CN102634026A - Hydrogen-based silicone resin containing trifunctional group chain element and preparation method thereof - Google Patents
Hydrogen-based silicone resin containing trifunctional group chain element and preparation method thereof Download PDFInfo
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- CN102634026A CN102634026A CN2012100964224A CN201210096422A CN102634026A CN 102634026 A CN102634026 A CN 102634026A CN 2012100964224 A CN2012100964224 A CN 2012100964224A CN 201210096422 A CN201210096422 A CN 201210096422A CN 102634026 A CN102634026 A CN 102634026A
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- silicone resin
- hydrogen
- organoalkoxysilane
- functionality
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Links
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 51
- 239000001257 hydrogen Substances 0.000 title claims abstract description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 239000003377 acid catalyst Substances 0.000 claims abstract description 8
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 3
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 229940071870 hydroiodic acid Drugs 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 3
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 abstract description 11
- -1 alkoxy silane Chemical compound 0.000 abstract description 10
- 239000000047 product Substances 0.000 abstract description 9
- 229920001296 polysiloxane Polymers 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 3
- 229910000077 silane Inorganic materials 0.000 abstract 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000005022 packaging material Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000005538 encapsulation Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 7
- 229920002545 silicone oil Polymers 0.000 description 7
- 230000004044 response Effects 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 229910018557 Si O Inorganic materials 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920000260 silastic Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002512 suppressor factor Substances 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 244000037666 field crops Species 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000567 intoxicating Toxicity 0.000 description 1
- 230000002673 intoxicating effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention relates to hydrogen-based silicone resin containing a trifunctional group chain element and a preparation method thereof. The hydrogen-based silicone resin containing the trifunctional group chain element has the following structural general formula: (R12HSiO1/2) a (R2SiO3/2) b, wherein a is not less than 3 and is of an integer, b is not less than 1 and is of an integer, the relation between a and b meets the condition that b/a is not less than 0.33 and not more than 4, R1 is of alkyl with 1-3 carbon atoms, and R2 is of phenyl or alkyl with 1-3 carbon atoms. The preparation method sequentially comprises the following steps of: 1) mixing trifunctional alkoxy silane, tetra-alkyl-dihydro-disiloxane, an organic solvent and an acid catalyst; 2) adding water to perform hydrolysis on the trifunctional alkoxy silane; and 3) evaporating out byproducts so as to get the hydrogen-based silicone resin disclosed by the invention. The hydrogen-based silicone resin disclosed by the invention can be used for cross-linking and curing reaction of LED (light-emitting diode) packaging materials and other addition type polysiloxane, and has the characteristics of high curing speed and smooth appearance of the obtained product.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of based hydrogen-based silicone resin that contains the trifunctional chain link and preparation method thereof.
Background technology
Photodiode is called for short LED (Light Emitting Diode), is the solid state device of a based electroluminescent, and its structure mainly is made up of PN junction chip, electrode and optical system.LED has little, the safe low voltage of volume, good characteristics such as the life-span is long, electro-optical efficiency is high, response speed is fast, energy-saving and environmental protection, and it is referred to as " green illumination light source ".LED Application Areas now is very extensive, and state shows, sign illumination, backlight of LCD, traffic sign, picture and text show full-color screen and need pointolite or the interior lighting of area source all is the application market of LED.
The structure and the complex process of LED encapsulation, the packaged material of its use directly has influence on use properties and life-span.Traditional epoxy resin encapsulating material is crisp, the easy of crack of quality under light wave radiation and high temperature action, and there are defectives such as the decay of xanthochromia, luminous efficiency is fast in it.Compare with epoxy resin; Organosilicon encapsulating material has excellent moisture resistance, insulativity and flexibility; And with its outstanding heat-proof aging and ultraviolet aging resistance performance, and characteristics such as optical attenuation is extremely low, become the best materials of current LED encapsulation; It is replacing traditional epoxy resin, and is widely used.
Organosilicon material is used in the LED encapsulation; Common main body system consists of; Organopolysiloxane to contain vinyl is a base polymer, and the organopolysiloxane that contains a plurality of Si-H keys is a linking agent, under the platinum group catalyst effect; Under room temperature or heating condition, carry out hydrogen silication addition reaction, thereby obtain having the Zylox and the silicone resin of cross-linked network structure.The organopolysiloxane linking agent that wherein contains a plurality of Si-H keys is generally low viscous line style methylhydrogenpolysi,oxane, is commonly called as containing hydrogen silicone oil.
For example, disclosing a kind of among the one Chinese patent application CN201010239022.5 is raw material with octamethylcyclotetrasiloxane, tetramethyl-tetrahydrochysene cyclotetrasiloxane and closure agent, and polymerization obtains the preparation method of line style containing hydrogen silicone oil under an acidic catalyst.But synthetic linking agent in this way, thus in carrying out the process of hydrogen silication addition reaction preparation LED encapsulation with silastic material, its speed of response is slower, and finished surface is prone to fold and decorative pattern, influences production efficiency and luminous efficiency that LED encapsulates.
One Chinese patent application 200910302074 discloses a kind of method for preparing the phenyl resin, and this method is not used solvent in the preparation process.Yet organic solvent is highly beneficial to preparation feedback.If solvent-free, stock yard is very easy to take place cross-linked network in the reaction process, produces gelation even becomes solid, thereby can not get the purpose product.In addition, all use two functionality organoalkoxysilanes among the embodiment of this application, so contained two functional group's link configuration in its product.And this product reactive behavior in addition-crosslinked reaction that contains two functional group's link configuration is low, thereby causes speed of response slow, and resulting addition-crosslinked reaction product fold has lines, can not reach the requirement of flat appearance light.
Summary of the invention
For solving existing problem in the above-mentioned prior art, the invention provides a kind of based hydrogen-based silicone resin that contains the trifunctional chain link and preparation method thereof.
Particularly, the invention provides:
(1) a kind of based hydrogen-based silicone resin that contains the trifunctional chain link, it has following general structure:
(R
1 2HSiO
1/2)
a(R
2SiO
3/2)
b，
Wherein, (R
1 2HSiO
1/2)
aBe simple function group chain link, (R
2SiO
3/2)
bBe the trifunctional chain link, a>=3 and be integer, b>=1 and be integer, the relation of a and b satisfies 0.33≤b/a≤4, R
1For having the alkyl of 1～3 carbon atom, R
2For phenyl or have the alkyl of 1～3 carbon atom.
(2) according to (1) described based hydrogen-based silicone resin, wherein, the relation of a and b satisfies 0.4≤b/a≤2.5.
(3) a kind of method for preparing according to (1) described based hydrogen-based silicone resin, it comprises the step that next coming in order carry out:
1) three-functionality-degree organoalkoxysilane, tetraalkyl dihydro sily oxide, organic solvent and acid catalyst are mixed; Wherein, Alkyl in the said tetraalkyl dihydro sily oxide comprises 1～3 carbon atom independently of one another, and the mol ratio of said three-functionality-degree organoalkoxysilane and said tetraalkyl dihydro sily oxide is (0.67～8): 1;
2) under 40 ℃～90 ℃, add entry, under refluxad continue reaction 1～4 hour afterwards;
3) 85 ℃～110 ℃ down distillations, add alkaline neutraliser after the gained residuum is cooled to 40 ℃～50 ℃, filter, with gained filtrating 70 ℃～140 ℃ following underpressure distillation, thereby obtain said based hydrogen-based silicone resin.
(4) according to (3) described method, wherein, in said step 1), the mol ratio of said three-functionality-degree organoalkoxysilane and said tetraalkyl dihydro sily oxide is (0.8～5): 1.
(5) according to (3) described method; Wherein, In said step 1), said three-functionality-degree organoalkoxysilane is to be selected from methyltrimethoxy silane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, ethyl trimethoxy silane, the ethyl triethoxysilane one or more.
(6) according to (3) described method, wherein, in said step 1), said organic solvent is to be selected from varsol, ketones solvent, alcoholic solvent, the esters solvent one or more; And wherein, the consumption of said organic solvent be said three-functionality-degree organoalkoxysilane and said tetraalkyl dihydro sily oxide the quality sum 10%～400%.
(7) according to (6) described method, wherein, said varsol is selected from toluene, YLENE and/or industrial naptha; Said ketones solvent is selected from methylethylketone, acetone, butanone and/or pimelinketone; Said alcoholic solvent is selected from methyl alcohol, ethanol and/or Virahol; Said esters solvent is selected from ETHYLE ACETATE and/or methyl-formiate.
(8) according to (3) described method; Wherein, In said step 1), said acid catalyst is to be selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, sulfonic acid, formic acid, acetate, oxalic acid, tartrate, phenylformic acid, tosic acid, Hydrogen bromide, hydroiodic acid HI, the acidic white earth one or more; And wherein, the consumption of said an acidic catalyst be said three-functionality-degree organoalkoxysilane and said tetraalkyl dihydro sily oxide the quality sum 0.1%～3%.
(9) according to (3) described method, wherein, in said step 2) in, said water dropwise adds, and the consumption of said water is 50%～200% of the required water total mass of the said three-functionality-degree organoalkoxysilane of complete hydrolysis.
(10) according to (3) described method, wherein, in said step 3), said alkaline neutraliser is to be selected from sodium hydrogencarbonate, TMAH, the pyridine one or more.
The present invention compared with prior art has the following advantages and positively effect:
1. the invention provides a kind of based hydrogen-based silicone resin that contains the trifunctional chain link; Compare with line style containing hydrogen silicone oil of the prior art; It has advantages such as reactive behavior height, speed of response be fast; Be particularly suitable for the linking agent as the LED organosilicon encapsulating material, also can in the cross-linking and curing reaction of the addition type polysiloxane of other purposes, use as linking agent.
2. its transparency of the based hydrogen-based silicone resin that contains the trifunctional chain link of the present invention is high, and specific refractory power is 1.41～1.53, and has radiation hardness, high-low temperature resistant, advantage such as weather-proof.The LED product that uses the based hydrogen-based silicone resin that contains the trifunctional chain link of the present invention to make has the characteristic of flat appearance light, and this can improve the production efficiency and the luminous efficiency of LED encapsulation.
Embodiment
Below description through embodiment the present invention is described further; But this is not to be limitation of the present invention; Those skilled in the art are according to basic thought of the present invention; Can make various modifications or improvement, but only otherwise break away from basic thought of the present invention, all within scope of the present invention.
The invention provides a kind of based hydrogen-based silicone resin that contains the trifunctional chain link, and a kind of preparation contains the method for the based hydrogen-based silicone resin of trifunctional chain link.
Particularly, one aspect of the present invention provides a kind of based hydrogen-based silicone resin that contains the trifunctional chain link, and it has following general structure:
(R
1 2HSiO
1/2)
a(R
2SiO
3/2)
b，
(R
1 2HSiO
1/2)
aBe simple function group chain link, (R
2SiO
3/2)
bBe the trifunctional chain link, a>=3 and be integer, b>=1 and be integer, the relation of a and b satisfies 0.33≤b/a≤4, R
1For having the alkyl of 1～3 carbon atom, R
2For phenyl or have the alkyl of 1～3 carbon atom.
Preferably, in above-mentioned general formula, the relation of a and b preferably satisfies 0.4≤b/a≤2.5.
The based hydrogen-based silicone resin that contains the trifunctional chain link of the present invention is owing to have the trifunctional link configuration, so reactive behavior is high, speed of response is fast, is particularly suitable for as the linking agent in the cross-linking and curing reaction of LED packaged material and other addition type polysiloxane.
In addition, the transparency height that contains the based hydrogen-based silicone resin of trifunctional chain link of the present invention utilizes ultraviolet-visible pectrophotometer, and under the 0.5cm thickness, between 500nm～860nm, its transsmissivity is all greater than 99%.Therefore based hydrogen-based silicone resin of the present invention has optically transparent characteristic, and the product that makes during as linking agent has the characteristic of appearance transparent, light.
Another aspect of the present invention provides a kind of preparation to contain the method for the based hydrogen-based silicone resin of trifunctional chain link.This method comprises the step that next coming in order carry out: 1) three-functionality-degree organoalkoxysilane, tetraalkyl dihydro sily oxide, organic solvent and acid catalyst are mixed; Wherein, Alkyl in the said tetraalkyl dihydro sily oxide comprises 1～3 carbon atom independently of one another, and the mol ratio of said three-functionality-degree organoalkoxysilane and said tetraalkyl dihydro sily oxide is (0.67～8): 1; 2) under 40 ℃～90 ℃, add entry, under refluxad continue reaction 1～4 hour afterwards; 3) under 85 ℃～110 ℃, steam partial solvent and by product (for example water, alcohol), add alkaline neutraliser after being cooled to 40 ℃～50 ℃, filter, with gained filtrating 70 ℃～140 ℃ following underpressure distillation, to steam whole solvents and by product (for example water, alcohol).
Preferably, in step 1), the mol ratio of said three-functionality-degree organoalkoxysilane and said tetraalkyl dihydro sily oxide is (0.8～5): 1 above-mentioned.
The simple function group chain link is also claimed the M chain link, is provided by tetraalkyl dihydro sily oxide, and the trifunctional chain link is also claimed the T chain link, is provided by the three-functionality-degree organoalkoxysilane.In the present invention, R
1 2HSiO
1/2Be the M chain link, R
2SiO
3/2Be the T chain link, therefore, the based hydrogen-based silicone resin that contains the trifunctional chain link also can be described as the MT based hydrogen-based silicone resin.
In step 1) and 2) in, under acidic conditions, the Si-O key of the tetraalkyl dihydro sily oxide of 1mol breaks off, and can produce the R of 2mol
1 2HSiO
1/2, i.e. M chain link.And in the presence of acid and enough water, the reaction that can be hydrolyzed of three-functionality-degree organoalkoxysilane, generation R
2SiO
3/2, i.e. T chain link.Three-functionality-degree organoalkoxysilane self carries out condensation reaction simultaneously, perhaps carries out condensation reaction with the M chain link, and dehydration also generates by-product alcohol, forms new Si-O chain.
Reacting with methyltrimethoxy silane and tetramethyl-dihydro sily oxide is example, and its reaction formula is:
Wherein, tetramethyl-dihydro sily oxide generates (CH under acidic conditions
3)
2HSiO
1/2, the reaction that partly is hydrolyzed of the methoxyl group in the methyltrimethoxy silane, methoxyl group is substituted by hydroxyl, and generates by-product carbinol.Simultaneously, carry out condensation reaction after the methyltrimethoxy silane hydrolysis each other, perhaps itself and (CH
3)
2HSiO
1/2Carry out condensation reaction.
In step 3), the purpose that steams by product is unnecessary water and alcohol are shifted out system, promotes reaction to carry out to the condensation direction, thereby forms the macromole product.In addition, can recently control product structure, the i.e. ratio of M chain link and T chain link through the mole of control three-functionality-degree organoalkoxysilane and tetraalkyl dihydro sily oxide.The present invention is controlled to be (0.67～8) with the mol ratio of three-functionality-degree organoalkoxysilane and tetraalkyl dihydro sily oxide: 1, be preferably (0.8～5): and 1, acquisition contains the based hydrogen-based silicone resin of trifunctional chain link thus.
In the present invention, preferably, the three-functionality-degree organoalkoxysilane has general formula R
2Si (OR
3), wherein, R
2For phenyl or have the alkyl of 1～3 carbon atom, R
3For having the saturated hydrocarbyl of 1～2 carbon atom, comprise methyl, ethyl.In the present invention, operable three-functionality-degree organoalkoxysilane is to be selected from methyltrimethoxy silane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, ethyl trimethoxy silane, the ethyl triethoxysilane one or more.
In the present invention, operable organic solvent is to be selected from varsol, ketones solvent, alcoholic solvent, the esters solvent one or more.Said varsol is selected from toluene, YLENE and/or industrial naptha; Said ketones solvent is selected from methylethylketone, acetone, butanone and/or pimelinketone; Said alcoholic solvent is selected from methyl alcohol, ethanol and/or Virahol; Said esters solvent is selected from ETHYLE ACETATE and/or methyl-formiate.Preferably, organic solvent used in the present invention is a varsol, for example one or more in toluene, YLENE, the industrial naptha.
Preferably, in the step 1) amount of employed organic solvent be said three-functionality-degree organoalkoxysilane and said tetraalkyl dihydro sily oxide the quality sum 10%～400%, be preferably 30%～200%.
In the present invention; Operable acid catalyst is to be selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, sulfonic acid, formic acid, acetate, oxalic acid, tartrate, phenylformic acid, tosic acid, Hydrogen bromide, hydroiodic acid HI, the acidic white earth one or more, is preferably in hydrochloric acid, sulfuric acid, sulfonic acid, the acidic white earth one or more.
Preferably, in the step 1) amount of employed catalyzer be said three-functionality-degree organoalkoxysilane and said tetraalkyl dihydro sily oxide the quality sum 0.1%～3%, be preferably 0.15%～2%.
In the present invention, employed water is deionized water preferably, step 2).More preferably, water dropwise adds, and the amount that is added is 50%～200% of the required water total mass of the said three-functionality-degree organoalkoxysilane of complete hydrolysis, is preferably 60%～150%.
In the present invention, operable alkaline neutraliser is to be selected from sodium hydrogencarbonate, TMAH, the pyridine one or more.
Do not limit the consumption of employed alkaline neutraliser in the step 3) is concrete, as long as can the acid that add before be neutralized fully.For example, the consumption of this alkaline neutraliser is 100%～500% of required total mass that the acid that adds is before neutralized fully.
According to a kind of specific embodiments of the present invention; The method that preparation contains the based hydrogen-based silicone resin of trifunctional chain link comprises the step that next coming in order carry out: 1) three-functionality-degree organoalkoxysilane and tetramethyl-dihydro sily oxide are (0.67～5) in molar ratio: 1 mixes; Join in the reaction flask that has backflow and whipping appts, add organic solvent and acid catalyst simultaneously; 2) under constant agitation, dropwise add deionized water in 40 ℃～90 ℃, continue afterwards to stir also and refluxed 1～4 hour, wherein, the consumption of deionized water is 50%～200% of the required deionized water total mass of complete hydrolysis three-functionality-degree organoalkoxysilane; 3) make water distilling apparatus into, be warmed up to 85 ℃～110 ℃ and steam by product.Cooling back adds alkaline neutraliser, filters, and filtrating is carried out the pump vacuum decompression, under 70 ℃～140 ℃, distills out low-boiling-point substance and discards, and obtains to contain the based hydrogen-based silicone resin of trifunctional chain link thus.
Below further explain or explain content of the present invention through the mode of example, but these examples should not be understood that the restriction to protection scope of the present invention.
Embodiment
In following examples; Methyltrimethoxy silane and Union carbide A-162 are available from Qufu morning twilight chemical industry ltd; Tetramethyl-dihydro sily oxide is available from ACROS company, and conventional reagent such as YLENE, toluene, sulfuric acid, hydrochloric acid, absolute ethyl alcohol, anhydrous methanol, pyridine, sodium hydrogencarbonate are available from the Beijing Chemical Plant, and trifluoromethanesulfonic acid is available from Japanese great achievement KCC; Vacuum pump is available from the Ke Rui of Gongyi City Instr Ltd., and NDJ-79 type rotational viscosimeter is available from dynamo-electric factory of Tongji University.
Embodiment 1
136g methyltrimethoxy silane, 67g tetramethyl-dihydro sily oxide, 70g YLENE and the 0.35g vitriol oil are added in the 500ml there-necked flask, under 55 ℃, constant agitation, dropwise add the 35g deionized water, carried out about 50 minutes, refluxed afterwards 1.5 hours.Make water distilling apparatus into, be warmed up to 105 ℃, distill out by product.After being cooled to 45 ℃, add the 0.8g pyridine, stir and made solution become neutrality in about 30 minutes.Utilize filter paper filtering, afterwards, under 130 ℃, utilize the vacuum pump underpressure distillation to go out solvent xylene and lower-molecular substance, thereby obtain the water white based hydrogen-based silicone resin that contains the trifunctional chain link of 123g.Utilize NDJ-79 type rotational viscosimeter to record its viscosity and be 15mPa.s, utilizing nuclear magnetic resonance method to record its active H massfraction is 0.7%.
Embodiment 2
267g Union carbide A-162,67g tetramethyl-dihydro sily oxide, 360g toluene and 3.3g concentrated hydrochloric acid are added in the 1000ml there-necked flask, under 85 ℃, constant agitation, dropwise add the 100g deionized water, carried out about 50 minutes, refluxed afterwards 3.5 hours.Make water distilling apparatus into, be warmed up to 100 ℃, distill out by product.After being cooled to 42 ℃, add the 3.5g sodium hydrogencarbonate, stir and made solution become neutrality in about 30 minutes.Utilize filter paper filtering, afterwards, under 120 ℃, utilize the vacuum pump underpressure distillation to go out solvent toluene and lower-molecular substance, thereby obtain the water white based hydrogen-based silicone resin that contains the trifunctional chain link of 150g.Utilize the mode identical with embodiment 1, recording its viscosity is 21mPa.s, and active H massfraction is 0.58%.
Embodiment 3
102g methyltrimethoxy silane, 67g tetramethyl-dihydro sily oxide, 10g absolute ethyl alcohol and 140g toluene, 0.33g trifluoromethanesulfonic acid are added in the 500ml there-necked flask; Under 60 ℃ of constant agitation; Dropwise add the 40g deionized water, carried out about 35 minutes, refluxed afterwards 2 hours.Make water distilling apparatus into, be warmed up to 105 ℃, distill out by product.After being cooled to 48 ℃, add the 1.5g sodium hydrogencarbonate, stir and made solution become neutrality in about 30 minutes.Utilize filter paper filtering, afterwards, under 130 ℃, utilize the vacuum pump underpressure distillation to go out solvent toluene, ethanol and lower-molecular substance, thereby obtain the water white based hydrogen-based silicone resin that contains the trifunctional chain link of 109g.Utilize the mode identical with embodiment 1, recording its viscosity is 12mPa.s, and active H massfraction is 0.79%.
Embodiment 4
With 31g methyltrimethoxy silane, 41g Union carbide A-162,67g tetramethyl-dihydro sily oxide, 15g anhydrous methanol and 150g industrial naptha, 1.8g concentration is that 70% perchloric acid adds in the 500ml there-necked flask; Under 70 ℃ of constant agitation; Dropwise add the 35g deionized water; Carried out about 40 minutes, refluxed afterwards 2.5 hours.Make water distilling apparatus into, be warmed up to 90 ℃, distill out by product.Be cooled to after 44 ℃, add the 4g sodium hydrogencarbonate, stir and made solution become neutrality in about 30 minutes.Utilize filter paper filtering, afterwards, under 85 ℃, utilize the vacuum pump underpressure distillation to go out industrial naptha, methyl alcohol, ethanol and lower-molecular substance, thereby obtain the water white based hydrogen-based silicone resin that contains the trifunctional chain link of 91g.Utilize the mode identical with embodiment 1, recording its viscosity is 9mPa.s, and active H massfraction is 0.95%.
Test Example 1
With α; ω-divinyl polydimethylsiloxane, the MQ resin (its silicone resin for being made up of simple function group Si-O unit (M unit) and four-functional group Si-O unit (Q unit)), suppressor factor and the platinum group catalyst that contain vinyl mix, and form basic pre-composition.Several kinds of different hydrogeneous linking agents (seeing table 2) are mixed with above-mentioned basic prepolymer respectively once more, and the addition of several kinds of different hydrogeneous linking agents makes that all the mol ratio of Si-H/Si-Vi is 1.1: 1.After vacuum defoamation, in the mould of 6 * 6cm, toasted one hour the external appearance characteristic (seeing table 1) of each Zylox print of observation post's acquisition afterwards down at 150 ℃.Respectively above-mentioned each sample for preparing of 20g is put into beaker, observe their gel time down at 25 ℃, thereby compare.Prescription and result see table 1.
Table 1
In above-mentioned prescription is formed, α, the viscosity of ω-divinyl polydimethylsiloxane is 5000mPa.s, the vinyl massfraction is 0.12%; The M/Q value that contains the MQ resin of vinyl is 0.8, and the massfraction of vinyl is 5.4%; Suppressor factor is the 1-ethynylcyclohexanol; Platinum group catalyst is the Karstedt platinum catalyst, and the platiniferous massfraction is 1%; Linking agent 1 is the based hydrogen-based silicone resin that contains the trifunctional chain link of embodiment 1; Linking agent 2 is the based hydrogen-based silicone resin that contains the trifunctional chain link of embodiment 2; Linking agent 3 is the based hydrogen-based silicone resin that contains the trifunctional chain link of embodiment 3; Linking agent 4 is the based hydrogen-based silicone resin that contains the trifunctional chain link of embodiment 4; Linking agent 5 is respectively the different line style of hydrogen content (two functional group's chain links) containing hydrogen silicone oil 1 and line style containing hydrogen silicone oil 2 (available from land for growing field crops, Panshi City auxiliary chemicals institute) with linking agent 6.The parameter of these hydrogeneous linking agents is seen table 2.
Table 2
Can know by table 1; In the reaction of silastic elastomer print; Compare with line style containing hydrogen silicone oil linking agent, the based hydrogen-based silicone resin linking agent that contains the trifunctional chain link of the present invention makes that the product that is obtained is attractive in appearance, smooth corrugationless phenomenon; This is extremely beneficial in the LED encapsulation field, and this can improve the production efficiency and the luminous efficiency of LED encapsulation.
In addition, can know, compare with line style containing hydrogen silicone oil linking agent by table 1; The gel time that contains the based hydrogen-based silicone resin of trifunctional chain link of the present invention significantly reduces, and this shows that its reactive behavior is high, and speed of response is fast; This also is favourable in the LED encapsulation field; It can eliminate the fluorescent material settlement issues, alleviates addition curing catalysts intoxicating phenomenon, and enhances productivity.
Claims (10)
1. based hydrogen-based silicone resin that contains the trifunctional chain link, it has following general structure:
(R
1 2HSiO
1/2)
a(R
2SiO
3/2)
b，
Wherein, (R
1 2HSiO
1/2)
aBe simple function group chain link, (R
2SiO
3/2)
bBe the trifunctional chain link, a>=3 and be integer, b>=1 and be integer, the relation of a and b satisfies 0.33≤b/a≤4, R
1For having the alkyl of 1～3 carbon atom, R
2For phenyl or have the alkyl of 1～3 carbon atom.
2. based hydrogen-based silicone resin according to claim 1, wherein, the relation of a and b satisfies 0.4≤b/a≤2.5.
3. method for preparing based hydrogen-based silicone resin according to claim 1, it comprises the step that next coming in order carry out:
1) three-functionality-degree organoalkoxysilane, tetraalkyl dihydro sily oxide, organic solvent and acid catalyst are mixed; Wherein, Alkyl in the said tetraalkyl dihydro sily oxide comprises 1～3 carbon atom independently of one another, and the mol ratio of said three-functionality-degree organoalkoxysilane and said tetraalkyl dihydro sily oxide is (0.67～8): 1;
2) under 40 ℃～90 ℃, add entry, under refluxad continue reaction 1～4 hour afterwards;
3) 85 ℃～110 ℃ down distillations, add alkaline neutraliser after the gained residuum is cooled to 40 ℃～50 ℃, filter, with gained filtrating 70 ℃～140 ℃ following underpressure distillation, thereby obtain said based hydrogen-based silicone resin.
4. method according to claim 3, wherein, in said step 1), the mol ratio of said three-functionality-degree organoalkoxysilane and said tetraalkyl dihydro sily oxide is (0.8～5): 1.
5. method according to claim 3; Wherein, In said step 1), said three-functionality-degree organoalkoxysilane is to be selected from methyltrimethoxy silane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, ethyl trimethoxy silane, the ethyl triethoxysilane one or more.
6. method according to claim 3, wherein, in said step 1), said organic solvent is to be selected from varsol, ketones solvent, alcoholic solvent, the esters solvent one or more; And wherein, the consumption of said organic solvent be said three-functionality-degree organoalkoxysilane and said tetraalkyl dihydro sily oxide the quality sum 10%～400%.
7. method according to claim 6, wherein, said varsol is selected from toluene, YLENE and/or industrial naptha; Said ketones solvent is selected from methylethylketone, acetone, butanone and/or pimelinketone; Said alcoholic solvent is selected from methyl alcohol, ethanol and/or Virahol; Said esters solvent is selected from ETHYLE ACETATE and/or methyl-formiate.
8. method according to claim 3; Wherein, In said step 1), said acid catalyst is to be selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, sulfonic acid, formic acid, acetate, oxalic acid, tartrate, phenylformic acid, tosic acid, Hydrogen bromide, hydroiodic acid HI, the acidic white earth one or more; And wherein, the consumption of said an acidic catalyst be said three-functionality-degree organoalkoxysilane and said tetraalkyl dihydro sily oxide the quality sum 0.1%～3%.
9. method according to claim 3, wherein, in said step 2) in, said water dropwise adds, and the consumption of said water is 50%～200% of the required water total mass of the said three-functionality-degree organoalkoxysilane of complete hydrolysis.
10. method according to claim 3, wherein, in said step 3), said alkaline neutraliser is to be selected from sodium hydrogencarbonate, TMAH, the pyridine one or more.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059301A (en) * | 2012-12-11 | 2013-04-24 | 曹坚林 | A kind of phenyl hydrogen-containing network silicone resin for LED encapsulation and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4615782A (en) * | 1984-06-11 | 1986-10-07 | Nippon Telegraph And Telephone Corporation | Intermediate layer material of three-layer resist system and method of forming resist pattern |
| CN101712800A (en) * | 2009-11-06 | 2010-05-26 | 陈俊光 | Organic silicon resin encapsulant of large power LED and preparing method thereof |
| CN101891893A (en) * | 2010-07-23 | 2010-11-24 | 深圳市安品有机硅材料有限公司 | Preparation method of phenyl-based hydrogen-based silicone resin for encapsulating LED |
-
2012
- 2012-04-01 CN CN201210096422.4A patent/CN102634026B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4615782A (en) * | 1984-06-11 | 1986-10-07 | Nippon Telegraph And Telephone Corporation | Intermediate layer material of three-layer resist system and method of forming resist pattern |
| CN101712800A (en) * | 2009-11-06 | 2010-05-26 | 陈俊光 | Organic silicon resin encapsulant of large power LED and preparing method thereof |
| CN101891893A (en) * | 2010-07-23 | 2010-11-24 | 深圳市安品有机硅材料有限公司 | Preparation method of phenyl-based hydrogen-based silicone resin for encapsulating LED |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059301A (en) * | 2012-12-11 | 2013-04-24 | 曹坚林 | A kind of phenyl hydrogen-containing network silicone resin for LED encapsulation and preparation method thereof |
| CN103540289A (en) * | 2013-05-23 | 2014-01-29 | 杭州师范大学 | Preparation method and application of organic silicon resin adhesive |
| CN103762298A (en) * | 2014-02-02 | 2014-04-30 | 芜湖市神龙新能源科技有限公司 | LED wafer combination package material and technology |
| CN104086771A (en) * | 2014-07-15 | 2014-10-08 | 广东万木新材料科技有限公司 | Preparation method of low-water-absorptivity phenyl hydrogen-containing silicon resin |
| CN104513644A (en) * | 2014-12-10 | 2015-04-15 | 东莞兆舜有机硅新材料科技有限公司 | Transparent pouring sealant and use thereof |
| CN105542167A (en) * | 2016-02-22 | 2016-05-04 | 山东省科学院新材料研究所 | Phenyl hydrogen polysiloxane and preparation method thereof |
| CN105542167B (en) * | 2016-02-22 | 2018-01-09 | 山东省科学院新材料研究所 | A kind of phenyl-based hydrogen-based polysiloxanes and preparation method thereof |
| CN109705801A (en) * | 2018-12-30 | 2019-05-03 | 苏州桐力光电股份有限公司 | A kind of addition-type silicon rubber |
| CN109796881A (en) * | 2018-12-30 | 2019-05-24 | 苏州桐力光电股份有限公司 | A kind of assemble method of the touch display screen of vehicle-mounted middle control |
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