CN105694047B - Main chain silicon modified organic polymer containing cyclic structure and preparation method thereof - Google Patents
Main chain silicon modified organic polymer containing cyclic structure and preparation method thereof Download PDFInfo
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- CN105694047B CN105694047B CN201610269653.9A CN201610269653A CN105694047B CN 105694047 B CN105694047 B CN 105694047B CN 201610269653 A CN201610269653 A CN 201610269653A CN 105694047 B CN105694047 B CN 105694047B
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 46
- 239000010703 silicon Substances 0.000 title claims abstract description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 21
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000010792 warming Methods 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 238000009835 boiling Methods 0.000 claims abstract description 18
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- -1 vinyl norbornenes Chemical class 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical class C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 235000001510 limonene Nutrition 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 150000002628 limonene derivativess Chemical class 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 claims 3
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 11
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 description 11
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 230000009466 transformation Effects 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003376 silicon Chemical class 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001558 organosilicon polymer Polymers 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- KAJRUHJCBCZULP-UHFFFAOYSA-N 1-cyclohepta-1,3-dien-1-ylcyclohepta-1,3-diene Chemical compound C1CCC=CC=C1C1=CC=CCCC1 KAJRUHJCBCZULP-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- NVYQDQZEMGUESH-UHFFFAOYSA-N dimethylsilyloxy(dimethyl)silane Chemical class C[SiH](C)O[SiH](C)C NVYQDQZEMGUESH-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G77/60—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- 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
- C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
-
- 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
- C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
- C08G77/52—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages containing aromatic rings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Silicon Polymers (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention relates to a series of main chain silicon modified organic polymers containing cyclic structure and preparation method thereof, and synthesis path is as follows：A certain amount of bi-vinyl monomer, solvent and a certain amount of noble metal catalyst are added into reactor, 10~90min is stirred at 10~90 DEG C, a certain amount of double Si H group monomers are then added, is warming up at 60~120 DEG C insulated and stirred reaction 4~for 24 hours；After reaction, solvent and the low boiling point volatile matter in removing system are evaporated under reduced pressure to get to silicon modified organic polymer of the main chain containing cyclic structure；The preparation method has the advantages that production cost is low, easy-operating, and the silicon modified organic polymer of preparation has the characteristics that low content of halogen, high refractive index, good weatherability, high and low temperature resistance are excellent.
Description
Technical field
The present invention relates to a series of main chain silicon modified organic polymers containing cyclic structure with and preparation method thereof, belonging to has
Machine --- inorganic hybrid material technical field.
Background technology
Organopolysiloxane is using Si-O-Si keys as molecular backbone, and methyl, phenyl, vinyl etc. are connected on silicon atom to be had
Half inorganic polymer of cross-linking type of machine group.The particularity of its structure makes it have excellent heat resistance, ageing-resistant, weatherability
And the advantages that electrical insulation capability, therefore be widely used in aerospace, nuclear power station, military weapon, LED encapsulation fields etc..
But since the main chain of conventional silicone is made of pure Si-O keys, " unbuttoning " formula easily occurs and " thermal rearrangement " degrades.
Cyclic hydrocarbon and aromatic ring structure are because its three-dimensional effect and rigidity are larger, for improving the rigid of organopolysiloxane
Property tool be very helpful, and help to improve the refractive index of organosilicon product.All the time, cyclic hydrocarbon radical or aromatic radical be mostly all
Exist with the pendant manner of organosilicon product, and in the majority with phenyl.If be introduced on the main chain of silicone product, instead of master
Part oxygen atom in chain can prevent main chain cyclization degradation at high temperature, improve the long-term thermal stability and machine of organosilicon product
Tool intensity, while increasing the compactness of intermolecular arrangements, the sulfidation-resistance to improving LED casting glues can have positive meaning.
Currently, some visible penylene organic silicon monomers on the market, but because its preparation process limits, hold at high price,
And content of halogen is higher, is not appropriate for the preparation applied to LED packaging plastics.High cost, high halogen content limits penylene has
The application of machine silicon monomer, while also limiting organosilicon polymer that main chain backbone contains aromatic radical or cyclic hydrocarbyl structure energetically
Exploitation and application.
This patent devises a series of silicon modified organic polymer of main chains containing cyclic structure, is not contained only in polymer architecture
There is element silicon, also contain phenylene and cyclic hydrocarbyl structure, while there is vinyl or Si -- H, there is hydrosilylation
Activity.Preparation method uses the mode of simple and practicable Si―H addition reaction, is easy industrialized production, while avoiding grignard examination
The method of agent can substantially reduce the content of halogen in product, in order to its application in dual composition addition type LED casting glues.
Invention content
Technical problem to be solved by the invention is to provide a series of silicon modified organic polymer of main chains containing cyclic structure
And preparation method thereof, the fields such as LED organosilicon encapsulating materials are can be applied to, with production cost is low, content of halogen is low, refractive index
The features such as height, good weatherability, excellent high and low temperature resistance.
A series of preparation method of silicon modified organic polymer of main chains containing cyclic structure of the present invention, feature exist
In using the method for Si―H addition reaction, synthesis path is as follows：
A certain amount of bi-vinyl monomer, solvent and a certain amount of noble metal catalyst are added into reactor, 10~
10~90min is stirred at 90 DEG C, and a certain amount of double Si -- H monomers are then added, are warming up to insulated and stirred at 60~120 DEG C
Reaction 4~for 24 hours.After reaction, the solvent being evaporated under reduced pressure in removing system is produced with low boiling point volatile matter to get to target
Silicon modified organic polymer of object --- the main chain containing cyclic structure.
As described above, bi-vinyl monomer can be divinylbenzene, dicyclopentadiene, vinyl norbornene, lemon
Alkene, cyclopentadiene, bicycloheptadiene, 1,5- cyclo-octadiene, two silica of 1,3- divinyl -1,3- dimethyl -1,3- diphenyl
One or more of alkane etc..Solvent can be toluene, benzene, tetrahydrofuran, cyclohexanone, glycol dimethyl ether, phthalic acid
One or more of dimethyl ester, isopropanol etc..Noble metal catalyst be Si―H addition reaction custom catalysts, can be rhodium, platinum,
Palladium, ruthenium and its complex compound catalyst.Double Si -- H monomers can be 1,1,3,3- tetramethyl disiloxanes or bis- (dimethyl-silicons
Base) mixing of one or both of benzene.
The molar ratio of bi-vinyl monomer and double Si -- H monomers is 0.4~2.5:1.Noble metal catalyst is in system
Content be 2ppm~0.5 ‰.The additive amount of solvent is 0~15 times (mass ratio) of bi-vinyl monomer, and includes 0.By upper
The synthetic method, a series of silicon modified organic polymer of main chains containing cyclic structure of the present invention of acquisition, knot
Structure is characterized in that silicon modified organic polymer is chain structure, and phenyl ring or cyclic hydrocarbyl structure are contained on its main chain backbone, and
Containing element silicon, there is Si-H bifunctional or vinyl active group.Raw material rate of charge is converted, reaction condition is changed, is held
Being easy to get has to molecular weight from modification of the main chain containing cyclic structure transformed to less than 1000 oligomer higher than tens of thousands of high polymers
Organosilicon polymer.The altered refractive index ranging from 1.45 of silicon modified organic polymer of the main chain of acquisition containing cyclic structure~
1.57, the formulary requirements of the organosilicon addition system with different refractivity can be met.
Embodiment
The main chain of 1 cycloalkenyl group of embodiment sealing end contains phenylene and the modified organic silicon of cyclic hydrocarbon radical
26.44g (0.2mol) dicyclopentadiene, 50g toluene and 20uL Pt contents are added into the three-necked flask of 250mL
For 25% Karstedt catalyst, 60min is stirred after being warming up to 60 DEG C, the Isosorbide-5-Nitrae-that 19.44g (0.1mol) is then added is bis-
(dimethyl silicon substrate) benzene, is warming up to 110 DEG C, is stirred to react 36h.After reaction, be evaporated under reduced pressure removing system in solvent with
Low boiling point volatile matter contains phenylene and the modified organic silicon of cyclic hydrocarbon radical to get to the main chain that cycloalkenyl group blocks.By this implementation
Example rate of charge, n=0, yield 79.4%, refractive index 1.56.Transformation raw material, which feeds intake, when changes reaction condition, and knot can be changed
The value of n in structure.
The modified organic silicon of the structure containing phenylene of 2 double styrene of embodiment sealing end
19.52g (0.15mol) divinylbenzene, 100g cyclohexanone and 0.06g are added into the three-necked flask of 250mL
Pt-C (5%) catalyst, stirs 30min at room temperature, is then slowly added into 1,1,3, the 3- tetramethyl two of 13.43g (0.1mol)
Siloxanes is warming up to 100 DEG C, is stirred to react 12h.After reaction, the solvent being evaporated under reduced pressure in removing system is waved with low boiling point
Object is sent out to get the modified organic silicon of the structure containing phenylene blocked to double styrene.By the present embodiment rate of charge, n=2, yield
It is 93.4%, refractive index 1.54.Transformation raw material, which feeds intake, when changes reaction condition, and the value of n in structure can be changed.
The modified organic silicon of 3 penylene silicon hydrogen of embodiment sealing end
31.05g (0.1mol) 1,3- divinyl -1,3- dimethyl -1,3- hexichol is added into the three-necked flask of 250mL
Base disiloxane, 65g isopropanols and 10uL speier catalyst (Pt 25%), stir 10min, are then slowly added at room temperature
Bis- (dimethyl silicon substrate) benzene of Isosorbide-5-Nitrae-of 24.30g (0.125mol), are warming up to 110 DEG C, are stirred to react 18h.After reaction, subtract
The solvent in system is distilled off with low boiling point volatile matter to get the modified organic silicon blocked to penylene silicon hydrogen in pressure.By this implementation
Example rate of charge, n=4, yield 95.4%, refractive index 1.55.Transformation raw material, which feeds intake, when changes reaction condition, and knot can be changed
The value of n in structure.
The main chain of 4 cycloolefin of embodiment sealing end contains the modified organic silicon of phenylene and cyclic hydrocarbyl structure
24.04g (0.2mol) vinyl norbornenes and 0.106g Pt-C (5%) are added into the three-necked flask of 250mL
Catalyst is warming up to 85 DEG C, stirs 60min, and the Isosorbide-5-Nitrae-for being then slowly added into 29.16g (0.15mol) is bis- (dimethyl silicon substrate)
Benzene is warming up to 100 DEG C, is stirred to react 36h.After reaction, the solvent and low boiling point volatile matter being evaporated under reduced pressure in removing system,
Obtain the modified organic silicon that the main chain of cycloolefin sealing end contains phenylene and cyclic hydrocarbyl structure.By the present embodiment rate of charge, n=
2, yield 88.4%, refractive index 1.55.Transformation raw material, which feeds intake, when changes reaction condition, and the value of n in structure can be changed.
The main chain of 5 silicon hydrogen of embodiment sealing end contains the modified organic silicon of cyclic hydrocarbyl structure
13.62g (0.1mol) limonene, 100g glycol dimethyl ethers and 0.12g are added into the three-necked flask of 250mL
Pd-C (5%) catalyst is warming up to 40 DEG C, stirs 30min, is then slowly added into 1,1,3, the 3- tetramethyl of 26.87g (0.2mol)
Base disiloxane is warming up to 110 DEG C, is stirred to react for 24 hours.After reaction, the solvent and low boiling being evaporated under reduced pressure in removing system
After point volatile matter, filtering is to get to target product.By the present embodiment rate of charge, n=1, yield 89.7%, refractive index is
1.47.Transformation raw material, which feeds intake, when changes reaction condition, and the value of n in structure can be changed.
The main chain of 6 silicon hydrogen group of embodiment sealing end contains the modified organic silicon of cyclic hydrocarbyl structure
Into the three-necked flask of 250mL be added 12.02g (0.1mol) vinyl norbornene, 80g tetrahydrofurans and
0.15g Ru-C (5%) catalyst is warming up to 40 DEG C, stirs 30min, is then slowly added into the 1,1 of 20.15g (0.15mol),
3,3- tetramethyl disiloxanes are warming up to 100 DEG C, are stirred to react for 24 hours.After reaction, it is evaporated under reduced pressure molten in removing system
Agent contains the modified organic silicon of cyclic hydrocarbyl structure to the main chain that silicon hydrogen group blocks with low boiling point volatile matter.By this implementation
Example rate of charge, n=2, yield 83.7%, refractive index 1.47.Transformation raw material, which feeds intake, when changes reaction condition, and knot can be changed
The value of n in structure.
The main chain of 7 cycloalkenyl group of embodiment sealing end contains the modified organic silicon of penylene and cyclic hydrocarbyl structure
34.06g (0.25mol) limonenes and 0.15g Rh-C (5%) catalyst are added into the three-necked flask of 250mL,
45 DEG C are warming up to, 30min is stirred, is then slowly added into bis- (dimethyl silicon substrate) benzene of Isosorbide-5-Nitrae-of 19.44g (0.1mol), is warming up to
It 100 DEG C, is stirred to react for 24 hours.After reaction, solvent and the low boiling point volatile matter in removing system are evaporated under reduced pressure to get to ring
The main chain of alkylene sealing end contains the modified organic silicon of penylene and cyclic hydrocarbyl structure.Yield is 91.7%, refractive index 1.55.Become
It changes raw material and feeds intake and when change reaction condition, the length of molecule segment can be increased, increase the quantity of repeating segment.
The main chain of 8 styrene of embodiment sealing end contains the modified organic silicon of phenylene structure
26.04g (0.2mol) divinylbenzene, 80g toluene and 0.25g Pt-C are added into the three-necked flask of 250mL
(5%) catalyst stirs 30min at room temperature, and the Isosorbide-5-Nitrae-for being then slowly added into 35.00g (0.18mol) is bis- (dimethyl silicon substrate)
Benzene is warming up to 100 DEG C, is stirred to react 8h.After reaction, the solvent and low boiling point volatile matter being evaporated under reduced pressure in removing system,
Obtain the modified organic silicon that the main chain of styrene sealing end contains phenylene structure.By the present embodiment rate of charge, n=8, yield is
93.1%, refractive index 1.55.Transformation raw material, which feeds intake, when changes reaction condition, and the value of n in structure can be changed.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of main chain silicon modified organic polymer containing cyclic structure, which is characterized in that including：To 250mL's
The Karstedt catalyst that 26.44g dicyclopentadienes, 50g toluene and 20uL Pt contents are 25% is added in three-necked flask, rises
Then temperature is added bis- (dimethyl silicon substrate) benzene of Isosorbide-5-Nitrae-of 19.44g, is warming up to 110 DEG C, is stirred to react to 60min is stirred after 60 DEG C
36h, after reaction, be evaporated under reduced pressure solvent and the low boiling point volatile matter in removing system to get.
2. a kind of preparation method of main chain silicon modified organic polymer containing cyclic structure, which is characterized in that including：To 250mL's
19.52g divinylbenzenes, 5% catalyst of 100g cyclohexanone and 0.06g Pt-C, Pt content are added in three-necked flask, at room temperature
30min is stirred, the 1 of 13.43g is then slowly added into, 1,3,3- tetramethyl disiloxane is warming up to 100 DEG C, is stirred to react 12h,
After reaction, be evaporated under reduced pressure solvent and the low boiling point volatile matter in removing system to get.
3. a kind of preparation method of main chain silicon modified organic polymer containing cyclic structure, which is characterized in that including：To 250mL's
Be added in three-necked flask 31.05g1,3- divinyl -1,3- dimethyl -1,3- diphenyl disiloxane, 65g isopropanols and
10uL speier catalyst, Pt 25% stir 10min at room temperature, are then slowly added into the bis- (dimethyl-silicons of Isosorbide-5-Nitrae-of 24.30g
Base) benzene, 110 DEG C are warming up to, 18h is stirred to react, after reaction, the solvent being evaporated under reduced pressure in removing system volatilizees with low boiling point
Object to get.
4. a kind of preparation method of main chain silicon modified organic polymer containing cyclic structure, which is characterized in that including：To 250mL's
24.04g vinyl norbornenes and 5% catalyst of 0.106g Pt-C, Pt content are added in three-necked flask, is warming up to 85 DEG C, stirs
60min is mixed, bis- (dimethyl silicon substrate) benzene of Isosorbide-5-Nitrae-of 29.16g is then slowly added into, is warming up to 100 DEG C, is stirred to react 36h, is reacted
After, be evaporated under reduced pressure solvent and the low boiling point volatile matter in removing system to get.
5. a kind of preparation method of main chain silicon modified organic polymer containing cyclic structure, which is characterized in that including：To 250mL's
13.62g limonenes, 5% catalyst of 100g glycol dimethyl ethers and 0.12g Pd-C, Pd content, heating are added in three-necked flask
To 40 DEG C, 30min is stirred, is then slowly added into the 1 of 26.87g, 1,3,3- tetramethyl disiloxane is warming up to 110 DEG C, stirring
Reaction for 24 hours, after reaction, is evaporated under reduced pressure the solvent in removing system with after low boiling point volatile matter, filtering is produced to get to target
Object.
6. a kind of preparation method of main chain silicon modified organic polymer containing cyclic structure, which is characterized in that including：To 250mL's
12.02g vinyl norbornenes, 5% catalyst of 80g tetrahydrofurans and 0.15g Ru-C, Ru content are added in three-necked flask, rises
Temperature stirs 30min, is then slowly added into the 1 of 20.15g, 1,3,3- tetramethyl disiloxane is warming up to 100 DEG C, stirs to 40 DEG C
Mix reaction for 24 hours, after reaction, be evaporated under reduced pressure solvent and the low boiling point volatile matter in removing system to get.
7. a kind of preparation method of main chain silicon modified organic polymer containing cyclic structure, which is characterized in that including：To 250mL's
34.06g limonenes and 5% catalyst of 0.15g Rh-C, Rh content are added in three-necked flask, is warming up to 45 DEG C, stirs 30min,
Bis- (dimethyl silicon substrate) benzene of Isosorbide-5-Nitrae-of 19.44g are then slowly added into, 100 DEG C is warming up to, is stirred to react for 24 hours, after reaction,
Be evaporated under reduced pressure solvent and the low boiling point volatile matter in removing system to get.
8. a kind of preparation method of main chain silicon modified organic polymer containing cyclic structure, which is characterized in that including：To 250mL's
26.04g divinylbenzenes, 5% catalyst of 80g toluene and 0.25g Pt-C, Pt content are added in three-necked flask, stirs at room temperature
30min is then slowly added into bis- (dimethyl silicon substrate) benzene of Isosorbide-5-Nitrae-of 35.00g, is warming up to 100 DEG C, is stirred to react 8h, reaction knot
Shu Hou, be evaporated under reduced pressure solvent and the low boiling point volatile matter in removing system to get.
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| CN106118582A (en) * | 2016-07-07 | 2016-11-16 | 烟台德邦先进硅材料有限公司 | A kind of high index of refraction low permeability low water suction LED packaging silicon rubber |
| CN106047278A (en) * | 2016-07-22 | 2016-10-26 | 烟台德邦先进硅材料有限公司 | High-refractive-index yellowing-resistant LED packaging silica gel |
| CN107760258B (en) * | 2016-08-16 | 2020-12-04 | 北京康美特科技股份有限公司 | Sealing agent for battery module, battery module and sealing method thereof |
| CN106831847A (en) * | 2016-12-28 | 2017-06-13 | 广州星业科技股份有限公司 | A kind of dendritic amphipathic silicone oligomer and preparation method and application |
| CN107033356A (en) * | 2017-05-12 | 2017-08-11 | 惠州市佳的利实业有限公司 | A kind of silicon systems polymer of silicon phenolic group block and preparation method thereof and composition |
| CN112574391B (en) * | 2020-09-09 | 2022-10-18 | 艾森半导体材料(南通)有限公司 | Organic silicon modified alicyclic epoxy resin with good optical transparency and preparation method thereof |
| CN114133574B (en) * | 2021-12-13 | 2023-03-10 | 山东省科学院新材料研究所 | Bridged naphthene toughened silicone resin and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191018A (en) * | 2006-11-29 | 2008-06-04 | 瓦克化学有限公司 | Liquid silicone rubber |
| CN101506309A (en) * | 2006-08-25 | 2009-08-12 | 陶氏康宁东丽株式会社 | Curable orgnopolysiloxane composition and semiconductor device |
| CN102167908A (en) * | 2011-05-31 | 2011-08-31 | 中昊晨光化工研究院 | Organopolysiloxane composition, and curing method and application thereof |
| CN102197092A (en) * | 2008-10-31 | 2011-09-21 | 道康宁东丽株式会社 | Curable organopolysiloxane composition, optical semiconductor element sealant, and optical semiconductor device |
| CN103122149A (en) * | 2013-03-18 | 2013-05-29 | 株洲时代新材料科技股份有限公司 | Silicon rubber with high refractive index and high transparency for optical encapsulation and preparation method thereof |
| CN105367593A (en) * | 2015-11-17 | 2016-03-02 | 烟台德邦先进硅材料有限公司 | Silicon phenylene / carbosilane compound and preparation method thereof |
| CN105431499A (en) * | 2013-08-01 | 2016-03-23 | 瓦克化学股份公司 | Silicone resin composition for optical semiconductors |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5198511A (en) * | 1991-12-20 | 1993-03-30 | Minnesota Mining And Manufacturing Company | Polymerizable compositions containing olefin metathesis catalysts and cocatalysts, and methods of use therefor |
| EP2953955B1 (en) * | 2013-02-06 | 2018-08-15 | Momentive Performance Materials Inc. | (meth)acryloxy-containing trisiloxane, siloxane-containing polymers and biomedical devices therefrom |
| US9822326B2 (en) * | 2014-03-31 | 2017-11-21 | Exxonmobil Research And Engineering Company | Low viscosity, low volatility lubricating oil basestocks |
-
2016
- 2016-04-26 CN CN201610269653.9A patent/CN105694047B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101506309A (en) * | 2006-08-25 | 2009-08-12 | 陶氏康宁东丽株式会社 | Curable orgnopolysiloxane composition and semiconductor device |
| CN101191018A (en) * | 2006-11-29 | 2008-06-04 | 瓦克化学有限公司 | Liquid silicone rubber |
| CN102197092A (en) * | 2008-10-31 | 2011-09-21 | 道康宁东丽株式会社 | Curable organopolysiloxane composition, optical semiconductor element sealant, and optical semiconductor device |
| CN102167908A (en) * | 2011-05-31 | 2011-08-31 | 中昊晨光化工研究院 | Organopolysiloxane composition, and curing method and application thereof |
| CN103122149A (en) * | 2013-03-18 | 2013-05-29 | 株洲时代新材料科技股份有限公司 | Silicon rubber with high refractive index and high transparency for optical encapsulation and preparation method thereof |
| CN105431499A (en) * | 2013-08-01 | 2016-03-23 | 瓦克化学股份公司 | Silicone resin composition for optical semiconductors |
| CN105367593A (en) * | 2015-11-17 | 2016-03-02 | 烟台德邦先进硅材料有限公司 | Silicon phenylene / carbosilane compound and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| LED电子器件封装用有机硅材料的研究进展;张军营，等;《粘接》;20140710(第7期);第35-40页 * |
| Thermo and Dynamic Mechanical Properties of the High Refractive Index Silicone Resin for Light Emitting Diode Packaging;Dan Dan Li，等;《IEEE TRANSACTIONS ON COMPONENTS, PACKAGING AND MANUFACTURING TECHNOLOGY》;20131217;第4卷(第2期);第190-197页 * |
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