CN108165201B - A kind of tackifier and preparation method thereof - Google Patents
A kind of tackifier and preparation method thereof Download PDFInfo
- Publication number
- CN108165201B CN108165201B CN201711441966.9A CN201711441966A CN108165201B CN 108165201 B CN108165201 B CN 108165201B CN 201711441966 A CN201711441966 A CN 201711441966A CN 108165201 B CN108165201 B CN 108165201B
- Authority
- CN
- China
- Prior art keywords
- tackifier
- phenyl
- preparation
- present
- reaction mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The present invention provides a kind of tackifier and preparation method thereof, the tackifier have general formula shown in formula (I)；Wherein, a+b+c+d=1,0≤a < 1,0≤b < 1,0≤c <, 1,0 < d < 1；R1Selected from one or both of phenyl and 3- glycydoxy；R2Selected from one of phenyl, 3- glycydoxy and methyl or a variety of；R3For alkoxysilyl group；Me is methyl, and Vi is vinyl.Compared with prior art, tackifier provided by the invention are three-dimensional-structure, include the groups such as phenyl, vinyl, epoxy group and alkoxy in structure, by controlling above-mentioned not isoplastic ratio, especially phenyl and epoxy group, make tackifier refractive index with higher and preferable Efficient Adhesive Promotion, while there can be good compatibility with different substrate materials, to be suitable for the thickening of different substrate materials silica gel.The experimental results showed that the refractive index of tackifier provided by the invention reachable 1.53 or more, and there is excellent Efficient Adhesive Promotion.
Description
Technical field
The present invention relates to tackifier technical fields, are to be related to a kind of tackifier and preparation method thereof more specifically.
Background technique
Organosilicon material has many advantages, such as excellent heat-resisting and ultraviolet light and aging performance, and high transparency, low internal stress are recognized
To be ideal organic packaging materials, just gradually substituted epoxy resinae encapsulating material, wherein the high refractive index silica gel containing phenyl
(refractive index > 1.5) has higher smooth extraction efficiency, more preferably high-low temperature resistant, resistance to vulcanization, the resistance to performances such as ultraviolet.But have
The bond effect of machine silica gel also has greater room for improvement, and there is also certain limitations for applicable base material range.The prior art passes through
Addition improves the tackifier with substrate bonding performance in silica gel, improves the bond effect of organic silica gel, is applied to various bases
The bonding of material, encapsulation have superior technique effect.
In recent years, the related invention patent of tackifier gradually increases.Such as the Chinese patent of Publication No. CN104910829A
Disclose one kind by polyborosiloxane, siloxane prepolymer, silane coupling agent, end-capping reagent in water, organic solvent environment in acid
The tackifier being condensed to yield under the action of property catalyst；But the step of preparation process of the tackifier is various, it is excessively complicated, and
And a certain amount of HCl can be discharged when preparing polyborosiloxane.And disclosed in the Chinese patent of Publication No. CN105400446A
A kind of tackifier preparation method, this method are that phenyl siloxane hydrolyzes to obtain silicone resin oligomer first, pass through catalyst action
Lower to carry out ester exchange reaction, catalyst neutralisation with the siloxanes with epoxy group, filtering, vacuum distillation obtain tackifier；But it should
The N-process of preparation method is difficult to be precisely controlled so that the two just fully reacting, obtains having in tackifier meta-acid or meta-alkali
Possibility, soda acid therein generate certain influence to the performance of packaging plastic at branch, it is often more important that, second is free of in the tackifier
Alkenyl or hydrogen based group, after hardening to packaging plastic side connection there are the missings of chemical bond, have one to the raising of adhesive property
Fixed influence.In addition, the Chinese patent of Publication No. CN103755963A discloses a kind of polysiloxane adhesion promoters and its preparation
Method, prepared tackifier refractive index is between 1.41-1.45；Publication No. CN10647939A's and CN106397771A
The refractive index of tackifier disclosed in Chinese patent is also substantially below 1.50.But the low tackifier of refractive index are for high refraction silicon
In glue, it is easy to appear muddy the case where whitening, will affect the transparency of product.
In conclusion the tackifier in the prior art technical problem that there is also Efficient Adhesive Promotions is bad, refractive index is lower.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of tackifier and preparation method thereof, thickening provided by the invention
Agent while refractive index with higher and preferable Efficient Adhesive Promotion.
The present invention provides a kind of tackifier, have general formula shown in formula (I):
Wherein, a+b+c+d=1,0≤a < 1,0≤b < 1,0≤c <, 1,0 < d < 1；R1It shrinks selected from phenyl and 3- sweet
One or both of oily ether oxygen base propyl；R2Selected from one of phenyl, 3- glycydoxy and methyl or more
Kind；R3For alkoxysilyl group；Me is methyl, and Vi is vinyl.
Preferably, the R1In include phenyl, the content of the phenyl is more than or equal to 50mol%.
The present invention also provides a kind of preparation methods of tackifier described in above-mentioned technical proposal, comprising the following steps:
A) tetramethyl divinyl disiloxane, phenyl siloxane and acid catalyst are mixed, adds water progress for the first time
Reaction, obtains the first reaction mixture；
B) the first reaction mixture that step a) is obtained is mixed with siloxanes, base catalyst containing epoxy group, is added water
The second secondary response is carried out, the second reaction mixture is obtained；
C) the second reaction mixture for obtaining step b) handle except small molecule, adds aromatic hydrocarbon and carries out third time
Reaction, reaction product is successively neutralized, rinses and is evaporated under reduced pressure, and obtains tackifier precursor；The aromatic hydrocarbon is toluene or diformazan
Benzene；
D) tackifier precursor, solvent and the platinum catalyst mixing obtained step c), adds alkoxy hydrogen-based silane, into
The 4th secondary response of row, obtains tackifier after vacuum distillation.
Preferably, phenyl siloxane described in step a) be selected from phenyltrimethoxysila,e, dimethoxydiphenylsilane,
Aminomethyl phenyl dimethoxysilane, phenyl triethoxysilane, diphenyl diethoxy silane and aminomethyl phenyl diethoxy silicon
One of alkane is a variety of.
Preferably, the temperature of first set reaction described in step a) is 30 DEG C~80 DEG C, and the time is 2h~6h.
Preferably, the siloxanes described in step b) containing epoxy group is selected from 3- glycydoxy trimethoxy silicon
Alkane, 3- glycidyl ether oxypropyltriethoxysilane, 3- glycidyl ether oxypropyl methyl dimethoxy silane and 3-
One of glycydoxy methyldiethoxysilane is a variety of.
Preferably, the temperature of the second secondary response described in step b) is 30 DEG C~80 DEG C, and the time is 2h~6h.
Preferably, the temperature of third secondary response described in step c) is 90 DEG C~120 DEG C, and the time is 2h~6h.
Preferably, alkoxy hydrogen-based silane described in step d) is selected from trimethoxy silane, triethoxysilane, methyl two
One of methoxy silane and methyldiethoxysilane are a variety of.
Preferably, the temperature of the 4th secondary response described in step d) is 60 DEG C~100 DEG C, and the time is 1h~4h.
The present invention provides a kind of tackifier and preparation method thereof, the tackifier have general formula shown in formula (I)；Wherein, a
+ b+c+d=1,0≤a < 1,0≤b < 1,0≤c <, 1,0 < d < 1；R1In phenyl and 3- glycydoxy
One or two；R2Selected from one of phenyl, 3- glycydoxy and methyl or a variety of；R3For alkoxyl silicone
Base；Me is methyl, and Vi is vinyl.Compared with prior art, tackifier provided by the invention are three-dimensional-structure, include in structure
The groups such as phenyl, vinyl, epoxy group and alkoxy, by controlling above-mentioned not isoplastic ratio, especially phenyl and epoxy
Base makes tackifier refractive index with higher and preferable Efficient Adhesive Promotion, while can have good phase with different substrate materials
Capacitive, to be suitable for the thickening of different substrate materials silica gel.The experimental results showed that the refractive index of tackifier provided by the invention can arrive
Up to 1.53 or more, and there is excellent Efficient Adhesive Promotion.
In addition, preparation method provided by the invention does not generate the not easy to handle by-product such as HCl；And simple process, raw material
It is easy to get, is easy to amplify, it is suitable for mass production.
Detailed description of the invention
Fig. 1 is the characterization map for the tackifier that the embodiment of the present invention 1 provides.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair
The range of bright protection.
The present invention provides a kind of tackifier, have general formula shown in formula (I):
Wherein, a+b+c+d=1,0≤a < 1,0≤b < 1,0≤c <, 1,0 < d < 1；R1It shrinks selected from phenyl and 3- sweet
One or both of oily ether oxygen base propyl；R2Selected from one of phenyl, 3- glycydoxy and methyl or more
Kind；R3For alkoxysilyl group；Me is methyl, and Vi is vinyl.
In the present invention, the R1In preferably include phenyl, the content of the phenyl is preferably greater than or equal to 50mol%.
Tackifier provided by the invention are three-dimensional-structure, include the bases such as phenyl, vinyl, epoxy group and alkoxy in structure
Group, by controlling above-mentioned not isoplastic ratio, especially phenyl and epoxy group, make tackifier refractive index with higher and
Preferable Efficient Adhesive Promotion, while can have good compatibility with different substrate materials, to be suitable for the increasing of different substrate materials silica gel
It is viscous.
The present invention also provides a kind of preparation methods of tackifier described in above-mentioned technical proposal, comprising the following steps:
A) tetramethyl divinyl disiloxane, phenyl siloxane and acid catalyst are mixed, adds water progress for the first time
Reaction, obtains the first reaction mixture；
B) the first reaction mixture that step a) is obtained is mixed with siloxanes, base catalyst containing epoxy group, is added water
The second secondary response is carried out, the second reaction mixture is obtained；
C) the second reaction mixture for obtaining step b) handle except small molecule, adds aromatic hydrocarbon and carries out third time
Reaction, reaction product is successively neutralized, rinses and is evaporated under reduced pressure, and obtains tackifier precursor；The aromatic hydrocarbon is toluene or diformazan
Benzene；
D) tackifier precursor, solvent and the platinum catalyst mixing obtained step c), adds alkoxy hydrogen-based silane, into
The 4th secondary response of row, obtains tackifier after vacuum distillation.
The present invention first by tetramethyl divinyl disiloxane, phenyl siloxane and acid catalyst mix, add water into
Row first set reaction obtains the first reaction mixture.In the present invention, the phenyl siloxane is preferably selected from phenyl trimethoxy
Silane, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxysilane, phenyl triethoxysilane, diphenyl diethoxy
One of silane and aminomethyl phenyl diethoxy silane are a variety of, more preferably phenyl front three oxosilane and/diphenyl diformazan
Oxysilane.The present invention is not particularly limited the source of the phenyl siloxane, on well known to those skilled in the art
State phenyltrimethoxysila,e, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxysilane, phenyl triethoxysilane,
The commercial goods of diphenyl diethoxy silane and aminomethyl phenyl diethoxy silane.In the present invention, the phenyl silicon
The ratio between amount of substance of oxygen alkane and tetramethyl divinyl disiloxane is preferably (1~10): 1.
In the present invention, the acid catalyst is preferably selected from one of hydrochloric acid, sulfuric acid, acetic acid and trifluoromethanesulfonic acid or more
Kind, more preferably trifluoromethanesulfonic acid.The present invention is not particularly limited the source of the acid catalyst, using those skilled in the art
The commercial goods of above-mentioned hydrochloric acid known to member, sulfuric acid, acetic acid and trifluoromethanesulfonic acid.In the present invention, the acid catalyst
Preferably (0.06~1) with the ratio between the amount of substance of phenyl siloxane: 100.
The present invention is not particularly limited the mixed mode, using mechanical stirring well known to those skilled in the art or
The technical solution manually stirred, it is therefore an objective to be uniformly mixed each reaction raw materials.
In the present invention, the amount of water before the first set reaction is preferably 1 times~the 1.3 of the amount of the substance of alkoxy
Times, it is added dropwise using constant temperature dropping funel well known to those skilled in the art, it is not specifically limited to this by the present invention.
In the present invention, the temperature of the first set reaction is preferably 30 DEG C~80 DEG C, more preferably 65 DEG C~75 DEG C；Institute
The time for stating first set reaction is preferably 2h~6h, more preferably 2h.
After obtaining first reaction mixture, the present invention is by the first obtained reaction mixture and the silicon oxygen containing epoxy group
Alkane, base catalyst mixing, add water and carry out the second secondary response, obtain the second reaction mixture.In the present invention, described to contain epoxy
The siloxanes of base is preferably selected from 3- glycidyl ether oxypropyltrimethoxysilane, three ethoxy of 3- glycydoxy
Base silane, 3- glycidyl ether oxypropyl methyl dimethoxy silane and 3- glycydoxy methyl diethoxy
One of silane is a variety of, more preferably 3- glycidyl ether oxypropyl methyl dimethoxy silane or 3- glycidol ether
Oxygroup propyl trimethoxy silicane.The present invention is not particularly limited the source of the siloxanes containing epoxy group, using ability
Above-mentioned 3- glycidyl ether oxypropyltrimethoxysilane, three second of 3- glycydoxy known to field technique personnel
Oxysilane, 3- glycidyl ether oxypropyl methyl dimethoxy silane and 3- glycydoxy methyl diethoxy
The commercial goods of base silane.In the present invention, the amount of the substance of the siloxanes and phenyl siloxane containing epoxy group it
Than preferably (0.1~2): 1.
In the present invention, the base catalyst is preferably selected from KOH, NaOH, LiOH and Ba (OH)2One of or it is a variety of,
More preferably KOH.The present invention is not particularly limited the source of the base catalyst, on well known to those skilled in the art
State KOH, NaOH, LiOH and Ba (OH)2Commercial goods.In the present invention, the base catalyst and above-mentioned phenyl silicon oxygen
The ratio between amount of substance of the sum of alkane and siloxanes containing epoxy group is preferably (0.3~5): 100.
The present invention is not particularly limited the mixed mode, using mechanical stirring well known to those skilled in the art or
The technical solution manually stirred, it is therefore an objective to be uniformly mixed each reaction raw materials.
In the present invention, the amount of water before second secondary response is preferably 1 times~3 times of the amount of the substance of alkoxy,
It is added dropwise using constant temperature dropping funel well known to those skilled in the art, it is not specifically limited to this by the present invention.
In the present invention, the temperature of second secondary response is preferably 30 DEG C~80 DEG C, more preferably 65 DEG C~75 DEG C；Institute
The time for stating the second secondary response is preferably 2h~6h, more preferably 2h.
After obtaining second reaction mixture, the present invention carries out the second obtained reaction mixture except at small molecule
Reason adds aromatic hydrocarbon and carries out third secondary response, and reaction product is successively neutralized, rinses and is evaporated under reduced pressure, before obtaining tackifier
Body.It is in the present invention, described except the process of small molecule processing is preferred specifically:
The second obtained reaction mixture is subjected to heating distillation, until the temperature for completing distillation.In the present invention, institute
Stating and completing the temperature of distillation is preferably 80 DEG C~90 DEG C, more preferably 85 DEG C.
In the present invention, the aromatic hydrocarbon is toluene or dimethylbenzene, preferably toluene.The present invention carrys out the aromatic hydrocarbon
Source is not particularly limited, using the commercial goods of above-mentioned toluene and dimethylbenzene well known to those skilled in the art.In this hair
In bright, the addition quality of the aromatic hydrocarbon is preferably 0.5 times~2 times of other material mass sums.
In the present invention, the temperature of the third secondary response is preferably 90 DEG C~120 DEG C, more preferably 110 DEG C；Described
The time of third-order reaction is preferably 2h~6h, more preferably 3h
In the present invention, acid used in the neutralization is preferably hydrochloric acid, sulfuric acid, formic acid, acetic acid, benzoic acid, ethanedioic acid, third
One of diacid and terephthalic acid (TPA) are a variety of, more preferably hydrochloric acid.
Reaction product is washed to neutrality through the rinse cycle by the present invention, and using vacuum distillation removing low molecule, originally
It is not specifically limited to this for invention.
After obtaining the tackifier precursor, the present invention mixes obtained tackifier precursor, solvent and platinum catalyst, then plus
Enter alkoxy hydrogen-based silane, carries out the 4th secondary response, obtain tackifier after vacuum distillation.In the present invention, the solvent is preferred
Selected from toluene or dimethylbenzene；It is not specifically limited to this by the present invention.In the present invention, the quality of the solvent and tackifier precursor
Than preferably (0.5~1.2): 1, more preferably 1:1.
In the present invention, the platinum catalyst is preferably selected from chloroplatinic acid, chloroplatinic acid in alcohol, complex compound four (triphenylphosphine)
One of platinum and platinum-vinyl siloxane complex compound are a variety of, more preferably platinum-vinyl siloxane complex compound.In this hair
In bright preferred embodiment, the platinum catalyst is the platinum-vinyl siloxane complex compound that concentration is 0.3%.The present invention is to institute
The source for stating platinum catalyst is not particularly limited, using above-mentioned chloroplatinic acid well known to those skilled in the art, chloroplatinic acid in alcohol,
The commercial goods of complex compound four (triphenylphosphine) platinum and platinum-vinyl siloxane complex compound.In the present invention, the platinum is urged
The additional amount of agent is preferably 5ppm~15ppm.
The present invention is not particularly limited the mixed mode, using mechanical stirring well known to those skilled in the art or
The technical solution manually stirred, it is therefore an objective to be uniformly mixed each reaction raw materials.
In the present invention, the mode that alkoxy hydrogen-based silane is added preferably is added dropwise with syringe, and the present invention does not have this
Have specifically limited.In the present invention, the alkoxy hydrogen-based silane is preferably selected from trimethoxy silane, triethoxysilane, first
One of base dimethoxysilane and methyldiethoxysilane are a variety of, more preferably triethoxysilane or trimethoxy
Silane.The present invention is not particularly limited the source of the alkoxy hydrogen-based silane, on well known to those skilled in the art
State the commercial goods of trimethoxy silane, triethoxysilane, methyl dimethoxysilane and methyldiethoxysilane.
In the present invention, the ratio between amount of substance of vinyl in the alkoxy hydrogen-based silane and above-mentioned tackifier precursor is preferably
(0.4~0.8): 1.
In the present invention, the temperature of the 4th secondary response is preferably 60 DEG C~100 DEG C, and more preferably 80 DEG C；Described
The time of third-order reaction is preferably 1h~4h, more preferably 3h.
In the present invention, the purpose of the vacuum distillation is to remove small molecule, and it is not specifically limited to this by the present invention.
The present invention provides a kind of tackifier and preparation method thereof, the tackifier have general formula shown in formula (I)；Wherein, a
+ b+c+d=1,0≤a < 1,0≤b < 1,0≤c <, 1,0 < d < 1；R1In phenyl and 3- glycydoxy
One or two；R2Selected from one of phenyl, 3- glycydoxy and methyl or a variety of；R3For alkoxyl silicone
Base；Me is methyl, and Vi is vinyl.Compared with prior art, tackifier provided by the invention are three-dimensional-structure, include in structure
The groups such as phenyl, vinyl, epoxy group and alkoxy, by controlling above-mentioned not isoplastic ratio, especially phenyl and epoxy
Base makes tackifier refractive index with higher and preferable Efficient Adhesive Promotion, while can have good phase with different substrate materials
Capacitive, to be suitable for the thickening of different substrate materials silica gel.The experimental results showed that the refractive index of tackifier provided by the invention can arrive
Up to 1.53 or more, and there is excellent Efficient Adhesive Promotion.
In addition, preparation method provided by the invention does not generate the not easy to handle by-product such as HCl；And simple process, raw material
It is easy to get, is easy to amplify, it is suitable for mass production.
In order to further illustrate the present invention, it is described in detail below by following embodiment.Following embodiment of the present invention
Raw material used is commercial goods.
Embodiment 1
(1) 158.6g phenyl front three oxosilane, two silicon of 83.9g tetramethyl divinyl are added into 1000mL three-necked flask
Oxygen alkane and 0.30g trifluoromethanesulfonic acid, stir evenly, and 51.8g deionized water then are added dropwise with constant temperature dropping funel, after being added dropwise to complete
65 DEG C are warming up to, 2h is reacted, obtains the first reaction mixture.
(2) be cooled to 50 DEG C hereinafter, in the reaction mixture obtained under stiring to step (1) be added 1.5g KOH,
141.8g 3- glycidyl ether oxypropyltrimethoxysilane, stirs evenly, and 64.8g then is added dropwise with constant temperature dropping funel
Deionized water is warming up to 65 DEG C after being added dropwise to complete, react 2h, obtain the second reaction mixture.
(3) the second reaction mixture that step (2) obtains is subjected to heating distillation to temperature to 85 DEG C, completes distillation, then
280g toluene is added, is warming up to 110 DEG C of reaction 3h, 3.04g concentrated hydrochloric acid is added after cooling, is washed to neutrality, oily mutually decompression is taken to steam
Removing low molecule is evaporated, colorless and transparent tackifier precursor 238.4g is obtained.
(4) under the protection of drying nitrogen, it is by tackifier precursor, 30g toluene, 0.2g concentration that 30g step (3) obtains
0.3% platinum-vinyl siloxane complex compound is added in 500mL three-necked flask, stirs evenly, while being warming up to 80 DEG C, uses needle
6.50g triethoxysilane is added dropwise in cylinder, and in 80 DEG C of heat preservation 3h after being added dropwise to complete, vacuum distillation removes small molecule, obtains tackifier.
The expression formula for the tackifier that the embodiment of the present invention 1 provides are as follows:
Wherein, R1For 3- glycydoxy, R3For triethoxy silicon substrate, Ph is phenyl,
Me is methyl, and Vi is vinyl.The characterization spectrogram of the tackifier is shown in Figure 1.Wherein, wave number 1259cm-1、
1408cm-1、2877cm-1、2958cm-1It is the symmetrical deformation vibration of methyl respectively in Me-Si structure, asymmetrical deformation vibration, right
Claim the characteristic peak of stretching vibration and asymmetric stretching vibration,
1595cm-1It is the characteristic peak of Vi-Si structure medium vinyl, 1431cm-1It is inhaled for the vibration of phenyl ring in Ph-Si structure
Receive peak, 831cm-1And 910cm-1For the stretching vibration absworption peak of epoxy group, 1146cm-1The big and wide absorption peak in one section of place is Si-
The characteristic peak of the stretching vibration of O-Si is overlapped with the absorption peak of Si-O-C, C-O-C.
Through detecting, the refractive index for the tackifier that the embodiment of the present invention 1 provides is 1.4863, and contents of ethylene is
3.85wt%.
Embodiment 2
(1) 158.6g phenyl front three oxosilane, two silicon of 83.9g tetramethyl divinyl are added into 1000mL three-necked flask
Oxygen alkane and 0.30g trifluoromethanesulfonic acid, stir evenly, and 51.8g deionized water then are added dropwise with constant temperature dropping funel, after being added dropwise to complete
65 DEG C are warming up to, 2h is reacted, obtains the first reaction mixture.
(2) be cooled to 50 DEG C hereinafter, in the reaction mixture obtained under stiring to step (1) be added 1.5g KOH,
141.8g 3- glycidyl ether oxypropyltrimethoxysilane, stirs evenly, and 64.8g then is added dropwise with constant temperature dropping funel
Deionized water is warming up to 65 DEG C after being added dropwise to complete, react 2h, obtain the second reaction mixture.
(3) the second reaction mixture that step (2) obtains is subjected to heating distillation to temperature to 85 DEG C, completes distillation, then
280g toluene is added, is warming up to 110 DEG C of reaction 3h, 3.04g concentrated hydrochloric acid is added after cooling, is washed to neutrality, oily mutually decompression is taken to steam
Removing low molecule is evaporated, colorless and transparent tackifier precursor 238.4g is obtained.
(4) under the protection of drying nitrogen, tackifier precursor, 30g dimethylbenzene, 0.3g concentration that 30g step (3) is obtained
It is added in 500mL three-necked flask, stirs evenly, while being warming up to 80 DEG C for 0.3% platinum-vinyl siloxane complex compound, use
4.86g trimethoxy silane is added dropwise in syringe, and in 80 DEG C of heat preservation 3h after being added dropwise to complete, vacuum distillation removes small molecule, viscosified
Agent.
The expression formula for the tackifier that the embodiment of the present invention 2 provides are as follows:
Wherein, R1For 3- glycydoxy, R3For trimethoxy silicon substrate, Ph is phenyl, and Me is methyl, and Vi is
Vinyl.
Through detecting, the refractive index for the tackifier that the embodiment of the present invention 2 provides is 1.4865, and contents of ethylene is
3.76wt%.
Embodiment 3
(1) 158.6g phenyl front three oxosilane, two silicon of 93.2g tetramethyl divinyl are added into 1000mL three-necked flask
Oxygen alkane and 0.35g trifluoromethanesulfonic acid, stir evenly, and 51.8g deionized water then are added dropwise with constant temperature dropping funel, after being added dropwise to complete
70 DEG C are warming up to, 2h is reacted, obtains the first reaction mixture.
(2) be cooled to 50 DEG C hereinafter, in the reaction mixture obtained under stiring to step (1) be added 1.34g KOH,
88.1g 3- glycidyl ether oxypropyl methyl dimethoxy silane, stirs evenly, and is then added dropwise with constant temperature dropping funel
28.8g deionized water is warming up to 75 DEG C after being added dropwise to complete, react 2h, obtain the second reaction mixture.
(3) the second reaction mixture that step (2) obtains is subjected to heating distillation to temperature to 85 DEG C, completes distillation, then
240g toluene is added, is warming up to 110 DEG C of reaction 3h, 1.73g acetic acid is added after cooling, is washed to neutrality, takes oily mutually vacuum distillation
Low molecule is removed, the tackifier precursor 218.6g of pale yellow transparent is obtained.
(4) under the protection of drying nitrogen, tackifier precursor, 30g dimethylbenzene, 0.3g concentration that 30g step (3) is obtained
It is added in 500mL three-necked flask, stirs evenly, while being warming up to 80 DEG C for 0.3% platinum-vinyl siloxane complex compound, use
7.02g triethoxysilane is added dropwise in syringe, and in 80 DEG C of heat preservation 3h after being added dropwise to complete, vacuum distillation removes small molecule, viscosified
Agent.
The expression formula for the tackifier that the embodiment of the present invention 3 provides are as follows:
Wherein, R2For 3- glycydoxy, R3For triethoxy silicon substrate, Ph is phenyl, and Me is methyl, and Vi is
Vinyl.
Through detecting, the refractive index for the tackifier that the embodiment of the present invention 3 provides is 1.4945, and contents of ethylene is
3.58wt%.
Embodiment 4
(1) 158.6g phenyl front three oxosilane, two silicon of 93.2g tetramethyl divinyl are added into 1000mL three-necked flask
Oxygen alkane and 0.35g trifluoromethanesulfonic acid, stir evenly, and 51.8g deionized water then are added dropwise with constant temperature dropping funel, after being added dropwise to complete
70 DEG C are warming up to, 2h is reacted, obtains the first reaction mixture.
(2) be cooled to 50 DEG C hereinafter, in the reaction mixture obtained under stiring to step (1) be added 1.34g KOH,
88.1g 3- glycidyl ether oxypropyl methyl dimethoxy silane, stirs evenly, and is then added dropwise with constant temperature dropping funel
28.8g deionized water is warming up to 75 DEG C after being added dropwise to complete, react 2h, obtain the second reaction mixture.
(3) the second reaction mixture that step (2) obtains is subjected to heating distillation to temperature to 85 DEG C, completes distillation, then
240g toluene is added, is warming up to 110 DEG C of reaction 3h, 1.73g acetic acid is added after cooling, is washed to neutrality, takes oily mutually vacuum distillation
Low molecule is removed, the tackifier precursor 218.6g of pale yellow transparent is obtained.
(4) under the protection of drying nitrogen, tackifier precursor, 30g dimethylbenzene, 0.3g concentration that 30g step (3) is obtained
It is added in 500mL three-necked flask, stirs evenly, while being warming up to 80 DEG C for 0.3% platinum-vinyl siloxane complex compound, use
5.24g trimethoxy silane is added dropwise in syringe, and in 80 DEG C of heat preservation 3h after being added dropwise to complete, vacuum distillation removes small molecule, viscosified
Agent.
The expression formula for the tackifier that the embodiment of the present invention 4 provides are as follows:
Wherein, R2For 3- glycydoxy, R3For trimethoxy silicon substrate, Ph is phenyl, and Me is methyl, and Vi is
Vinyl.
Through detecting, the refractive index for the tackifier that the embodiment of the present invention 4 provides is 1.4948, and contents of ethylene is
3.72wt%.
Embodiment 5
(1) 158.6g phenyl front three oxosilane, two silicon of 93.2g tetramethyl divinyl are added into 1000mL three-necked flask
Oxygen alkane and 0.35g trifluoromethanesulfonic acid, stir evenly, and 51.8g deionized water then are added dropwise with constant temperature dropping funel, after being added dropwise to complete
70 DEG C are warming up to, 2h is reacted, obtains the first reaction mixture.
(2) be cooled to 50 DEG C hereinafter, in the reaction mixture obtained under stiring to step (1) be added 1.34g KOH,
88.1g 3- glycidyl ether oxypropyl methyl dimethoxy silane, stirs evenly, and is then added dropwise with constant temperature dropping funel
28.8g deionized water is warming up to 75 DEG C after being added dropwise to complete, react 2h, obtain the second reaction mixture.
(3) the second reaction mixture that step (2) obtains is subjected to heating distillation to temperature to 85 DEG C, completes distillation, then
240g toluene is added, is warming up to 110 DEG C of reaction 3h, 1.73g acetic acid is added after cooling, is washed to neutrality, takes oily mutually vacuum distillation
Low molecule is removed, the tackifier precursor 218.6g of pale yellow transparent is obtained.
(4) under the protection of drying nitrogen, tackifier precursor, 30g dimethylbenzene, 0.3g concentration that 30g step (3) is obtained
It is added in 500mL three-necked flask, stirs evenly, while being warming up to 80 DEG C for 0.3% platinum-vinyl siloxane complex compound, use
7.0g trimethoxy silane is added dropwise in syringe, and in 80 DEG C of heat preservation 3h after being added dropwise to complete, vacuum distillation removes small molecule, viscosified
Agent.
The expression formula for the tackifier that the embodiment of the present invention 5 provides are as follows:
Wherein, R2For 3- glycydoxy, R3For trimethoxy silicon substrate, Ph is phenyl, and Me is methyl, and Vi is
Vinyl.
Through detecting, the refractive index for the tackifier that the embodiment of the present invention 5 provides is 1.4934, and contents of ethylene is
2.68wt%.
Embodiment 6
(1) 158.6g phenyl front three oxosilane, two silicon of 55.9g tetramethyl divinyl are added into 1000mL three-necked flask
Oxygen alkane and 0.35g trifluoromethanesulfonic acid, stir evenly, and 51.8g deionized water then are added dropwise with constant temperature dropping funel, after being added dropwise to complete
75 DEG C are warming up to, 2h is reacted, obtains the first reaction mixture.
(2) be cooled to 50 DEG C hereinafter, in the reaction mixture obtained under stiring to step (1) be added 1.5g KOH,
110.2g 3- glycidyl ether oxypropyl methyl dimethoxy silane, stirs evenly, and is then added dropwise with constant temperature dropping funel
36.0g deionized water is warming up to 75 DEG C after being added dropwise to complete, react 2h, obtain the second reaction mixture.
(3) the second reaction mixture that step (2) obtains is subjected to heating distillation to temperature to 85 DEG C, completes distillation, then
230g toluene is added, is warming up to 110 DEG C of reaction 3h, 1.87g acetic acid is added after cooling, is washed to neutrality, takes oily mutually vacuum distillation
Low molecule is removed, the tackifier precursor 204.9g of pale yellow transparent is obtained.
(4) under the protection of drying nitrogen, tackifier precursor, 30g dimethylbenzene, 0.3g concentration that 30g step (3) is obtained
It is added in 500mL three-necked flask, stirs evenly, while being warming up to 80 DEG C for 0.3% platinum-vinyl siloxane complex compound, use
5.14g trimethoxy silane is added dropwise in syringe, and in 80 DEG C of heat preservation 3h after being added dropwise to complete, vacuum distillation removes small molecule, viscosified
Agent.
The expression formula for the tackifier that the embodiment of the present invention 5 provides are as follows:
Wherein, R2For 3- glycydoxy, R3For trimethoxy silicon substrate, Ph is phenyl, and Me is methyl, and Vi is
Vinyl.
Through detecting, the refractive index for the tackifier that the embodiment of the present invention 6 provides is 1.4992, and contents of ethylene is
2.04wt%.
It is separately added into organic silica gel by the tackifier for providing Examples 1 to 6, the embodiment of the present invention 1~6 is provided
The Efficient Adhesive Promotion of tackifier is tested, method particularly includes:
(1) by base-material that 40.2g viscosity is 14000cp, (phenyl vinyl polysiloxane and phenyl that mass ratio is 3:1 are hydrogeneous
Silicone oil) base-material, 7.03g phenyl-vinyl silicon oil, 2.77g phenyl hydrogen-containing silicon oil, 0.65g tackifier (respectively embodiment 1~
6 provide tackifier), 0.12g inhibitor mixed it is uniform, add 0.25g high refractive index platinum catalyst be uniformly mixed, in vacuum
Degree is deaeration 30min under 0.1MPa, obtains organic packages silica gel.
(2) the LED high folding encapsulation respectively using PPA, aluminium flake and steel disc as substrate, by 100 DEG C/1h+150 DEG C/3h to obtaining
Silica gel is solidified, and sample to be tested is prepared.
Comparative example 1
(1) by base-material that 40.2g viscosity is 14000cp, (phenyl vinyl polysiloxane and phenyl that mass ratio is 3:1 are hydrogeneous
Silicone oil) base-material, 7.03g phenyl-vinyl silicon oil, 2.77g phenyl hydrogen-containing silicon oil, 0.12g inhibitor mixed it is uniform, add
0.25g high refractive index platinum catalyst is uniformly mixed, the deaeration 30min in the case where vacuum degree is 0.1MPa, obtains LED high folding encapsulation silicon
Glue.
(2) the LED high folding encapsulation respectively using PPA, aluminium flake and steel disc as substrate, by 100 DEG C/1h+150 DEG C/3h to obtaining
Silica gel is solidified, and sample to be tested is prepared.
Comparative example 2
(1) by base-material that 40.2g viscosity is 14000cp, (phenyl vinyl polysiloxane and phenyl that mass ratio is 3:1 are hydrogeneous
Silicone oil) base-material, 7.03g phenyl-vinyl silicon oil, 2.77g phenyl hydrogen-containing silicon oil, 0.65gKH560,0.12g inhibitor mixed
Uniformly, it adds 0.25g high refractive index platinum catalyst to be uniformly mixed, the deaeration 30min in the case where vacuum degree is 0.1MPa obtains LED
Height folding packaging silicon rubber.
(2) the LED high folding encapsulation respectively using PPA, aluminium flake and steel disc as substrate, by 100 DEG C/1h+150 DEG C/3h to obtaining
Silica gel is solidified, and sample to be tested is prepared.
Using tensilon according to GB/T 7124-2008 respectively to Examples 1 to 6 and comparative example 1~2 provide to
Test specimens are tested for the property, and as a result ginseng is shown in Table 1.
The performance data for the sample to be tested that 1 embodiment 8~14 of table and comparative example 1~2 provide
As shown in Table 1, the tackifier that the embodiment of the present invention 1~6 provides have preferable Efficient Adhesive Promotion, have wide answer
Use prospect.
The above description of the disclosed embodiments, enables those skilled in the art to implement or use the present invention.It is right
A variety of modifications of these embodiments will be readily apparent to those skilled in the art, and as defined herein one
As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will
It will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with the principles and novel features disclosed herein
Widest scope.
Claims (10)
1. a kind of tackifier have general formula shown in formula (I):
Wherein, a+b+c+d=1,0≤a < 1,0≤b < 1,0≤c <, 1,0 < d < 1；R1Selected from phenyl and 3- glycidyl ether oxygen
One or both of base propyl；R2Selected from one of phenyl, 3- glycydoxy and methyl or a variety of；R3For
Alkoxysilyl group；Me is methyl, and Vi is vinyl.
2. tackifier according to claim 1, which is characterized in that the R1In include phenyl, the content of the phenyl is greater than
Equal to 50mol%.
3. a kind of preparation method of the described in any item tackifier of claim 1~2, comprising the following steps:
A) tetramethyl divinyl disiloxane, phenyl siloxane and acid catalyst are mixed, add water carry out first set reaction,
Obtain the first reaction mixture；
B) the first reaction mixture that step a) is obtained is mixed with siloxanes, base catalyst containing epoxy group, adds water progress
Second secondary response obtains the second reaction mixture；
C) the second reaction mixture for obtaining step b) handle except small molecule, and it is anti-to add aromatic hydrocarbon progress third time
It answers, reaction product is successively neutralized, rinses and is evaporated under reduced pressure, and obtains tackifier precursor；The aromatic hydrocarbon is toluene or dimethylbenzene；
D) the tackifier precursor that obtains step c), solvent and platinum catalyst mixing, add alkoxy hydrogen-based silane, carry out the
Four secondary responses obtain tackifier after vacuum distillation.
4. preparation method according to claim 3, which is characterized in that phenyl siloxane described in step a) is selected from phenyl three
Methoxy silane, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxysilane, phenyl triethoxysilane, diphenyl two
One of Ethoxysilane and aminomethyl phenyl diethoxy silane are a variety of.
5. preparation method according to claim 3, which is characterized in that the temperature of first set reaction described in step a) is 30
DEG C~80 DEG C, the time is 2h~6h.
6. preparation method according to claim 3, which is characterized in that the siloxanes described in step b) containing epoxy group is selected from
3- glycidyl ether oxypropyltrimethoxysilane, 3- glycidyl ether oxypropyltriethoxysilane, 3- glycidol
One of ether oxygen base hydroxypropyl methyl dimethoxysilane and 3- glycydoxy methyldiethoxysilane are more
Kind.
7. preparation method according to claim 3, which is characterized in that the temperature of the second secondary response described in step b) is 30
DEG C~80 DEG C, the time is 2h~6h.
8. preparation method according to claim 3, which is characterized in that the temperature of third secondary response described in step c) is 90
DEG C~120 DEG C, the time is 2h~6h.
9. preparation method according to claim 3, which is characterized in that alkoxy hydrogen-based silane described in step d) is selected from three
One of methoxy silane, triethoxysilane, methyl dimethoxysilane and methyldiethoxysilane are a variety of.
10. preparation method according to claim 3, which is characterized in that the temperature of the 4th secondary response described in step d) is
60 DEG C~100 DEG C, the time is 1h~4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711441966.9A CN108165201B (en) | 2017-12-27 | 2017-12-27 | A kind of tackifier and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711441966.9A CN108165201B (en) | 2017-12-27 | 2017-12-27 | A kind of tackifier and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108165201A CN108165201A (en) | 2018-06-15 |
| CN108165201B true CN108165201B (en) | 2019-03-01 |
Family
ID=62521886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711441966.9A Active CN108165201B (en) | 2017-12-27 | 2017-12-27 | A kind of tackifier and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108165201B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110982077B (en) * | 2019-12-03 | 2022-02-18 | 万华化学集团股份有限公司 | Modified tackifier, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755963A (en) * | 2013-12-27 | 2014-04-30 | 深圳市安品有机硅材料有限公司 | Polysiloxane thickening agent and preparation method thereof |
| CN103755964A (en) * | 2013-12-27 | 2014-04-30 | 深圳市安品有机硅材料有限公司 | Polysiloxane tackifying resin and preparation method thereof |
| CN106397771A (en) * | 2016-09-08 | 2017-02-15 | 烟台德邦先进硅材料有限公司 | Preparation method of tackifier used for organosilicone LED packaging colloidal system |
-
2017
- 2017-12-27 CN CN201711441966.9A patent/CN108165201B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755963A (en) * | 2013-12-27 | 2014-04-30 | 深圳市安品有机硅材料有限公司 | Polysiloxane thickening agent and preparation method thereof |
| CN103755964A (en) * | 2013-12-27 | 2014-04-30 | 深圳市安品有机硅材料有限公司 | Polysiloxane tackifying resin and preparation method thereof |
| CN106397771A (en) * | 2016-09-08 | 2017-02-15 | 烟台德邦先进硅材料有限公司 | Preparation method of tackifier used for organosilicone LED packaging colloidal system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108165201A (en) | 2018-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108148525B (en) | A kind of organic silicon rigidity-increasing stick and its preparation method and application | |
| CN104877138B (en) | A kind of silicones with adhesive property and preparation method thereof | |
| JP6073213B2 (en) | Process for producing polyorganosiloxane and novel organopolysiloxane | |
| CN102146091B (en) | Bis-silane coupling agent and preparation method thereof | |
| CN106496565B (en) | A kind of tackifier, preparation method and silicone rubber compound | |
| CN102597065A (en) | Process for preparing clustered functional polyorganosiloxanes, and methods for their use | |
| CN106478953A (en) | A kind of metal hybrid POSS complex and its preparation method and application | |
| CN104558612B (en) | A kind of alkoxy end-capped polysiloxane polymer and preparation method thereof | |
| JPH034594B2 (en) | ||
| CN108383967A (en) | A kind of organosilicon preformed polymer and preparation method thereof that urethane acrylate is modified | |
| CN105754087B (en) | A kind of preparation method of end polyether silicon | |
| CN108165201B (en) | A kind of tackifier and preparation method thereof | |
| CN108473684A (en) | The manufacturing method of siloxane polymer | |
| CN109705352A (en) | A kind of vinyl polysiloxane and its preparation method and application | |
| CN106831845A (en) | Boracic organo-silicon compound, Preparation Method And The Use | |
| CN107573372B (en) | Preparation method of amino silane and epoxy silane copolymer | |
| CN105778100B (en) | A kind of organic silicon rigidity-increasing stick and preparation method thereof and a kind of addition-type silicon rubber composition | |
| CN102643547A (en) | Ablation-resistant room temperature vulcanized silicone rubber and preparation method thereof | |
| TWI757308B (en) | Formulation containing a metal aprotic organosilanoxide compound | |
| CN104387590B (en) | Antenna-structure cage-type organic silicon resin, and preparation method and application thereof | |
| CN104411771B (en) | Curable resin composition | |
| JP3465391B2 (en) | Reactive organopolysiloxane | |
| CN106010423B (en) | A kind of preparation method of addition-type silicon rubber adhesion promoters | |
| CN105368339B (en) | Additional organosilicon is bonded and sealed glue tackifier, preparation method and composition therefor | |
| CN104356392B (en) | Cage-type dendritic organic silicon resin as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |