CN103387672B - A kind of preparation method of the polyorganosiloxane resin containing Allyl end groups - Google Patents
A kind of preparation method of the polyorganosiloxane resin containing Allyl end groups Download PDFInfo
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- CN103387672B CN103387672B CN201310364451.9A CN201310364451A CN103387672B CN 103387672 B CN103387672 B CN 103387672B CN 201310364451 A CN201310364451 A CN 201310364451A CN 103387672 B CN103387672 B CN 103387672B
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Abstract
A kind of preparation method of the polyorganosiloxane resin containing Allyl end groups, it relates to a kind of preparation method of polyorganosiloxane resin, the present invention is the problem of the temperature tolerance difference that will solve existing silicone body thermostable resin, the present invention is a kind of polyorganosiloxane resin containing Allyl end groups, by volume number be refining by 1 part after allyl silicane, 1-5 part organic solvent, 1 ~ 3 part of deionized water and 0.05 ~ 0.1 part of catalyzer make.Polyorganosiloxane resin containing Allyl end groups of the present invention is larger than vinyl system molecular weight, and narrowly distributing, cage structure ratio does not reduce, and theoretical temperature tolerance is better, and the present invention is applied to high-performance organic materials field.
Description
Technical field
The present invention relates to a kind of preparation method of polyorganosiloxane resin.
Background technology
Many great Model engineerings of man of China etc. are badly in need of high temperature resistant, thin-walled high wave transparent sandwich.Although there is the technology of preparing of many fire resistant resins in China, the subject matter existed is the requirement that matrix resin can not meet applied at elevated temperature and moulding process, and current high-speed and high-temperature occasion is still based on ceramic and metallic substance.Overall in high-temperature resin system existing prior art set out with vinyl silanes and prepare the technology of vinyl sesquialter polysiloxane (Vi-POSS), this hybrid inorganic-organic materials is the main direction of studying of current silicone body thermostable resin, form product, but its functional group's synthesis technique is comparatively complicated, silicone hydroxyl content is higher, hydrolysis reaction is incomplete, and molecular weight is relatively low, and temperature tolerance is also undesirable.
Summary of the invention
The present invention is the problem of the temperature tolerance difference that will solve existing silicone body thermostable resin, provides a kind of polyorganosiloxane resin containing Allyl end groups.
The present invention is a kind of polyorganosiloxane resin containing Allyl end groups, by volume number be refining by 1 part after allyl silicane, 1-5 part organic solvent, 1 ~ 3 part of deionized water and 0.05 ~ 0.1 part of catalyzer make.
The present invention has synthesized a kind of normal temperature liquid resin, main component is the silicone resin containing Allyl end groups, allyl group silicon sesquialter cage structure wherein containing high level, due to the confession electrical effect of allyl group, the hydrolysis reaction activity of monomer is better than traditional vinyl groups, and hydrolysis is comparatively complete, and molecular weight of product is larger, narrow distribution, has better theoretical temperature tolerance.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the allyltriethoxysilane in test 1;
Fig. 2 is the infrared spectrum after the hydrolysis of the polyorganosiloxane resin containing Allyl end groups of test 1 preparation.
Embodiment:
Embodiment one: a kind of polyorganosiloxane resin containing Allyl end groups of present embodiment, by volume number be refining by 1 part after allyl silicane, 1-5 part organic solvent, 1 ~ 3 part of deionized water and 0.05 ~ 0.1 part of catalyzer make.
Present embodiment has synthesized a kind of normal temperature liquid resin, main component is the silicone resin containing Allyl end groups, allyl group silicon sesquialter cage structure wherein containing high level, due to the confession electrical effect of allyl group, the hydrolysis reaction activity of monomer is better than traditional vinyl groups, and hydrolysis is comparatively complete, and molecular weight of product is larger, narrow distribution, has better theoretical temperature tolerance.
Embodiment two: present embodiment and embodiment one unlike: described refining after allyl silicane be by water distilling apparatus distillating material allyltriethoxysilane, collect that 160 DEG C of-170 DEG C of cuts obtain.Other are identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: described organic solvent be one or more of methyl alcohol, acetone, toluene, tetrahydrofuran (THF) and dehydrated alcohol by arbitrarily than the mixture formed.Other are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: described catalyzer to be mass concentration be 35 ~ 38% concentrated hydrochloric acid or mass concentration be 96% organotin solution.Other steps are identical with one of embodiment one to three with parameter.
Embodiment five: one of present embodiment and embodiment one to four unlike: described is 15 ~ 25% containing the volumetric molar concentration containing Allyl end groups cage group in the polyorganosiloxane resin of Allyl end groups.Other steps are identical with one of embodiment one to four with parameter.
Embodiment six: one of present embodiment and embodiment one to five unlike: the preparation method of the described polyorganosiloxane resin containing Allyl end groups is undertaken by following steps: one, by water distilling apparatus distillating material allyltriethoxysilane, collect 160 DEG C of-170 DEG C of cuts, obtain the allyl silicane after refining; Two, the allyl silicane that by volume number gets refining latter 1 part mixes with 1-5 part organic solvent and adds in reactor, from room temperature to 20 ~ 80 DEG C, adds deionized water and 0.05 ~ 0.1 part of catalyzer of 1-3 part, hydrolysis reaction 3-5h in temperature-rise period; Then continue to be warming up to water, alcohols and the micromolecule catalyst in 80 ~ 120 DEG C of use water trap separated products, obtain crude product resin; Three, gained crude product resin is inserted layering in separating funnel, get organic phase resin, twice underpressure distillation is carried out under 60-150 DEG C of temperature range and 0.05-0.09Mpa vacuum tightness, after removing solvent wherein, i.e. the obtained polyorganosiloxane resin containing Allyl end groups.Other steps are identical with one of embodiment one to five with parameter.
By following verification experimental verification beneficial effect of the present invention:
Test 1, this test contain the polyorganosiloxane resin of Allyl end groups, volume parts is the allyl silicane after refining by 1 part, 2 parts of organic solvents, 1 part of deionized water and 0.05 part of catalyzer are made, wherein organic solvent is toluene, catalyzer to be mass concentration be 35% ~ 38% hydrochloric acid.
The preparation method of the polyorganosiloxane resin containing Allyl end groups in this test is: one, by water distilling apparatus distillating material allyltriethoxysilane, collect 160 DEG C of-170 DEG C of cuts, obtains the allyl silicane after refining; Two, the allyl silicane that by volume number gets refining latter 1 part mixes with 2 parts of organic solvents and adds in reactor, from room temperature to 80 DEG C, adds deionized water and 0.05 part of catalyzer of 1 part, hydrolysis reaction 4h; Then continue to be warming up to water, alcohols and the micromolecule catalyst in 120 DEG C of use water trap separated products, obtain crude product resin; Three, gained crude product resin is inserted layering in separating funnel, get organic phase resin, twice underpressure distillation is carried out under 60-150 DEG C of temperature range and 0.05-0.09Mpa vacuum tightness, after removing solvent wherein, i.e. the obtained polyorganosiloxane resin containing Allyl end groups.
The infrared spectrum (see Fig. 1) polyorganosiloxane resin containing Allyl end groups of this test preparation being carried out to the raw material allyltriethoxysilane of FTIR spectrum sign (see Fig. 2) simultaneous test step one can find that synthetic product is at 1081cm
-1and 1105cm
-1the sharply bimodal of place becomes wider bimodal 1097cm
-1and 1166cm
-1, the Si-O key illustrating in raw material there occurs hydrolytic condensation and defines Si-O-Si key, and part defines silicon sesquialter cage structure, and another part defines the silicone resin structure of irregularity.1632cm in product
-1the allyl group group double bond characteristic peak at place is unchanged, and proves double bond C in allyl group and have neither part nor lot in reaction, so characterize according to infrared structure, can determine to obtain the silicone resin with Allyl end groups, wherein containing part silicon sesquialter cage structure.
Gel chromatography test (THF, 1ml/min, PS are carried out to the polyorganosiloxane resin containing Allyl end groups of this test preparation, 303K), record synthetic product and contain two components, component one Mn is about about 3000, dispersion coefficient is about 1.50, and peak area is 82.1%; Component 2Mn is about 650, and dispersion coefficient is about 1.21, and peak area is 17.9%, and describe the silicone resin that in the product of this experiment acquisition, major part is irregularity structure, small part is silicon times half structure polysiloxane.
Claims (1)
1. the preparation method containing the polyorganosiloxane resin of Allyl end groups, it is characterized in that the method is undertaken by following steps: one, by water distilling apparatus distillating material allyltriethoxysilane, collect 160 DEG C of-170 DEG C of cuts, obtain the allyl silicane after refining; Two, the allyl silicane that by volume number gets refining latter 1 part mixes with 1-5 part organic solvent and adds in reactor, is warming up to 20 ~ 80 DEG C, adds deionized water and 0.05 ~ 0.1 part of catalyzer of 1-3 part, hydrolysis reaction 3-5h in temperature-rise period; Then continue to be warming up to water, alcohols and the micromolecule catalyst in 80 ~ 120 DEG C of use water trap separated products, obtain crude product resin; Three, gained crude product resin is inserted layering in separating funnel, get organic phase resin, twice underpressure distillation is carried out under 60-150 DEG C of temperature range and 0.05-0.09MPa vacuum tightness, after removing solvent wherein, i.e. the obtained polyorganosiloxane resin containing Allyl end groups;
Wherein said catalyzer to be mass concentration be 35 ~ 38% concentrated hydrochloric acid or mass concentration be 96% organotin solution; Described is 15 ~ 25% containing the volumetric molar concentration containing Allyl end groups cage group in the polyorganosiloxane resin of Allyl end groups; Described organic solvent is that one or more of methyl alcohol, acetone, toluene, tetrahydrofuran (THF) and dehydrated alcohol are by arbitrarily than the mixture formed.
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| CN102181159A (en) * | 2011-03-15 | 2011-09-14 | 杭州师范大学 | Polysilsesquioxane reinforced light emitting diode (LED) encapsulation organic silicon rubber and preparation method thereof |
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| CN102181159A (en) * | 2011-03-15 | 2011-09-14 | 杭州师范大学 | Polysilsesquioxane reinforced light emitting diode (LED) encapsulation organic silicon rubber and preparation method thereof |
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Inventor after: Jiang Haijian Inventor after: Fang Xue Inventor after: Liu Xiaodong Inventor after: Wang Jue Inventor after: Su Guiming Inventor after: Gong Yu Inventor after: Yao Liming Inventor after: Li Peng Inventor after: Song Meihui Inventor after: Chen Mingyue Inventor after: Li Yan Inventor after: Yu Qian Inventor before: Jiang Haijian Inventor before: Su Guiming Inventor before: Gong Yu Inventor before: Yao Liming Inventor before: Li Peng Inventor before: Song Meihui Inventor before: Chen Mingyue Inventor before: Li Yan Inventor before: Yu Qian |
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