CN104910829B - Tackifying agent for LED sealed packaging adhesive and preparation method thereof - Google Patents
Tackifying agent for LED sealed packaging adhesive and preparation method thereof Download PDFInfo
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- CN104910829B CN104910829B CN201510225282.XA CN201510225282A CN104910829B CN 104910829 B CN104910829 B CN 104910829B CN 201510225282 A CN201510225282 A CN 201510225282A CN 104910829 B CN104910829 B CN 104910829B
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Abstract
The invention discloses a tackifying agent for an LED sealed packaging adhesive and a preparation method thereof. The tackifying agent is prepared by the steps: carrying out a condensation reaction on polyborosiloxane, a siloxane prepolymer, a silane coupling agent and an end-capping agent in a water and organic solvent environment and under the action of an acid catalyst, then washing with water to neutral, carrying out reduced pressure distillation to remove an organic solvent and a low-boiling-point substance, and thus obtaining the colorless transparent viscous tackifying agent. The polyborosiloxane is obtained by carrying out a reaction of boric acid and phenyl chlorosilane under a reduced pressure condition, and the siloxane prepolymer is obtained by dehydration condensation of phenyl siloxane under the action of an acid catalyst. The tackifying agent used for the LED sealed packaging adhesive and prepared by the method has good adhesion ability on PPA and a silver plated layer of an aluminum base plate simultaneously, and has the advantages of high refractive index and yellowing resistance.
Description
Technical field
The present invention relates to LED packaging plastic technical fields, more particularly to a kind of LED packaging plastics viscosifier and its preparation side
Method.
Background technology
The internal characteristicses of light emitting diode (LED) such as small volume, power consumption is low, long service life, high brightness, it is low in calories,
The advantages of environmentally friendly, sturdy and durable, changeable, determine that LED will occupy an important position in following lighting field, at present
LED is used widely in fields such as illumination, backlight, display screens rapidly.
Phenyl addition type polysiloxane is due to its high index of refraction, high-low temperature resistant, ultraviolet aging resistance, insulation, hydrophobic, anti-ageing
The performances such as change, sulfuration resistant, are increasingly becoming the development trend of LED encapsulation, but phenyl addition type polysiloxane is due to its molecular weight
On have substantial amounts of nonpolar phenyl group, cause the metal base and polar plas of phenyl addition type polysiloxane and support
PPA adhesive properties are poor so that phenyl addition type polysiloxane is easily peeled off from support, makes chip lose protection, and this is main
It is, because addition-type silicon rubber molecule itself is in nonpolar, when using as embedding, coating, inserts injecting forming material, to glue
Connecing property is very poor.At present, improve packaging plastic mainly has three kinds with the method for the cementability of various materials：One is to base material with silane coupling agent
Surface is processed, and the method increased production process and production time, reduce production efficiency, while using inflammable more than silane coupling agent
Solvent, causes peril of transportation and environmental pollution；Two is to strengthen cementability by changing base rubber molecular structure, but this method due to
Actual production process is more complicated, and cost is of a relatively high；Three is that cementability is improved by adding viscosifier, this method operation
It is convenient and easy, so synthesizing new viscosifier become study hotspot.
The Chinese patent application of Publication No. CN103275325A, entitled " Borosiloxane and preparation method thereof ", utilizes
Boron and the cementability of metal, are prepared for a kind of polyborosiloxane viscosifier, but due to the property of boron element, boron is to LED support
Middle metal adhesive power is excellent, but weaker to the PPA plastic bonding power on support, packaging plastic easily in hot environment with PPA
Peel off so that oxygen and water enter support, cause the failure of LED.Publication No. CN1993427A, entitled " curable has
The Chinese patent application of machine organopolysiloxane composition, its curing, semiconductor device and adhesion promotor ", is prepared for one
The polymer comprising epoxide group and ester group is planted, but such viscosifier are after packaging plastic is added to, through the aging examination of long-time
Test, tend to jaundice, cause LED lamp bead light decay serious.
The content of the invention
The present invention provides a kind of while having viscosifier and its preparation of excellent bonds ability to PPA, aluminium base silver coating
Method, the viscosifier are provided simultaneously with the advantage of high index of refraction and yellowing-resistant.
According to the first aspect of the invention, the present invention provides a kind of LED packaging plastics viscosifier, and the viscosifier are poly- borosilicates
Oxygen alkane, siloxane prepolymer, silane coupler and end-capping reagent in water, organic solvent environment in the presence of acidic catalyst,
Condensation reaction is carried out, neutrality, and vacuum distillation removing organic solvent and low-boiling-point substance is then washed to, and the water white transparency for obtaining is viscous
The viscosifier of thick shape；Wherein above-mentioned polyborosiloxane is that boric acid and phenyl chlorosilane react obtain at reduced pressure conditions, above-mentioned
Siloxane prepolymer is that phenyl siloxane is obtained in the presence of acidic catalyst by dehydrating condensation.
Used as the preferred version of the present invention, above-mentioned phenyl chlorosilane is selected from diphenyl dichlorosilane, aminomethyl phenyl dichloro silicon
One or more in alkane and α, ω-dichloro PSI, preferred diphenyl dichlorosilane.
Used as the preferred version of the present invention, above-mentioned phenyl siloxane is selected from dimethoxydiphenylsilane, diphenyl diethyl
TMOS, aminomethyl phenyl dimethoxysilane, aminomethyl phenyl diethoxy silane, phenyltrimethoxysila,e, the second of phenyl three
One or more in TMOS and triphenylmethoxy silane, preferred phenyltrimethoxysila,e.
Used as the preferred version of the present invention, above-mentioned silane coupler is selected from 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicon
Alkane, γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, 3- aminopropyl trimethoxysilanes,
One or more in gamma-aminopropyl-triethoxy-silane and 3- (2,3 the third oxygen of epoxy) hydroxypropyl methyl diethoxy silane, preferably
3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicanes or γ-methacryloxypropyl trimethoxy silane.
Used as the preferred version of the present invention, above-mentioned end-capping reagent is selected from tetramethyl disiloxane, the silicon of tetramethyl divinyl two
One or more in oxygen alkane and hexamethyl disiloxane, preferred tetramethyl disiloxane.
According to the second aspect of the invention, the present invention provides a kind of preparation method of LED packaging plastics viscosifier, the method
Comprise the steps：
(1) boric acid and phenyl chlorosilane is reacted at reduced pressure conditions and obtain polyborosiloxane；
(2) phenyl siloxane is made to obtain siloxane prepolymer by dehydrating condensation in the presence of acidic catalyst；
(3) above-mentioned polyborosiloxane and above-mentioned siloxane prepolymer, silane coupler, end-capping reagent, water, organic solvent are existed
Condensation reaction is carried out in the presence of acidic catalyst, neutrality, vacuum distillation removing organic solvent and low-boiling-point substance is then washed to, is obtained
To the LED packaging plastic viscosifier that water white transparency is thick.
Used as the preferred version of the present invention, said method comprises the steps：
(1) at 80-100 DEG C, the boric acid of 50-80 mass parts and the phenyl chlorosilane of 200-300 mass parts are made in decompression
Under the conditions of react 8-12h obtain polyborosiloxane；
(2) at 50-80 DEG C, the phenyl siloxane of 100-200 mass parts is made in the work of the acidic catalyst of 1-2 mass parts
Siloxane prepolymer is obtained with lower dehydration condensation 3-5h；
(3) at 50-80 DEG C, make 5-8 mass parts above-mentioned polyborosiloxane and 30-50 mass parts above-mentioned siloxanes it is pre-
Polymers, the silane coupler of 30-50 mass parts, the end-capping reagent of 2-5 mass parts, the deionized water of 5-10 mass parts, 100-150 matter
The organic solvent of amount part condensation reaction 10-15h in the presence of the acidic catalyst of 0.1-1 mass parts, is then washed to neutrality,
Vacuum distillation removes organic solvent and low-boiling-point substance, obtains viscosifier.
Used as the preferred version of the present invention, above-mentioned phenyl chlorosilane is selected from diphenyl dichlorosilane, aminomethyl phenyl dichloro silicon
One or more in alkane and α, ω-dichloro PSI, preferred diphenyl dichlorosilane.
Used as the preferred version of the present invention, above-mentioned reduced pressure is the feelings that vacuum is -0.075MPa to -0.096MPa
Condition.
Used as the preferred version of the present invention, above-mentioned phenyl siloxane is selected from dimethoxydiphenylsilane, diphenyl diethyl
TMOS, aminomethyl phenyl dimethoxysilane, aminomethyl phenyl diethoxy silane, phenyltrimethoxysila,e, the second of phenyl three
One or more in TMOS and triphenylmethoxy silane, preferred phenyltrimethoxysila,e.
Used as the preferred version of the present invention, above-mentioned acidic catalyst is selected from hydrochloric acid, sulphuric acid, trifluoromethayl sulfonic acid, cation
One or more in exchanger resin SK1BH, phosphoric acid and phosphonitrilic chloride, preferred trifluoromethayl sulfonic acid.
Used as the preferred version of the present invention, above-mentioned silane coupler is selected from 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicon
Alkane, γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, 3- aminopropyl trimethoxysilanes,
One or more in gamma-aminopropyl-triethoxy-silane and 3- (2,3 the third oxygen of epoxy) hydroxypropyl methyl diethoxy silane, preferably
3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicanes or γ-methacryloxypropyl trimethoxy silane.
Used as the preferred version of the present invention, above-mentioned end-capping reagent is selected from tetramethyl disiloxane, the silicon of tetramethyl divinyl two
One or more in oxygen alkane and hexamethyl disiloxane, preferred tetramethyl disiloxane.
Used as the preferred version of the present invention, above-mentioned organic solvent is selected from toluene, dimethylbenzene, normal hexane, hexamethylene, four chlorinations
One or more in carbon and ethyl acetate, preferred toluene or dimethylbenzene.
The LED packaging plastics viscosifier that the method for the present invention is prepared have good to PPA, aluminium base silver coating simultaneously
Adhesive power, is provided simultaneously with the advantage of high index of refraction and yellowing-resistant.
Specific embodiment
The present invention is described in further detail below by specific embodiment.
The present inventor passes through at reduced pressure conditions to react (1) boric acid and phenyl chlorosilane to obtain poly- borosilicate oxygen
Alkane；(2) phenyl siloxane is obtained into siloxane prepolymer in the presence of acidic catalyst by dehydrating condensation；(3) by poly- boron
Siloxanes and siloxane prepolymer, silane coupler, end-capping reagent, water, organic solvent are contracted in the presence of acidic catalyst
Reaction is closed, neutrality, vacuum distillation removing organic solvent and low-boiling-point substance is then washed to, obtains a kind of while to PPA, aluminium base plating
Silver layer has excellent bonds ability and is provided simultaneously with the thick LED encapsulation of water white transparency of high index of refraction and yellowing-resistant advantage
Glue viscosifier.
Present inventors have surprisingly discovered that, made with viscosifier using the LED packaging plastics prepared by said method
For the composition of packaging plastic, enable to packaging plastic and 10-20 times is improved to the adhesive power of PPA, aluminium base silver coating, exceed significantly
The expectation of those skilled in the art.
It should be noted that the order of above-mentioned steps (1) and (2) is simultaneously unrestricted, can first carry out step (1) and be walked again
Suddenly (2), it is also possible to which first carrying out step (2) carries out again step (1), because the two steps are independent.Although in claim
Marked (1) and (2), it should be understood that the scope of claim not only includes that first carrying out step (1) carries out again the feelings of step (2)
Condition, also carries out again the situation of step (1) including first carrying out step (2).
On the basis of the such scheme of the present invention, the present inventor is to the raw material dosage in reaction, reaction temperature
Further optimization has been carried out with the response time, a kind of preferred technical scheme has been obtained.By obtained by the preferred technical scheme
Viscosifier as the composition of LED packaging plastics, can unexpectedly improve packaging plastic to PPA, the bonding of aluminium base silver coating
Performance, and it is provided simultaneously with the advantage of high index of refraction and yellowing-resistant.
The preferred technical scheme is as follows：
(1) at 80-100 DEG C, the boric acid of 50-80 mass parts and the phenyl chlorosilane of 200-300 mass parts are made in decompression
Under the conditions of react 8-12h obtain polyborosiloxane；
(2) at 50-80 DEG C, the phenyl siloxane of 100-200 mass parts is made in the work of the acidic catalyst of 1-2 mass parts
Siloxane prepolymer is obtained with lower dehydration condensation 3-5h；
(3) at 50-80 DEG C, make 5-8 mass parts above-mentioned polyborosiloxane and 30-50 mass parts above-mentioned siloxanes it is pre-
Polymers, the silane coupler of 30-50 mass parts, the end-capping reagent of 2-5 mass parts, the deionized water of 5-10 mass parts, 100-150 matter
The organic solvent of amount part condensation reaction 10-15h in the presence of the acidic catalyst of 0.1-1 mass parts, is then washed to neutrality,
Vacuum distillation removes organic solvent and low-boiling-point substance, obtains viscosifier.
In certain embodiments of the present invention, above-mentioned phenyl chlorosilane is selected from diphenyl dichlorosilane, aminomethyl phenyl dichloro
One or more in silane and α, ω-dichloro PSI, that is to say, that can be used alone one of which,
Two or more can be used in mixed way, and the present invention is not limited for the mixed proportion being used in mixed way.It is typical but non-
The determinate example being used in mixed way is such as：The mixing of diphenyl dichlorosilane and dichloromethyl phenylsilane, diphenyl dichloro
The mixing of silane and α, ω-dichloro PSI, dichloromethyl phenylsilane and α, ω-dichloro polymethyl-benzene base silicon
The mixing of oxygen alkane, the mixing of diphenyl dichlorosilane, dichloromethyl phenylsilane and α, ω-dichloro PSI.
It is preferred that diphenyl dichlorosilane.
In certain embodiments of the present invention, above-mentioned reduced pressure is the feelings that vacuum is -0.075MPa to -0.096MPa
Condition, such as vacuum -0.080MPa, -0.082MPa, -0.085MPa, -0.087MPa, -0.090MPa, -0.092MPa, -
0.095MPa, -0.096MPa, -0.080~-0.092MPa or -0.082~-0.090MPa.
In certain embodiments of the present invention, above-mentioned phenyl siloxane is selected from dimethoxydiphenylsilane, diphenyl two
Ethoxysilane, aminomethyl phenyl dimethoxysilane, aminomethyl phenyl diethoxy silane, phenyltrimethoxysila,e, phenyl three
One or more in Ethoxysilane and triphenylmethoxy silane, that is to say, that can be used alone one of which, also may be used
To be used in mixed way two or more, and the present invention is not limited for the mixed proportion being used in mixed way.Typical but non-limit
The example being qualitatively used in mixed way is such as：The mixing of dimethoxydiphenylsilane and diphenyl diethoxy silane, diphenyl
The mixing of dimethoxysilane and aminomethyl phenyl dimethoxysilane, diphenyl diethoxy silane and aminomethyl phenyl dimethoxy
The mixing of silane, the mixing of dimethoxydiphenylsilane, diphenyl diethoxy silane and aminomethyl phenyl dimethoxysilane.
It is preferred that phenyltrimethoxysila,e.
In certain embodiments of the present invention, above-mentioned acidic catalyst selected from hydrochloric acid, sulphuric acid, trifluoromethayl sulfonic acid, sun from
One or more in sub-exchange resin SK1BH, phosphoric acid and phosphonitrilic chloride, that is to say, that can be used alone one of which,
Two or more can be used in mixed way, and the present invention is not limited for the mixed proportion being used in mixed way.It is typical but non-
The determinate example being used in mixed way is such as：The mixing of the mixing of sulphuric acid and trifluoromethayl sulfonic acid, sulphuric acid and phosphonitrilic chloride, trifluoro
The mixing of Loprazolam and phosphonitrilic chloride, the mixing of sulphuric acid, trifluoromethayl sulfonic acid and phosphonitrilic chloride.It is preferred that trifluoromethayl sulfonic acid.
In certain embodiments of the present invention, above-mentioned silane coupler is selected from 3- (2,3- the third oxygen of epoxy) propyl trimethoxy
Silane (KH560), γ-methacryloxypropyl trimethoxy silane (KH570), vinyltrimethoxy silane, 3- ammonia
Propyl trimethoxy silicane (KH-540), gamma-aminopropyl-triethoxy-silane (KH550) and 3- (2,3 the third oxygen of epoxy) propyl group first
One or more in base diethoxy silane, that is to say, that can be used alone one of which, it is also possible to be used in mixed way two kinds
Or it is two or more, and the present invention do not limited for the mixed proportion being used in mixed way.Typical case but indefiniteness is used in mixed way
Example such as：The mixing of the mixing of KH560 and KH570, KH570 and vinyltrimethoxy silane, vinyl trimethoxy
The mixing of the mixing of silane and KH-540, KH-540 and 3- (2,3 the third oxygen of epoxy) hydroxypropyl methyl diethoxy silane.It is preferred that
KH560 and KH570.
In certain embodiments of the present invention, above-mentioned end-capping reagent is selected from tetramethyl disiloxane, tetramethyl divinyl two
One or more in siloxanes and hexamethyl disiloxane, that is to say, that can be used alone one of which, it is also possible to mix
Using two or more, and the present invention is not limited for the mixed proportion being used in mixed way.Typical but indefiniteness
The example being used in mixed way is such as：The mixing of tetramethyl disiloxane and tetramethyl divinyl disiloxane, the silica of tetramethyl two
The mixing of the mixing of alkane and hexamethyl disiloxane, tetramethyl divinyl disiloxane and hexamethyl disiloxane, tetramethyl
The mixing of disiloxane, tetramethyl divinyl disiloxane and hexamethyl disiloxane.It is preferred that tetramethyl disiloxane.
In certain embodiments of the present invention, above-mentioned organic solvent is selected from toluene, dimethylbenzene, normal hexane, hexamethylene, tetrachloro
Change in carbon and ethyl acetate one or more, that is to say, that can be used alone one of which, it is also possible to be used in mixed way two kinds
Or it is two or more, and the present invention do not limited for the mixed proportion being used in mixed way.Typical case but indefiniteness is used in mixed way
Example such as：The mixing of the mixing of the mixing of toluene and dimethylbenzene, toluene and normal hexane, dimethylbenzene and normal hexane, toluene, two
The mixing of the mixing of the mixing of toluene and normal hexane, hexamethylene and carbon tetrachloride, carbon tetrachloride and ethyl acetate, hexamethylene, four
The mixing of chlorination carbon and ethyl acetate.It is preferred that toluene or dimethylbenzene.
In above-mentioned preferred technical scheme, raw material dosage, reaction temperature and response time, all further optimization was obtained.
Wherein, reaction temperature 80-100 DEG C in step (1), such as 82 DEG C, 85 DEG C, 87 DEG C, 89 DEG C, 91 DEG C, 93 DEG C, 95
DEG C, 96 DEG C, 98 DEG C, 99 DEG C, 82-95 DEG C, 85-90 DEG C, 88-95 DEG C or 90-98 DEG C；The consumption 50-80 mass parts of boric acid, for example
52 mass parts, 55 mass parts, 58 mass parts, 62 mass parts, 64 mass parts, 67 mass parts, 69 mass parts, 71 mass parts, 73 matter
Amount part, 75 mass parts, 78 mass parts, 60-75 mass parts or 65-70 mass parts；The consumption 200-300 mass of phenyl chlorosilane
Part, such as 200 mass parts, 220 mass parts, 235 mass parts, 250 mass parts, 270 mass parts, 280 mass parts, 285 mass parts,
295 mass parts, 220-270 mass parts or 230-250 mass parts；Response time 8-12h, such as 8.5h, 8.8h, 9.2h, 9.5h,
9.7h, 10h, 10.5h, 10.8h, 11h, 11.25h, 11.5h, 11.7h, 11.9h, 8.5-11h or 9-10h.
Reaction temperature 50-80 DEG C in step (2), such as 52 DEG C, 54 DEG C, 56 DEG C, 59 DEG C, 61 DEG C, 65 DEG C, 68 DEG C, 72
DEG C, 75 DEG C, 78 DEG C, 60-75 DEG C or 65-70 DEG C；The consumption 100-200 mass parts of phenyl siloxane, such as 110 mass parts, 120
Mass parts, 130 mass parts, 150 mass parts, 160 mass parts, 180 mass parts, 190 mass parts, 195 mass parts, 120-180 matter
Amount part or 130-150 mass parts；The consumption 1-2 mass parts of acidic catalyst, such as 1.1 mass parts, 1.2 mass parts, 1.3 mass
Part, 1.5 mass parts, 1.7 mass parts, 1.8 mass parts, 1.9 mass parts, 1.2-1.8 mass parts or 1.3-1.5 mass parts；Dehydration
Condensation reaction 3-5h, such as 3.2h, 3.5h, 3.8h, 4.1h, 4.3h, 4.5h, 4.7h, 4.9h, 3.5-4.8h or 3.8-4.2h.
Reaction temperature 50-80 DEG C in step (3), such as 52 DEG C, 54 DEG C, 56 DEG C, 59 DEG C, 61 DEG C, 65 DEG C, 68 DEG C, 72
DEG C, 75 DEG C, 78 DEG C, 60-75 DEG C or 65-70 DEG C；The consumption 5-8 mass parts of polyborosiloxane, such as 5.5 mass parts, 5.8 mass
Part, 6.2 mass parts, 6.7 mass parts, 7.3 mass parts, 7.5 mass parts, 7.7 mass parts, 7.8 mass parts, 5.5-7.5 mass parts
Or 6.0-7.0 mass parts；The consumption 30-50 mass parts of siloxane prepolymer, such as 33 mass parts, 35 mass parts, 37 mass parts,
41 mass parts, 43 mass parts, 45 mass parts, 48 mass parts, 35-45 mass parts or 38-42 mass parts；The consumption of silane coupler
30-50 mass parts, such as 33 mass parts, 35 mass parts, 37 mass parts, 41 mass parts, 43 mass parts, 45 mass parts, 48 mass
Part, 35-45 mass parts or 38-42 mass parts；The consumption 2-5 mass parts of end-capping reagent, such as 2.1 mass parts, 2.3 mass parts, 2.5
Mass parts, 2.8 mass parts, 3.2 mass parts, 3.5 mass parts, 3.8 mass parts, 4.2 mass parts, 4.5 mass parts, 4.8 mass parts,
2.5-4.5 mass parts or 3-4 mass parts；The consumption 5-10 mass parts of deionized water, such as 5.2 mass parts, 5.5 mass parts, 6 matter
Amount part, 6.5 mass parts, 7 mass parts, 7.5 mass parts, 8 mass parts, 8.5 mass parts, 9 mass parts, 9.5 mass parts, 9.8 mass
Part, 6-9 mass parts or 7-8 mass parts；The consumption 100-150 mass parts of organic solvent, such as 110 mass parts, 115 mass parts,
120 mass parts, 130 mass parts, 135 mass parts, 140 mass parts, 145 mass parts, 110-140 mass parts or 120-130 mass
Part；The consumption 0.1-1 mass parts of acidic catalyst, such as 0.1 mass parts, 0.2 mass parts, 0.3 mass parts, 0.4 mass parts,
0.5 mass parts, 0.6 mass parts, 0.7 mass parts, 0.8 mass parts, 0.9 mass parts, 0.95 mass parts, 0.2-0.8 mass parts or
0.4-0.6 mass parts；Condensation reaction 10-15h, such as 11h, 11.5h, 12h, 12.5h, 13.5h, 14h, 14.5h, 15h, 13-
14.5h or 13.5-14h.
Below by way of specific embodiment, the LED packaging plastics of the present invention are carried out specifically with viscosifier and preparation method thereof
It is bright.It should be appreciated that following examples are only exemplary, the present invention is not limited to following examples.
The viscosifier prepared in following examples are used as the composition of LED packaging plastics, the survey of its firming body bonding strength
Amount method is as follows：Using Vinylphenyl silicon resin RH-SP605-3 (Zhejiang Run He new chemical materialses company limited) and Silicon Containing Hydrogen
Resin RH-SP303 (Zhejiang Run He new chemical materialses company limited) is according to vinyl (RH-SP605-3 offers) mole/silicon hydrogen
The proportions of key (RH-SP303 offers) mole=1.3 obtain base rubber, and sequentially add the acetylene of 0.5% base rubber mass parts
(An Biya special types are organic for the Andisil 785Catalyst of cyclohexanol (Aladdin Reagent Company) and 0.5% base rubber mass parts
Silicon company) catalyst, it is subsequently adding the LED packaging plastics thickening of the high index of refraction of each embodiment synthesis of 1% base rubber mass parts
Agent is configured to packaging plastic to be tested.
According to the method for testing of GB/T13936-1992, in two silver-plated aluminium sheet (or PPA plates) (width：25mm；It is long
Degree：50mm；Thickness：Fill packaging plastic obtained above in space between 1mm).Protect in the circulating baking oven of 150 DEG C of hot-airs
Hold the encapsulation adhesive curing.After being cooled to room temperature, by stretching institute in horizontal direction relative to each other in cupping machine
The sample of acquisition is measuring the bonding strength of firming body.
Embodiment 1
Under conditions of 80 DEG C, using the boric acid (Aladdin Reagent Company) and the methylbenzene of 200 mass parts of 50 mass parts
Base dichlorosilane (Dalian Yuan Yong organosilicons factory) reacts 8h under the reduced pressure that vacuum is -0.096MPa and obtains a kind of poly- boron
Siloxanes；
Under conditions of 50 DEG C, using the phenyl triethoxysilane (Dalian Yuan Yong organosilicons factory) of 100 mass parts in 1 matter
Dehydrating condensation 3h obtains a kind of silica in the presence of the cation exchange resin SK1BH (Mitsubishi KCC) of amount part
Alkane prepolymer；
The polyborosiloxane of 5 mass parts that synthesis is obtained and the siloxane prepolymer of 30 mass parts, the 3- of 15 mass parts
(2,3 the third oxygen of epoxy) hydroxypropyl methyl diethoxy silane (Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei), 15 mass parts
KH570 (Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei), tetramethyl disiloxane (the auspicious Cenda in Quzhou of 2 mass parts
Chemical Co., Ltd.), the deionized water of 5 mass parts, the ethyl acetate (Xilong Chemical Co., Ltd) of 100 mass parts is 50
Under the conditions of DEG C, 10h is condensed in the presence of the cation exchange resin SK1BH of 1 mass parts, is then washed to neutrality, vacuum distillation
Removing ethyl acetate and low-boiling-point substance, obtain a kind of thick high index of refraction LED packaging plastic viscosifier of water white transparency.
Embodiment 2
Under conditions of 90 DEG C, using the boric acid (Aladdin Reagent Company) and the diphenyl of 240 mass parts of 60 mass parts
Dichlorosilane (Dalian Yuan Yong organosilicons factory) reacts 9h under the reduced pressure that vacuum is -0.096MPa and obtains a kind of poly- borosilicate
Oxygen alkane；
Under conditions of 60 DEG C, using the phenyltrimethoxysila,e (Dalian Yuan Yong organosilicons factory) of 100 mass parts in 1 matter
Dehydrating condensation 4h obtains a kind of siloxane prepolymer in the presence of the phosphonitrilic chloride (Aladdin Reagent Company) of amount part；
The polyborosiloxane of 6 mass parts that synthesis is obtained and the siloxane prepolymer of 40 mass parts, 20 mass parts
KH550 (the military big organosilicon new materials in Hubei of KH540 (Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei), 20 mass parts
Limited company), the tetramethyl divinyl disiloxane (Quzhou Ruilijie Chemical Co., Ltd.) of 3 mass parts, 6 mass parts
Deionized water, 120 mass parts hexamethylene (Xi Long Chemical Co., Ltd.s) under the conditions of 60 DEG C, the phosphorus chloride of 0.1 mass parts
12h is condensed in the presence of nitrile, neutrality, vacuum distillation removing hexamethylene and low-boiling-point substance is then washed to, a kind of water white transparency is obtained
Thick high index of refraction LED packaging plastic viscosifier.
Embodiment 3
Under conditions of 85 DEG C, using the boric acid (Aladdin Reagent Company) and the methylbenzene of 250 mass parts of 70 mass parts
Base dichlorosilane (Dalian Yuan Yong organosilicons factory) reacts 10h under the reduced pressure that vacuum is -0.096MPa and obtains a kind of poly-
Borosiloxane；
Under conditions of 70 DEG C, using the phenyltrimethoxysila,e (Dalian Yuan Yong organosilicons factory) of 150 mass parts 1.5
Dehydrating condensation 4h obtains a kind of siloxane prepolymer in the presence of the trifluoromethayl sulfonic acid (Aladdin Reagent Company) of mass parts；
The polyborosiloxane of 7 mass parts that synthesis is obtained and the siloxane prepolymer of 40 mass parts, 25 mass parts
KH570 (the military big organosilicon new materials in Hubei of KH560 (Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei), 25 mass parts
Limited company), the hexamethyl disiloxane (Quzhou Ruilijie Chemical Co., Ltd.) of 4 mass parts, the deionization of 7 mass parts
Water, 130 mass parts normal hexane (Xilong Chemical Co., Ltd) under the conditions of 80 DEG C, the fluoroform sulphur of 0.5 mass parts
13h is condensed in the presence of acid, neutrality, vacuum distillation removing normal hexane and low-boiling-point substance is then washed to, a kind of water white transparency is obtained
Thick high index of refraction LED packaging plastic viscosifier.
Embodiment 4
Under conditions of 100 DEG C, using the boric acid (Aladdin Reagent Company) and the methylbenzene of 270 mass parts of 80 mass parts
Base dichlorosilane (Dalian Yuan Yong organosilicons factory) reacts 11h under the reduced pressure that vacuum is -0.096MPa and obtains a kind of poly-
Borosiloxane；
Under conditions of 70 DEG C, using 50 mass parts aminomethyl phenyl diethoxy silanes (Dalian Yuan Yong organosilicons factory), 150
In 2 mass parts sulphuric acid, (concentration 98%, western Gansu Province chemical industry share has mass parts phenyltrimethoxysila,e (Dalian Yuan Yong organosilicons factory)
Limit company) in the presence of dehydrating condensation 5h obtain a kind of siloxane prepolymer；
The polyborosiloxane of 8 mass parts that synthesis is obtained and the siloxane prepolymer of 50 mass parts, 50 mass parts
Tetramethyl disiloxane (the auspicious Cenda in Quzhou of KH570 (Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei), 3 mass parts
Work company limited), the hexamethyl disiloxane (Quzhou Ruilijie Chemical Co., Ltd.) of 2 mass parts, the deionization of 10 mass parts
Water, 150 mass parts dimethylbenzene (Xilong Chemical Co., Ltd) under the conditions of 80 DEG C, the effect of the sulphuric acid of 0.5 mass parts
Lower condensation 15h, is then washed to neutrality, vacuum distillation removing dimethylbenzene and low-boiling-point substance, obtains a kind of water white transparency thick
High index of refraction LED packaging plastic viscosifier.
Embodiment 5
Under conditions of 95 DEG C, using the boric acid (Aladdin Reagent Company) and the diphenyl of 280 mass parts of 75 mass parts
Dichlorosilane (Dalian Yuan Yong organosilicons factory) reacts 12h under the reduced pressure that vacuum is -0.075MPa and obtains a kind of poly- boron
Siloxanes；
At 75 DEG C, using the dimethoxydiphenylsilane (Dalian Yuan Yong organosilicons factory) and 100 mass of 100 mass parts
(concentration 36%, western Gansu Province chemical industry share is limited in 2 mass parts hydrochloric acid for the phenyltrimethoxysila,e (Dalian Yuan Yong organosilicons factory) of part
Company) in the presence of dehydrating condensation 4.5h obtain a kind of siloxane prepolymer；
The polyborosiloxane of 8 mass parts that synthesis is obtained and the siloxane prepolymer of 45 mass parts, 45 mass parts
Hexamethyl disiloxane (the auspicious Cenda in Quzhou of KH560 (Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei), 4 mass parts
Work company limited), the deionized water of 10 mass parts, the toluene (Xilong Chemical Co., Ltd) of 150 mass parts is in 80 DEG C of bars
Under part, 15h is condensed in the presence of the hydrochloric acid of 1 mass parts, is then washed to neutrality, vacuum distillation removing toluene and low-boiling-point substance, obtained
To the high index of refraction LED packaging plastic viscosifier that a kind of water white transparency is thick.
Viscosifier obtained in above-described embodiment 1-5 are used as the composition of LED packaging plastics, the refractive index for measuring, high-temperature baking
Can and it is as shown in table 1 with the performance data of aluminium sheet silver coating and the firming body bonding force of PPA plastics.Using be not added with thickening
Agent and the base rubber containing other all the components are as a comparison case.
The test data of LED encapsulation viscosifier obtained in embodiment 1-5 of table 1
As a result show：Using viscosifier obtained in embodiments of the invention 1-5 as LED packaging plastics adding ingredient, energy
Packaging plastic is enough significantly improved to aluminium sheet silver coating and the firming body bonding force of PPA plastics, adhesive power even improves 10-20 times,
Far beyond the expectation of those skilled in the art.
Above content is to combine specific embodiment further description made for the present invention, it is impossible to assert this
It is bright to be embodied as being confined to these explanations.For general technical staff of the technical field of the invention, do not taking off
On the premise of present inventive concept, some simple deduction or replace can also be made.
Claims (24)
1. a kind of LED packaging plastics viscosifier, it is characterised in that the viscosifier are polyborosiloxane, siloxane prepolymer, silicon
Alkane coupling agent and end-capping reagent in the presence of acidic catalyst, carry out condensation reaction in water, organic solvent environment, then wash
To neutral, and vacuum distillation removing organic solvent and low-boiling-point substance, and the thick viscosifier of the water white transparency that obtains；It is wherein described
Polyborosiloxane is that boric acid and phenyl chlorosilane react obtain at reduced pressure conditions, and the siloxane prepolymer is phenyl silica
What alkane was obtained in the presence of acidic catalyst by dehydrating condensation.
2. viscosifier according to claim 1, it is characterised in that the phenyl chlorosilane selected from diphenyl dichlorosilane,
One or more in dichloromethyl phenylsilane and α, ω-dichloro PSI.
3. viscosifier according to claim 2, it is characterised in that the phenyl chlorosilane is diphenyl dichlorosilane.
4. viscosifier according to claim 1, it is characterised in that the phenyl siloxane is selected from diphenyl dimethoxy silicon
Alkane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxysilane, aminomethyl phenyl diethoxy silane, phenyl trimethoxy
One or more in silane, phenyl triethoxysilane and triphenylmethoxy silane.
5. viscosifier according to claim 4, it is characterised in that the phenyl siloxane is phenyltrimethoxysila,e.
6. viscosifier according to claim 1, it is characterised in that the silane coupler is selected from 3- (2,3- the third oxygen of epoxy)
Propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, 3- ammonia third
In base trimethoxy silane, gamma-aminopropyl-triethoxy-silane and 3- (2,3 the third oxygen of epoxy) hydroxypropyl methyl diethoxy silane
One or more.
7. viscosifier according to claim 6, it is characterised in that the silane coupler is 3- (2,3- the third oxygen of epoxy) third
Base trimethoxy silane or γ-methacryloxypropyl trimethoxy silane.
8. viscosifier according to claim 1, it is characterised in that the end-capping reagent is selected from tetramethyl disiloxane, tetramethyl
One or more in base divinyl disiloxane and hexamethyl disiloxane.
9. viscosifier according to claim 8, it is characterised in that the end-capping reagent is tetramethyl disiloxane.
10. a kind of preparation method of LED packaging plastics viscosifier, it is characterised in that methods described comprises the steps：
(1) boric acid and phenyl chlorosilane is reacted at reduced pressure conditions and obtain polyborosiloxane；
(2) phenyl siloxane is made to obtain siloxane prepolymer by dehydrating condensation in the presence of acidic catalyst；
(3) by the polyborosiloxane and the siloxane prepolymer, silane coupler, end-capping reagent, water, organic solvent in acidity
Condensation reaction is carried out in the presence of catalyst, neutrality, vacuum distillation removing organic solvent and low-boiling-point substance is then washed to, nothing is obtained
The LED packaging plastic viscosifier of color clear viscous shape.
11. methods according to claim 10, it is characterised in that methods described comprises the steps：
(1) at 80-100 DEG C, make 50-80 mass parts boric acid and 200-300 mass parts phenyl chlorosilane in reduced pressure
Lower reaction 8-12h obtains the polyborosiloxane；
(2) at 50-80 DEG C, the phenyl siloxane of 100-200 mass parts is made in the presence of the acidic catalyst of 1-2 mass parts
Dehydration condensation 3-5h obtains the siloxane prepolymer；
(3) at 50-80 DEG C, the polyborosiloxane of 5-8 mass parts and the siloxanes pre-polymerization of 30-50 mass parts are made
Thing, the silane coupler of 30-50 mass parts, the end-capping reagent of 2-5 mass parts, the deionized water of 5-10 mass parts, 100-150 mass
The organic solvent of part condensation reaction 10-15h in the presence of the acidic catalyst of 0.1-1 mass parts, is then washed to neutrality, subtracts
Pressure distillation removing organic solvent and low-boiling-point substance, obtain the viscosifier.
12. methods according to claim 10 or 11, it is characterised in that the phenyl chlorosilane is selected from diphenyl dichloro silicon
One or more in alkane, dichloromethyl phenylsilane and α, ω-dichloro PSI.
13. methods according to claim 12, it is characterised in that the phenyl chlorosilane is diphenyl dichlorosilane.
14. methods according to claim 10 or 11, it is characterised in that the reduced pressure be vacuum for-
The situation of 0.075MPa to -0.096MPa.
15. methods according to claim 10 or 11, it is characterised in that the phenyl siloxane is selected from diphenyl dimethoxy
Base silane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxysilane, aminomethyl phenyl diethoxy silane, phenyl front three
One or more in TMOS, phenyl triethoxysilane and triphenylmethoxy silane.
16. methods according to claim 15, it is characterised in that the phenyl siloxane is phenyltrimethoxysila,e.
17. methods according to claim 10 or 11, it is characterised in that the acidic catalyst selected from hydrochloric acid, sulphuric acid, three
One or more in fluoromethane sulfonic acid, cation exchange resin SK1BH, phosphoric acid and phosphonitrilic chloride.
18. methods according to claim 17, it is characterised in that the acidic catalyst is trifluoromethayl sulfonic acid.
19. methods according to claim 10 or 11, it is characterised in that the silane coupler is selected from 3- (2,3- epoxies
Third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, 3-
Aminopropyl trimethoxysilane, gamma-aminopropyl-triethoxy-silane and 3- (2,3 the third oxygen of epoxy) hydroxypropyl methyl diethoxy silane
In one or more.
20. methods according to claim 19, it is characterised in that the silane coupler is 3- (2,3- the third oxygen of epoxy) third
Base trimethoxy silane or γ-methacryloxypropyl trimethoxy silane.
21. methods according to claim 10 or 11, it is characterised in that the end-capping reagent selected from tetramethyl disiloxane,
One or more in tetramethyl divinyl disiloxane and hexamethyl disiloxane.
22. methods according to claim 21, it is characterised in that the end-capping reagent is tetramethyl disiloxane.
23. methods according to claim 10 or 11, it is characterised in that the organic solvent is selected from toluene, dimethylbenzene, just
One or more in hexane, hexamethylene, carbon tetrachloride and ethyl acetate.
24. methods according to claim 23, it is characterised in that the organic solvent is toluene or dimethylbenzene.
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| CN105131291B (en) * | 2015-09-29 | 2017-10-17 | 肇庆皓明有机硅材料有限公司 | Tackifier and its preparation, cementability add-on type liquid silicon rubber and its preparation |
| CN106800655A (en) * | 2015-11-26 | 2017-06-06 | 比亚迪股份有限公司 | A kind of organic silicon rigidity-increasing stick and preparation method thereof and a kind of silica-gel composition |
| CN105504833A (en) * | 2016-01-22 | 2016-04-20 | 蒋柱明 | Single-component power-type organosilicon insulation paste for LED (light-emitting diode) packaging and preparation method thereof |
| CN105524281B (en) * | 2016-01-25 | 2018-06-26 | 广东恒大新材料科技有限公司 | A kind of borosilicate alkane modified silicone resin and add-on type resin combination and application |
| CN105802532B (en) * | 2016-05-26 | 2018-06-26 | 清远市美佳乐环保新材股份有限公司 | A kind of silicon boron tackifier and preparation method thereof and the application in two-component LED packaging plastics |
| CN106008983A (en) * | 2016-07-11 | 2016-10-12 | 广州双桃精细化工有限公司 | Silicon-boron tackifier and preparation method and application thereof |
| CN106543957B (en) * | 2016-10-14 | 2019-10-25 | 沈阳理工大学 | The poly- diphenyl Borosiloxane adhesive of bi-component toughening type and its methods for making and using same |
| CN107312496B (en) * | 2017-05-14 | 2020-05-29 | 杭州师范大学 | Adhesive addition type liquid silicone rubber |
| CN107275465B (en) * | 2017-06-29 | 2019-01-04 | 华中科技大学鄂州工业技术研究院 | LED encapsulation and preparation method thereof |
| CN108047449A (en) * | 2017-12-30 | 2018-05-18 | 汕头市骏码凯撒有限公司 | A kind of synthetic method of boracic tackifier |
| CN111154453B (en) * | 2020-01-19 | 2022-01-28 | 厦门艾贝森电子有限公司 | Heat-resistant single-component addition type organic silicon adhesive and preparation method thereof |
| CN112143258B (en) * | 2020-08-14 | 2022-04-19 | 杭州师范大学 | Preparation method and application of borosilicate siloxane modified white carbon black containing silicon-chlorine bonds |
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| CN103755964B (en) * | 2013-12-27 | 2016-03-30 | 深圳市安品有机硅材料有限公司 | Polysiloxane tackifying resin and preparation method thereof |
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