.
(4) N-heterocyclic carbine platinum complex catalyst preparation:
In 250ml single port bottle, and adding 0.592g [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNEt})] I, the 0.26g Platinic chloride, 100ml acetone stirs down 8h at 30 ℃, heating under vacuum is removed acetone, and the gained solid is placed 60 ℃ of dried overnight in the vacuum drying oven, part be [3,5- tBu 2-2-(O) C 6H 2CH=NCH 2CH 2(C-{NCHCHNEt})] the catalyzer 0.754g of I, yield 88.5%, gained catalyzer n (L)/n (Pt)=2: 1.
(5) LED packaging adhesive film preparation:
Get Me by 10g 2ViSiO (Me 2SiO) 135.1(MeViSiO) 4SiViMe 2The A component of forming is by 10g Me 2HSiO (Me 2SiO) 137.1(MeHSiO) 4.9SiHMe 2In the silica gel of the B component of forming, add gained platinum catalyst among the 0.045g (about 12ppm) (1), after mixing, obtain LED encapsulation silica gel, its refractive index 1.41 is 24h at 25 ℃ of following operable times.Through vacuum defoamation 15min, under 150 ℃, solidify 3h, cured article hardness is 60shore A, tensile strength 3.2MPa records transmittance 99.2% with ultraviolet spectrophotometer.
Embodiment 12:
(1) part [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN nPr})] F preparation:
In the 250ml there-necked flask, add 23.6g (0.1mol) 3,5-di-tert-butyl salicylaldehyde, 15.8g (0.1mol) H 2NCH 2CH 2(C-{NCHCHN nPr})] F and 39.4g absolute ethyl alcohol, 60 ℃ are stirred down, reaction 1h, recrystallization is three times then, vacuum-drying 24h under the room temperature, acquisition 31.2g part [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN nPr})] F.
(2) Me 2ViSiO (MePhSiO) 121.6(MePhSiO) 15.5(MeViSiO) 4SiViMe 2Preparation is with embodiment 1.
(3) Me 2HSiO (MePhSiO) 121.6(Me 2SiO) 15.5(MeHSiO) 4.9SiHMe 2Preparation is with embodiment 1.
(4) N-heterocyclic carbine platinum complex catalyst preparation:
In 250ml single port bottle, and adding 0.7752g [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN nPr})] F, the 0.51g Platinic chloride, 100ml ethanol stirs down 1h at 80 ℃, heating under vacuum is removed ethanol, and the gained solid is placed 60 ℃ of dried overnight in the vacuum drying oven, part be [3,5- tBu 2-2-(O) C 6H 2CH=NCH 2CH 2(C-{NCHCHN nPr})] the catalyzer 1.207g of F, yield 94.2%, gained catalyzer n (L)/n (Pt)=2: 1.
(5) LED packaging adhesive film preparation:
Get Me by 10g 2ViSiO (MePhSiO) 121.6(MePhSiO) 15.5(MeViSiO) 4SiViMe 2The A component of forming is by 10g Me 2HSiO (MePhSiO) 121.6(Me 2SiO) 15.5(MeHSiO) 4.9In the silica gel of the B component that SiHMe forms, add gained platinum catalyst among the 0.045g (about 12ppm) (1), after mixing, obtain LED encapsulation silica gel, its refractive index 1.54 is 14h at 25 ℃ of following operable times.Through vacuum defoamation 15min, in 25 ℃ of curing 24h, cured article hardness is 65shore A, and tensile strength 3.5MPa records transmittance 99.6% with ultraviolet spectrophotometer.
Embodiment 13:
(1) part [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN tBu})] Br preparation:
In the 250ml there-necked flask, add 23.6g (0.1mol) 3,5-di-tert-butyl salicylaldehyde, 20.5g (0.1mol) H 2NCH 2CH 2(C-{NCHCHNMe})] Br and 44.1g absolute ethyl alcohol, 60 ℃ are stirred down, reaction 1h, recrystallization is three times then, vacuum-drying 24h under the room temperature, acquisition 39.8g part [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN tBu})] Br.
(2) Me 2ViSiO (MePhSiO) 82(Me 2SiO) 55(MeViSiO) 4SiViMe 2Preparation is with embodiment 6.
(3) Me 2HSiO (MePhSiO) 82(Me 2SiO) 55(MeHSiO) 4.9SiHMe 2Preparation is with embodiment 6.
(4) N-heterocyclic carbine platinum complex catalyst preparation:
In 250ml single port bottle, and adding 0.922g [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN tBu})] Br, the 0.51g Platinic chloride, the 80ml Virahol stirs down 7h at 80 ℃, heating under vacuum is removed Virahol, and the gained solid is placed 60 ℃ of dried overnight in the vacuum drying oven, part be [3,5- tBu 2-2-(O) C 6H 2CH=NCH 2CH 2(C-{NCHCHN tBu})] the catalyzer 1.317g of Br, yield 92.0%, gained catalyzer n (L)/n (Pt)=2: 1.
(4) LED packaging adhesive film preparation:
Get Me by 10g 2ViSiO (MePhSiO) 82(MePhSiO) 55(MeViSiO) 4SiViMe 2The A component of forming is by 10g Me 2HSiO (MePhSiO) 82(MePhSiO) 55(MeHSiO) 4.9In the silica gel of the B component that SiHMe forms, add gained platinum catalyst among the 0.045g (about 12ppm) (1), after mixing, obtain LED encapsulation silica gel, its refractive index 1.50 is 3h at 25 ℃ of following operable times.Through vacuum defoamation 15min, in 150 ℃ of curing 2h, cured article hardness is 78shore A, and tensile strength 2.8MPa records transmittance 99.8% with ultraviolet spectrophotometer.
Embodiment 14: the N-heterocyclic carbine Preparation of catalysts
(1) part [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNPh})] Br preparation:
In the 250ml there-necked flask, add 23.6g (0.1mol) 3,5-di-tert-butyl salicylaldehyde, 25.3g (0.1mol) H 2NCH 2CH 2(C-{NCHCHNPh})] Br and 48.9g absolute ethyl alcohol, 60 ℃ are stirred down, reaction 1h, recrystallization is three times then, vacuum-drying 24h under the room temperature, acquisition 41.7g part [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHNPh})] Br.
(2) Me 2ViSiO (MePhSiO) 82(Me 2SiO) 55(MeViSiO) 4SiViMe 2Preparation is with embodiment 6.
(3) Me 2HSiO (MePhSiO) 82(Me 2SiO) 55(MeHSiO) 4.9SiHMe 2Preparation is with embodiment 6.
(4) N-heterocyclic carbine platinum complex catalyst preparation:
In 250ml single port bottle, and adding 0.962g [3,5- tBu 2-2-(OH) C 6H 2CH=NCH 2CH 2(C-{NCHCHN nPh})] Br, the 0.51g Platinic chloride, the 50ml methyl aceto acetate stirs down 20h at 50 ℃, heating under vacuum is removed methyl aceto acetate, and the gained solid is placed 60 ℃ of dried overnight in the vacuum drying oven, part be [3,5- tBu 2-2-(O) C 6H 2CH=NCH 2CH 2(C-{NCHCHN nPh})] the catalyzer 1.273g of Br, yield 86.5%, gained catalyzer n (L)/n (Pt)=2: 1.
(5) LED packaging adhesive film preparation:
Get Me by 10g 2ViSiO (MePhSiO) 82(MePhSiO) 55(MeViSiO) 4SiViMe 2The A component of forming is by 10g Me 2HSiO (MePhSiO) 82(MePhSiO) 55(MeHSiO) 4.9In the silica gel of the B component that SiHMe forms, add gained platinum catalyst among the 0.045g (about 12ppm) (1), after mixing, obtain LED encapsulation silica gel, its refractive index 1.50 is 3h at 25 ℃ of following operable times.Through vacuum defoamation 15min, in 150 ℃ of curing 2h, cured article hardness is 78shore A, and tensile strength 2.8MPa records transmittance 99.8% with ultraviolet spectrophotometer.

Claims (5)

1. N-heterocyclic carbine platinum complex, structure is suc as formula shown in (I):
Figure FDA0000117496500000011
In the formula (I), R 1=R 2=H or tBu, X=F, Cl, Br or I, R 3=H, Me, Et, nPr, iPr, nBu, tBu or Ph.
2. method for preparing N-heterocyclic carbine platinum complex as claimed in claim 1; Said method comprises: adding metal platinum precursor compound and the aza ring carbene precursor of structure shown in (II) in the solvent; 30～80 ℃ were reacted 1～20 hour; Reaction finishes the back except that desolvating, and vacuum-drying obtains said N-heterocyclic carbine platinum complex;
Figure FDA0000117496500000012
In the formula (II), R 1=R 2=H or tBu, X=F, Cl, Br or I, R 3=H, Me, Et, nPr, iPr, nBu, tBu or Ph;
Said metal platinum precursor compound is one of following: Platinic chloride, potassium platinichloride, potassium chloroplatinite; Said metal platinum precursor compound and aza ring carbene precursor molar feed ratio are 1: 10～100; Said solvent is one of following or wherein two or more mixture: water, THF, acetone, ether, sherwood oil, toluene, YLENE, methyl alcohol, ethanol, Virahol, the trimethyl carbinol, ETHYLE ACETATE, methyl aceto acetate.
3. method as claimed in claim 2 is characterized in that: said metal platinum precursor compound is a Platinic chloride, and said solvent is one of following or wherein two or more mixture: water, THF, acetone, ethanol.
4. N-heterocyclic carbine platinum complex as claimed in claim 1 is as the application of catalyzer in LED packaging adhesive film curing reaction.
5. application as claimed in claim 4 is characterized in that said curing reaction carries out, reaction times 0.5～48h under 25～200 ℃.
CN201110405370XA 2011-12-08 2011-12-08 N-heterocyclic carbene complex catalyst and preparation and application thereof Pending CN102516314A (en)

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Application publication date: 20120627