CN107400239B - A kind of trapezoidal/cage type polysiloxanes and its preparation method and application from sealing end - Google Patents

A kind of trapezoidal/cage type polysiloxanes and its preparation method and application from sealing end Download PDF

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CN107400239B
CN107400239B CN201610339775.0A CN201610339775A CN107400239B CN 107400239 B CN107400239 B CN 107400239B CN 201610339775 A CN201610339775 A CN 201610339775A CN 107400239 B CN107400239 B CN 107400239B
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polysiloxanes
sealing end
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organic
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CN107400239A (en
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曹新宇
汪洁
尚欣欣
马永梅
张香兰
段珊
张榕本
方世璧
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Institute of Chemistry CAS
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Abstract

The present invention relates to a kind of trapezoidal/cage type polysiloxanes and its preparation method and application from sealing end, the polysiloxanes from sealing end includes the ladder polysiloxane (a) and the cage type polysiloxanes (b) from sealing end from sealing end, and the molar content of polysiloxanes (a) and polysiloxanes (b) is more than or equal to 50mol%.Polysiloxanes of the invention has higher high temperature resistance (such as the temperature of weightlessness 5% is greater than 430 DEG C under nitrogen atmosphere, preferably greater than 450 DEG C, yet more preferably greater than 460 DEG C) and light transmission rate, and (such as light transmission rate is greater than 90%；Refractive index is 1.500-1.600, preferably 1.520-1.560), and there is soluble and fusible property, it is used in mixed way when with other materials, the side reaction as caused by end group will not be brought.

Description

A kind of trapezoidal/cage type polysiloxanes and its preparation method and application from sealing end
Technical field
The present invention relates to a kind of polysiloxanes and its preparation method and application, and in particular to a kind of poly- silicon oxygen of trapezoidal/cage type Alkane and its preparation method and application belongs to technical field of polymer.
Background technique
With trapezoidal or cage structure polysiloxanes, what is reported before is mostly polysilsesquioxane type, i.e. molecule Skeleton is by (- RSiO1.5) repeating segment composition (wherein R be organic group).Just have early in generation nineteen sixty about trapezoidal poly- Report [J.Am.Chem.Soc.1960,82 (23): 6194 of silsesquioxane and cage type polysilsesquioxane； J.Am.Chem.Soc.1946,68:356；And J.Am.Chem.Soc.1965,87:4313].They are usually from trifunctional Silane sets out, and is obtained by hydrolytic condensation under given conditions.It is obtained different from common trifunctional silane hydrolytic condensation Random branched product or cross-linking products, under given conditions, they have obtained molecular self-assembling and have polymerize to be formed with one Determine the polymer of ordered structure.
As its name suggests, the molecular structure of ladder-like polysiloxane (ladder-PSSQ) is that one kind by abutment forms class Like the structure of ladder, wherein-O- connection siloxane main chain, forms the structure of double main chains or multiple main chain, connects the composition of main chain Structure is visually referred to as " abutment ".For polysilsesquioxane, abutment is exactly "-O- ".
Ladder-PSSQ can be with molecularly dispersed structure in solvent, other small molecule compounds or polymer, silicon, oxygen member The inorganic constituents skeleton that element is constituted has both the double grading of organic material and inorganic material in conjunction with organic group side group, has excellent Different high temperature resistant, radiation resistance, while there is excellent electrical insulating property, higher chemical stability, good hydrophobic moisture-proof again Property, it is widely used in terms of semiconductor material, optical material and polymer modification.
Nineteen sixty, Brown etc., which takes the lead in having reported, prepares a kind of pair by trifunctional silane monomer using balance method of condensing The soluble phenyl ladder-like polysiloxane (PPSQ) of chain.Subsequent people have delivered the ladder that different side groups are prepared with similar method The article and patent of shape polysilsesquioxane (R-LPSQ, R are side group).As United States Patent (USP) US3017386 disclose it is a kind of solvable , the phenyl sesquisiloxane with trapezium structure and preparation method thereof.United States Patent (USP) 5081202, United States Patent (USP) 6153689 The ladder-like polysiloxane that there are different side groups with trichlorosilane synthesis is also disclosed with Japan Patent 200159892 etc.. Generation nineteen ninety, Zhang Rongben etc. propose the method that use " gradually coupling polymerization reaction " prepares ladder-PSSQ, It is phenyl, methyl, vinyl etc. that side group is disclosed in CN1105677, PCT/CN2008/072588, WO2010/034161 A1 The preparation of high regular ladder-PSSQ.It is organic group rather than the organic abutment of "-O- " that they, which also study be prepared for abutment in turn, Ladder polysiloxane, in CN1280995, United States Patent (USP) US6423772B1 and J.Am.Chem.Soc.2002,124,10482, A variety of organic bridges reported in the documents such as Angew.Chem.Int.Ed.2006,45,3112 and Chem.Commun.2009,4079 The preparation of base ladder polysiloxane.These organic abutments pass through chemical bond, such as Si-C, Si-O-C, Si-N etc. and trapezoidal poly- times Half siloxane main chain is connected.2013, Cao Xinyu etc. disclosed one kind in Chinese patent CN104045831A with siloxanes and is Abutment, the siloxanes abutting ladder poly-siloxane that main chain is siloxanes, with RSiX3、R’SiX3With α, ω-silicon diol carries out first Condensation reaction is walked, intermediate is formed；Second step condensation and end capping reaction are further carried out with intermediate, separation is then carried out and mentions The pure ladder polysiloxane for obtaining that there is siloxanes abutment.Since its siloxanes abutment is with the silicon atom of-O- (Si) key and main chain Be connected, relative to the ladder polysiloxane that above-mentioned organic abutment is directly connected with backbone silicon atoms, have better heat resistance with The flexibility of strand.But the above ladder polysiloxane end group is the unstable groups such as hydroxyl or alkoxy, directly applies to material Material is possible to substantially reduce its thermal stability, or causes side reaction in material modification, solidification process.It is typically necessary and blocks Agent reaction, to eliminate the hydroxyl or alkoxy of end group, increases the stability of molecule, or be further introduced into functional groups.But it is right In the siloxanes abutting ladder poly-siloxane that rigidity is strong or steric hindrance is big, it is difficult to reach high ending ratio, or need harsh reaction Condition, and cause many unnecessary side reactions.
Cage type polysilsesquioxane (cage-POSS) then has the polyhedral structure of similar cage, the cage- reported so far There are many polyhedron type of POSS, are more typically octahedron, decahedron, dodecahedron etc. [Chem.Rev.95 (5) (1995)1409；Adv.Mater.2008,20,2970–2976；Chem.Rev.2010,110,2081-2173, PCT/US00/ 21455].Cage-POSS is also classified into condensation or incomplete condensed type completely, and incomplete condensed type cage-POSS has imperfect Or not closed cage structure, such as the angle missing of cage structure, adjacent Si atom cannot then reach complete condensation, deposit In silicone hydroxyl or siloxy.In practical applications to improve its performance, for incomplete condensed type cage-POSS, can be used " nut cap " method makes its condensation completely and introduces functional groups；In addition, for be condensed completely or not exclusively condensed type cage- POSS can be derived compatibility or structure is more suitable for by the reactivity of side group with other siloxanes or copolymer compound Product [Macromolecules 2007；40:682–8；Macromolecular Rapid Communications 2009； 30:1015–20】。
It can be seen that having focused largely on ladder- although many for trapezoidal and cage type polysiloxanes research at present Preparation, modification and the application of PSSQ and cage-POSS；Moreover the existing ladder containing " organic abutment " or " siloxanes abutment " Shape polysiloxanes all still needs end capping reaction, to eliminate the unstable group such as ladder polysiloxane terminal hydroxy group, complex process, And it is possible to influence the performance of former ladder polysiloxane.
Summary of the invention
In view of the deficienciess of the prior art, trapezoidal/cage type that an object of the present invention is to provide a kind of sealing end certainly is poly- Siloxanes, the advantages of combining siloxanes abutting ladder poly-siloxane, and overcome and need further to subtract using end capping reaction Less and eliminate the defect of the unstable group such as terminal hydroxy group；In addition, the polysiloxanes has higher high temperature resistance and stabilization Property, and it is dissolvable or fusible, carries out processing and forming, or modified other polymers or organosilicon material with can be convenient.
The second object of the present invention is to provide a kind of preparation method of above-mentioned trapezoidal/cage type polysiloxanes from sealing end.
The third object of the present invention is to provide the application of above-mentioned trapezoidal/cage type polysiloxanes from sealing end.
The purpose of the present invention is achieved through the following technical solutions:
A kind of ladder polysiloxane from sealing end, with structure shown in lower formula (I):
In formula (I), R, R ', A, A ' are identical or different, are independently from each other alkyl, alkenyl, aryl, aryloxy group or aryl Alkoxy；The alkyl be it is substituted or unsubstituted, the aryl be it is substituted or unsubstituted；The substituent group is-NR1R2、- SR3、-OR4, halogen or alkenyl；The R1、R2And R3It is identical or different, it is independently from each other H, C1-10Alkyl or amino replace C1-10Alkyl；The R4Selected from glycidyl ether, acryloyl group or α-C1-4Alkyl acyl group；
M is 0 or z independently of one another, but is not all 0；The z is the integer of 1-10；
N is the integer of 1-500.
Wherein, the alkyl can be C1-10Alkyl, preferably C1-6Alkyl, also preferably C1-4Alkyl, for example methyl, second Base, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl etc..
Wherein, the alkenyl can be C2-10Alkenyl, preferably C2-6Alkenyl, for example vinyl, 1- acrylic, 1- cyclobutenyl Deng.
Wherein, the aryl can be C6-20Aryl, preferably C6-10Aryl, for example phenyl, naphthalene etc..
Wherein, the aryloxy group or " aryl " or " alkyl " in alkoxy aryl are as defined above.
Wherein, the substituent group can be-NH2、-NH(CH2CH2NH2) ,-SH ,-OH or-Cl.
Wherein, described R, R ', A, A ' are identical or different, be independently from each other methyl, ethyl, isopropyl, isobutyl group, Vinyl, allyl, phenyl, glycydoxy, methacryloxypropyl, acryloxypropyl, ammonia third Base, 3- (2- aminoethyl)-aminopropyl, chloropropyl, the groups such as mercapto propyl, chlorophenyl, phenylol or benzyl alcohol base.
Wherein, the ratio for the repetitive unit that m is 0 is preferably smaller than equal to 10% less than 50%.
Wherein, n 2-100 may further be 3-50, may further also be 4-20.
The present invention also provides a kind of cage type polysiloxanes from sealing end, with structure shown in lower formula (II):
In formula (II), R, R ', A, A ', m and n are defined as above.
The present invention also provides a kind of polysiloxanes from sealing end comprising structure shown in formula (I) is gathered from the trapezoidal of sealing end The cage type polysiloxanes (b) from sealing end of siloxanes (a) and structure shown in formula (II), and polysiloxanes (a) and polysiloxanes (b) Molar content be more than or equal to 50mol%.
Preferably, the molar content of polysiloxanes (a) and polysiloxanes (b) is more than or equal to 70mol%, further preferably More than or equal to 80mol%, further preferably be more than or equal to 90mol%.
Wherein, it is to arrive greater than 0 that polysiloxanes (a), which accounts for the molar content of the sum of polysiloxanes (a) and polysiloxanes (b), It can also be 5-50mol% less than 100mol%, for example, 1~99mol%.
The present invention also provides a kind of preparation methods of above-mentioned polysiloxanes from sealing end comprising following steps:
(1) siloxanes abutment intermediate is synthesized, includes RSiX in raw material3And/or R ' SiX3And HO (AA ' SiO)zH； Wherein, R, R ', A, A ', z are defined as above；X is identical or different, is independently from each other OH, Cl, alkoxy (such as C1-10Alkane Oxygroup, specially methoxyl group, ethyoxyl, isopropoxy or isobutoxy) one of or it is a variety of；
(2) intermediate is hydrolyzed；
(3) it is condensed in the presence of basic catalyst, obtains the polysiloxanes from sealing end.
Wherein, step (1) specifically: in the reactor, RSiX is added3And/or R ' SiX3, add HO (AA ' SiO)zH、 First organic solvent and the first catalyst reaction obtain silane oxygen bridge base intermediate.
Preferably, temperature when reaction is -20 DEG C to 60 DEG C；Reaction time is 30 minutes to 10 hours.
Preferably, further include post-processing step after reaction, specially neutralize, filter and/or distill, obtain silane oxygen bridge base Midbody solution.
Preferably, RSiX3With R ' SiX3Molar ratio be (0~1): 1, alternatively, R ' SiX3With RSiX3Molar ratio be (0 ~1): 1.
Preferably, RSiX3And/or R ' SiX3With HO (AA ' SiO)zThe molar ratio of H is (1.8~20): 1.
Preferably, the dosage of the first catalyst is HO (AA ' SiO)z0.0001 to 10 times of the molal quantity of H.Preferably It is 0.0001 to 1 times.
Preferably, first catalyst be selected from ammonia, pyridine, hydrochloric acid, sulfuric acid, nitric acid, sulfonic acid, phosphoric acid, organic amine (ammonium), One of organic acid, metallo-organic compound, ion exchange resin are a variety of.It is further preferred that first catalyst is selected from One of ammonia, organic amine (ammonium).
Preferably, the first organic solvent in step (1) is selected from: benzene,toluene,xylene, methanol, ethyl alcohol, isopropanol, different Butanol, hexane, hexamethylene, acetone, butanone, tetrahydrofuran, cyclohexanone, dioxane, ether, petroleum ether, acetonitrile, dichloromethane One of alkane, dichloroethanes, tetrachloromethane, chloroform, ethyl acetate, dimethyl sulfoxide, dimethylformamide are a variety of.
Wherein, step (2) specifically: it is organic that water, the second catalyst and second are added in the intermediate obtained to step (1) Solvent, alternatively, alcohol, the second catalyst and the second organic solvent is added；Hydrolysis obtains hydrolysate.
Preferably, in step (2), the amount of the water or alcohol that are added is the HO (AA ' SiO) being added in step (1)zH's 0~20 times of molal quantity, but be not 0；For example, 0.0001~20 times.The dosage of second catalyst in step (1) by being added HO (AA ' SiO)z0.0001 to 10 times of molal quantity.
Preferably, the temperature of the hydrolysis in step (2) is 0 DEG C to 150 DEG C, and the reaction time is 30 minutes to 10 small When.
It preferably, further include post-processing step after the completion of step (2) hydrolysis, it specially will reaction gained mixture warp It removes water, be separated by filtration, obtain hydrolysising product solution.
Preferably, second catalyst be selected from ammonia, pyridine, hydrochloric acid, sulfuric acid, nitric acid, sulfonic acid, phosphoric acid, organic amine (ammonium), One of organic acid, metallo-organic compound, ion exchange resin are a variety of.It is further preferred that second catalyst is selected from One of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, organic acid.
Preferably, in step (2), second organic solvent is selected from: benzene,toluene,xylene, ether, methyl phenyl ethers anisole, benzene second Ether, ethyl acetate, tetrahydrofuran, dioxane, chloroform, dichloroethanes it is one or more.This is because on the one hand, this A little solvents and water form azeotropic system, can steam micro-moisture in lower temperature；On the other hand, followed by condensation reaction It needs to carry out in the even nonpolar environment of low pole, terminal hydroxy group is effectively condensed, and reduce branching and friendship The generation of connection.
It wherein, is to be condensed in the presence of basic catalyst by solvent azeotropic dehydration in step (3).
Wherein, the step (3) specifically: basic catalyst is added in the hydrolysising product solution obtained to step (2), into Row condensation reaction constantly steams the water of condensation reaction generation in reaction process；Obtain the polysiloxanes from sealing end.
The water that condensation reaction generation is constantly steamed in described step (3) reaction process, is by solvent azeotropic water removing Method removes the water generated in condensation reaction by solvent azeotrope with water, so that reaction forward carries out.
Preferably, in step (3), the dosage of the basic catalyst is by the HO (AA ' SiO) that is added in step (1)z's 0.0001~10 times of molal quantity.The basic catalyst is selected from the hydroxide of metal or its hydrate, Organometallic close One of object, organic amine (ammonium) are a variety of.
Preferably, in step (3), the temperature of condensation reaction is more than 0~40 DEG C of point of solvent azeotrope with water, and the reaction time is 30 minutes to 48 hours.
It preferably, further include post-processing step after condensation reaction in step (3), it specifically will be obtained by condensation reaction Mixture is neutralized, removes water, is separated by filtration and purifies, and obtains the polysiloxanes from sealing end.
In above-mentioned first catalyst, the second catalyst or basic catalyst, the organic acid be preferably formic acid, acetic acid, One of ethanedioic acid, citric acid, trifluoroacetic acid are a variety of；The organic amine (ammonium) be preferably triethylamine, triethanolamine, One of tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide are a variety of；Institute The metallo-organic compound stated is selected from sodium methoxide, sodium ethoxide, dibutyltin dilaurate, dioctyl tin dilaurate, two Alkyl diaryl tin, butyl titanate, tetraethyl titanate, tetraethoxy zirconium, zirconium-n-propylate, tetrabutyl zirconate, zirconium tetraisopropoxide One of or it is a variety of；The ion exchange resin is selected from the quaternary ammonium type ion that styrene divinylbenzene copolymer is matrix and hands over Change resin, styrene divinylbenzene copolymer is the sulfonic acid ion exchange resin of matrix, styrene divinylbenzene copolymer is One of the carboxylic acid type ion exchange resin of matrix, carboxylic acid type ion exchange resin that polyacrylic acid is matrix are a variety of；Institute The hydroxide for the metal stated is in lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide It is one or more.
Polysiloxanes (a), polysiloxanes (b) and/or the polysiloxanes from sealing end of the invention can be used for organic coating The improvement of the performances such as high molecular heatproof, radiation hardness and weather-resistant；And High Power LED (LED) encapsulation can be improved The heat resistance of glue and organic pressure-sensitive gel, index of refraction, caking property, air-tightness and mechanical property, such as: intensity, modulus, hardness etc..
Wherein, the organic coating macromolecule be, for example, end hydroxyl silicone oil, hydroxy resin, can be cured by Si―H addition reaction Resin, polyurethane resin, epoxy resin, acrylic resin, alkyd resin etc..Include in the packaging plastic or organic pressure-sensitive gel Organic siliconresin.
It include polysiloxanes of the invention in raw material the present invention also provides a kind of coating high molecular material of modification (a), polysiloxanes (b) and/or the polysiloxanes from sealing end.
Wherein, the high molecular material be, for example, end hydroxyl silicone oil, hydroxy resin, can be by the cured tree of Si―H addition reaction Rouge, polyurethane resin, epoxy resin, acrylic resin, alkyd resin etc..
The present invention also provides a kind of packaging plastic or organic pressure-sensitive gels comprising modified organic siliconresin, the modification Organic siliconresin raw material in include polysiloxanes (a) of the invention, polysiloxanes (b) and/or from sealing end polysiloxanes.
The beneficial effects of the present invention are:
Polysiloxanes of the invention has higher high temperature resistance, and (such as the temperature of weightlessness 5% is greater than under nitrogen atmosphere 430 DEG C, preferably greater than 450 DEG C, yet more preferably greater than 460 DEG C) and light transmission rate (such as light transmission rate be greater than 90%；Refractive index is 1.500-1.600, preferably 1.520-1.560), and there is soluble and fusible property, it is used in mixed way when with other materials, The side reaction as caused by end group will not be brought.
Polysiloxanes of the invention can be used for the performances such as the high molecular heatproof of organic coating, radiation hardness and weather-resistant Improvement；And heat resistance, index of refraction, the bonding of High Power LED (LED) packaging plastic and organic pressure-sensitive gel can be improved Property, air-tightness and mechanical property, such as: intensity, modulus, hardness etc..
Detailed description of the invention
The FTIR spectrogram of 1 products therefrom of Fig. 1 embodiment of the present invention.
The XRD spectra of 1 products therefrom of Fig. 2 embodiment of the present invention.
Specific embodiment
As described above, the present invention provides a kind of ladder polysiloxanes from sealing end, a kind of poly- silicon oxygen of cage type from sealing end Alkane and a kind of polysiloxanes from sealing end, this refers to that one kind is higher than known siloxanes abutting ladder poly without using end-capping reagent and condensation degree It is polysiloxanes or cage type polysiloxanes, soluble, with three-dimensional trapezoidal or cage-like molecular structure polysiloxanes.
What the present invention innovated discloses a kind of polysiloxanes blocked from the trapezoidal/cage type polysiloxanes blocked, certainly, this is poly- Siloxanes combines the advantages of existing siloxanes abutting ladder poly-siloxane, while overcoming again and needing to subtract using end capping reaction Less or eliminate the defect of the unstable group such as terminal hydroxy group.
Condensation degree in the present invention is calculated through following formula and is obtained:
Condensation degree formulaDxOr TxIn, x represents Si atom with Si-O- (Si) quantity for the key that key is connected with other Si atoms, D are representedT is representedR is side group.
It is calculated by the formula, the condensation degree of trapezoidal/cage type polysiloxanes of the present invention from sealing end is obviously high It significantly reduces in condensation degree, the end group of original siloxanes abutting ladder poly-siloxane, without carrying out end capping reaction, reduces anti- Answer the generation of program and side reaction.Polysiloxanes of the invention has higher high temperature resistance and stability, and having can Dissolubility and fusible property, are used in mixed way when with other materials, will not bring the side reaction as caused by end group.It can be used for being modified Semiconductor material, encapsulating material, medical material etc. improve its thermal stability, processability, adjustment refractive index etc..
Embodiment 1
Caged and trapezoidal from terminated polysiloxane is prepared by vinyltrimethoxysilane, diphenyl silanediol.
(1) under dry nitrogen protection, in the more neck bottles for being mounted with condenser pipe and dropping funel, 30.7 grams are placed in (0.21 mole) vinyltrimethoxysilane, by 30 grams of tetrahydrofurans and 10.3 grams of (0.05 mole) diphenyl at -20 DEG C The mixed liquor of silicon diol is added drop-wise in more neck bottles, while being passed through ammonia；After being added dropwise 4 hours, stops logical ammonia, be gradually warming up to 70 DEG C reaction 1 hour to remove ammonia；After stopping reaction, distill to remove the tetrahydrofuran, methanol and unreacted vinyl of part Trimethoxy silane obtains the midbody solution that concentration is about 30%；
(2) at 40 DEG C, step (1) is obtained into the midbody solution and 7.2 grams of (0.40 mole) water that concentration is about 30% With 0.044 gram (4.00 × 10-4Mole HCl) mixed in hydrochloric acid, it is reacted 4 hours at 40 DEG C；Reaction gained mixture is removed water, It is separated by filtration to obtain the presoma from end-cap product；
(3) 0.0043 gram of potassium hydroxide (7.68 × 10 is added in the presoma obtained to step (2)-5Mole), 65 90 DEG C, which are warming up to, after reacting 4 hours at DEG C distills out tetrahydrofuran and water；Neutralized gained mixture, water removal, filtering will be reacted Separation and purification are obtained from terminated polysiloxane (being denoted as P1), and the P1 includes that caged shown in logical formula (II) blocks poly- silicon oxygen certainly It is trapezoidal from terminated polysiloxane shown in alkane and logical formula (I), wherein R=R '=vinyl, A=A '=phenyl, m=1.Gained P1's Yield is 75%.
Gained P1 is dissolved in toluene, and FTIR is as shown in Figure 1, XRD spectra is as shown in Figure 2；?29In Si-NMR spectrogram ,- Appearance near 48.4ppm and -81.6ppm, calculating condensation degree according to the ratio of each peak value is 97.3%.According to VPO (vapour pressure Osmometer) test product average value polymerization degree n be 7.
Polysiloxanes of the invention has excellent optical property, and the P1 is higher than 93% in visible light wave range transmitance, Refractive index is 1.547.
Polysiloxanes of the invention has excellent heat resistance simultaneously, according to TGA the results show that the P1 is in nitrogen atmosphere Enclosing lower weightless 5% temperature is 480 DEG C.
Embodiment 2
Pass through methacryloxypropyl trimethoxy silane, methyltrimethoxysilane and HO (Ph2SiO)2H preparation Caged and trapezoidal from terminated polysiloxane.
(1) under dry nitrogen protection, in the more neck bottles for being mounted with condenser pipe and dropping funel, 24.8 grams are placed in (0.10 mole) methacryloxypropyl trimethoxy silane and 13.6 grams of (0.10 mole) methyltrimethoxysilane are mixed It closes, by 36 grams of toluene and dioxane and 20.7 grams of (0.05 mole) HO (Ph at -20 DEG C2SiO)2The mixed liquor of H is added drop-wise to more In neck bottle, while being added 0.002 gram (8 × 10-4Mole) tetrabutylammonium hydroxide；After being added dropwise 10 hours, stops reaction, be washed to Neutrality after dry filter, is distilled to remove toluene, dioxane, methanol, unreacted methacryloxypropyl trimethoxy Base silane and unreacted methyltrimethoxysilane obtain pure intermediate；
(2) intermediate and the tetrahydrofuran mixing obtained step (1), it is molten to obtain the intermediate that concentration is about 40wt% Liquid；At 0 DEG C, by midbody solution and 9.0 grams of (0.50 mole) water and 0.05 gram (5.00 × 10-4Mole) sulfuric acid mixing, 0 It is reacted 3 hours at DEG C；Reaction gained mixture is removed water, is separated by filtration to obtain the presoma from end-cap product；
(3) barium hydroxide (Ba (OH) of 1.42 grams (0.005 mole) is added in the presoma obtained to step (2)2· 8H2O), 90 DEG C, which are warming up to, after reacting 4 hours at 40 DEG C distills out tetrahydrofuran and water；Reaction gained mixture is neutralized, It removes water, be separated by filtration and purify, obtain from terminated polysiloxane (being denoted as P2), the P2 includes that caged shown in logical formula (II) is self-styled Hold trapezoidal from terminated polysiloxane shown in polysiloxanes and logical formula (I), wherein R=methacryloxypropyl, R '=methyl, A=A '=phenyl, m=2.The yield of gained P2 is 70%.
By FTIR spectrogram it is found that in 1071cm-1, 1130cm-1, 1262cm-1, 1429cm-1, 2843cm-1And 2940cm-1Out Existing absorption peak.By1H-NMR spectrum is it is found that there is peak in 7.7ppm, 7.4ppm, 5.6ppm, 4.1ppm 3.4ppm and 0.6ppm. By its molecular weight of VPO (vapour-pressure osmometer) test analysis, the average value for obtaining n is 7.It dissolves in tetrahydrofuran.Condensation Degree is 96.7%.
Polysiloxanes of the invention has excellent optical property, and the P2 is higher than 93% in visible light wave range transmitance, Refractive index is 1.550.
Polysiloxanes of the invention has excellent heat resistance simultaneously, according to TGA the results show that the P2 is in nitrogen atmosphere Enclosing lower weightless 5% temperature is 471 DEG C.
Embodiment 3
Pass through phenyl trichlorosilane, methyl trichlorosilane and HO (MePhSiO)3H prepares caged and the trapezoidal poly- silicon of sealing end certainly Oxygen alkane.
(1) under dry nitrogen protection, in the more neck bottles for being mounted with condenser pipe and dropping funel, 10.6 grams are placed in (0.05 mole) phenyl trichlorosilane and 14.9 grams of (0.10 mole) methyl trichlorosilane mixing, by 60 grams of tetrahydro furans at 0 DEG C It mutters and dichloroethanes and 41.3 grams of (0.08 mole) HO (MePhSiO)3The mixed liquor of H is added drop-wise in more neck bottles, is added simultaneously 80.8 grams of (0.8 mole) triethylamines；After being added dropwise 20 hours, stop reaction, be washed to neutrality, after dry filter, distills to remove Tetrahydrofuran, dichloroethanes, unreacted phenyl trichlorosilane and unreacted methyl trichlorosilane obtain pure intermediate；
(2) intermediate and the methylene chloride mixing obtained step (1), it is molten to obtain the intermediate that concentration is about 40wt% Liquid；At -10 DEG C, by midbody solution and 14.4 grams of (0.80 mole) water and 0.0005 gram (8.00 × 10-6Mole) nitric acid is mixed It closes, is reacted 5 hours at -10 DEG C；Reaction gained mixture is removed water, is separated by filtration to obtain the presoma from end-cap product；
(3) 0.005 gram (8.00 × 10 is added in the presoma obtained to step (2)-5Mole) sodium ethoxide, at 0 DEG C Reaction is warming up to 50 DEG C after 2 hours and distills out methylene chloride and water；Mixture will be neutralized obtained by reacting, removes water, is separated by filtration And purification, obtain from terminated polysiloxane (being denoted as P3), the P3 include caged shown in logical formula (II) from terminated polysiloxane and It is trapezoidal from terminated polysiloxane shown in logical formula (I), wherein R=phenyl, R '=methyl, A=methyl, A '=phenyl, m=3.Gained The yield of P3 is 83%.
By FTIR spectrogram it is found that in 1070cm-1, 1120cm-1, 1430cm-1, 1601cm-1, 2942cm-1And 3380cm-1Out Existing absorption peak.It dissolves in acetone or tetrahydrofuran.By its molecular weight of VPO (vapour-pressure osmometer) test analysis, obtain n's Average value is 8.Condensation degree is 97.5%.
Polysiloxanes of the invention has excellent optical property, and the P3 is higher than 91% in visible light wave range transmitance, Refractive index is 1.543.
Polysiloxanes of the invention has excellent heat resistance simultaneously, according to TGA the results show that the P3 is in nitrogen atmosphere Enclosing lower weightless 5% temperature is 469 DEG C.
Embodiment 4
Caged and trapezoidal is prepared by vinyltrimethoxysilane, aminopropyl trimethoxysilane and diphenyl silanediol From terminated polysiloxane.
(1) under dry nitrogen protection, in the more neck bottles for being mounted with condenser pipe and dropping funel, 29.6 grams are placed in (0.20 mole) vinyltrimethoxysilane and 10.8 grams of (0.06 mole) aminopropyl trimethoxysilanes, by 40 at 10 DEG C The mixed liquor of gram ethyl alcohol and acetone and 20.7 grams of (0.05 mole) diphenyl silanediols is added drop-wise in more neck bottles, while being added 22.8 Gram (0.25 mole) tetramethylammonium hydroxide；After being added dropwise 1 hour, stop reaction, be washed to neutrality, after dry filter, distillation with Ethyl alcohol, acetone, methanol, unreacted vinyltrimethoxysilane and unreacted aminopropyl trimethoxysilane is removed to obtain Pure intermediate；
(2) intermediate and the carbon tetrachloride mixing obtained step (1), it is molten to obtain the intermediate that concentration is about 30wt% Liquid；At 20 DEG C, the midbody solution and 1.0 grams of (1.00 moles) water and 19.2 grams (0.4 mole) that are about 30wt% by concentration Formic acid mixing, reacts 4 hours at 30 DEG C；Reaction gained mixture is removed water, is separated by filtration to obtain from before end-cap product Drive body；
(3) tetrabutylammonium hydroxide of 2.58 grams (0.01 mole) is added in the presoma obtained to step (2), at 40 DEG C Lower reaction is warming up to 85 DEG C after 4 hours and distills out carbon tetrachloride and water；Neutralized gained mixture, water removal, filtering point will be reacted From and purification, obtain from terminated polysiloxane (being denoted as P4), the P4 includes caged shown in logical formula (II) from terminated polysiloxane With trapezoidal from terminated polysiloxane shown in logical formula (I), wherein R=vinyl, R '=aminopropyl, A=A '=phenyl, m=1.Institute The yield for obtaining P4 is 74%.
By FTIR spectrogram it is found that in 1070cm-1, 1120cm-1, 1430cm-1, 1601cm-1, 2942cm-1And 3380cm-1Out Existing absorption peak.By XRD spectra it is found that thering is obvious peak to occur in the position that 2 θ are 8.5 ° and 19.5 °.Pass through VPO (vapour pressure infiltration Meter) test analysis its molecular weight, the average value for obtaining n is 7.It dissolves in dimethylbenzene.Condensation degree is 94.9%.
Polysiloxanes of the invention has excellent optical property, and the P4 is higher than 90% in visible light wave range transmitance, Refractive index is 1.544.
Polysiloxanes of the invention has excellent heat resistance simultaneously, according to TGA the results show that the P4 is in nitrogen atmosphere Enclosing lower weightless 5% temperature is 477 DEG C.
Embodiment 5
Pass through glycidyl ether oxypropyltrimethoxysilane and HO (Me2SiO)5H prepares caged and trapezoidal block certainly is gathered Siloxanes.
(1) under dry nitrogen protection, in the more neck bottles for being mounted with condenser pipe and dropping funel, 47.2 grams are placed in (0.20 mole) glycidyl ether oxypropyltrimethoxysilane, by 25 grams of benzene and hexamethylene and 7.76 grams at 60 DEG C (0.02 mole) HO (Me2SiO)5The mixed liquor of H is added drop-wise in more neck bottles, while being passed through ammonia；After being added dropwise 1 hour, stop logical ammonia Gas is gradually warming up to 70 DEG C of reactions 1 hour to remove ammonia, distills with benzene removal, hexamethylene, methanol and unreacted glycidol Ether oxygen base propyl trimethoxy silicane obtains pure intermediate；
(2) intermediate and toluene, the ether obtained step (1) mixes, and it is molten to obtain the intermediate that concentration is about 1wt% Liquid；At 30 DEG C, by midbody solution and 7.2 grams of (0.40 mole) water and 0.044 gram (4.00 × 10-4Mole HCl) salt acid-mixed It closes, is reacted 1 hour at 30 DEG C；Reaction gained mixture is removed water, is separated by filtration to obtain the presoma from end-cap product；
(3) 0.006 gram (1 × 10 is added in the presoma obtained to step (2)-5Mole) dibutyltindilaurylmercaptide cinnamic acid Ester is warming up to 90 DEG C after reacting 40 hours at -20 DEG C and distills out toluene, ether and water；Reaction gained mixture is neutralized, It removes water, be separated by filtration and purify, obtain from terminated polysiloxane (being denoted as P5), the P5 includes that caged shown in logical formula (II) is self-styled Hold trapezoidal from terminated polysiloxane shown in polysiloxanes and logical formula (I), wherein R=R '=glycydoxy, A=benzene Base, A '=phenyl, m=5.The yield of gained P5 is 88%.
By FTIR spectrogram it is found that in 1068cm-1, 1121cm-1, 1429cm-1, 1601cm-1, 2842cm-1And 3080cm-1Out Existing absorption peak.By XRD spectra it is found that thering is obvious peak to occur in the position that 2 θ are 8.0 ° and 19.1 °.Pass through VPO (vapour pressure infiltration Meter) test analysis its molecular weight, the average value for obtaining n is 6.It dissolves in petroleum ether.Condensation degree is 94.3%.
Polysiloxanes of the invention has excellent optical property, and the P5 is higher than 90% in visible light wave range transmitance, Refractive index is 1.539
Polysiloxanes of the invention has excellent heat resistance simultaneously, according to TGA the results show that the P5 is in nitrogen atmosphere Enclosing lower weightless 5% temperature is 479 DEG C.
Embodiment 6
Caged and trapezoidal self-styled is prepared by phenyl trichlorosilane, 3- acryloyl-oxy base trichlorosilane and diphenyl silanediol Hold polysiloxanes.
(1) under dry nitrogen protection, in the more neck bottles for being mounted with condenser pipe and dropping funel, 21.2 grams are placed in (0.10 mole) phenyl trichlorosilane and 24.8 grams of (0.10 mole) 3- acryloyl-oxy base trichlorosilane mixing, by 75 at 30 DEG C The mixed liquor of gram dimethylbenzene and petroleum ether and 21.6 grams of (0.10 mole) diphenyl silanediols is added drop-wise in more neck bottles, is added simultaneously 151.5 grams of (1.5 moles) triethylamines；After being added dropwise 48 hours, stop reaction, be washed to neutrality, after dry filter, distills to remove Dimethylbenzene, petroleum ether, unreacted phenyl trichlorosilane and unreacted 3- acryloyl-oxy base trichlorosilane obtain pure centre Body；
(2) intermediate and the ethyl acetate mixing obtained step (1), it is molten to obtain the intermediate that concentration is about 65wt% Liquid；At 0 DEG C, midbody solution is mixed with 14.4 grams of (0.80 mole) water and 1.80 grams of (0.30 mole) acetic acid, at -20 DEG C Lower reaction 25 hours；Reaction gained mixture is removed water, is separated by filtration to obtain the presoma from end-cap product；
(3) butyl titanate of 51 grams (0.15 mole) is added in the presoma obtained to step (2), reacts 15 at 60 DEG C 75 DEG C, which are warming up to, after hour distills out ethyl acetate and water；Mixture will be neutralized obtained by reacting, removes water, is separated by filtration and mentions It is pure, it obtains from terminated polysiloxane (being denoted as P6), the P6 includes leading to caged shown in formula (II) from terminated polysiloxane and general formula (I) trapezoidal from terminated polysiloxane shown in, wherein R=phenyl, R '=3- acryloyl-oxy base trichlorosilane, A=A '=phenyl, m =1.The yield of gained P6 is 79%.
By FTIR spectrogram it is found that in 1069cm-1, 1130cm-1, 1261cm-1, 1429cm-1, 2842cm-1And 3010cm-1Out Existing absorption peak.By1H-NMR spectrum is it is found that there is peak in 7.8ppm, 7.4ppm, 5.4ppm, 4.0ppm 3.3ppm and 0.3ppm. By its molecular weight of VPO (vapour-pressure osmometer) test analysis, the average value for obtaining n is 8.It dissolves in petroleum ether.Condensation degree It is 95.7%.
Polysiloxanes of the invention has excellent optical property, and the P6 is higher than 95% in visible light wave range transmitance, Refractive index is 1.556.
Polysiloxanes of the invention has excellent heat resistance simultaneously, according to TGA the results show that the P6 is in nitrogen atmosphere Enclosing lower weightless 5% temperature is 469 DEG C.
Embodiment 7
Pass through aminopropyl trimethoxysilane and HO (MePhSiO)5H prepares caged and trapezoidal from terminated polysiloxane.
(1) under dry nitrogen protection, in the more neck bottles for being mounted with condenser pipe and dropping funel, 35.8 grams are placed in (0.20 mole) aminopropyl trimethoxysilane, by 115 grams of tetrahydrofurans and isobutanol and 34.9 grams (0.05 mole) at 0 DEG C The mixed liquor of diphenyl silanediol is added drop-wise in more neck bottles, while being passed through ammonia；After being added dropwise 35 hours, stop logical ammonia, gradually 70 DEG C of reactions are warming up to 2 hours to remove ammonia, are distilled to remove tetrahydrofuran, isobutanol, methanol and unreacted aminopropyl three Methoxy silane obtains pure intermediate；
(2) intermediate and the trichloroethanes mixing obtained step (1), it is molten to obtain the intermediate that concentration is about 15wt% Liquid；At 110 DEG C, by midbody solution and 9.0 grams of (0.50 mole) water and 0.05 gram (5.00 × 10-4Mole) sulfuric acid mixing, It is reacted 30 minutes at 110 DEG C；Reaction gained mixture is removed water, is separated by filtration to obtain the presoma from end-cap product；
(3) calcium hydroxide of 5.7 grams (0.10 mole) is added in the presoma obtained to step (2), is reacted at 110 DEG C It is warming up to 150 DEG C after 6 hours and distills out trichloroethanes and water；Mixture will be neutralized obtained by reacting, removes water, is separated by filtration and mentions It is pure, it obtains from terminated polysiloxane (being denoted as P7), the P7 includes leading to caged shown in formula (II) from terminated polysiloxane and general formula (I) trapezoidal from terminated polysiloxane shown in, wherein R=R '=aminopropyl, A=methyl, A '=phenyl, m=5.The production of gained P7 Rate is 77%.
By FTIR spectrogram it is found that in 1072cm-1, 1129cm-1, 1429cm-1, 1595cm-1And 3080cm-1It absorbs Peak.Condensation degree is 96.6%.By XRD spectra it is found that thering is obvious peak to occur in the position that 2 θ are 7.6 ° and 19.3 °.Pass through VPO Its molecular weight of (vapour-pressure osmometer) test analysis, the average value for obtaining n is 8.Dissolve in benzene, in toluene.Condensation degree is 95.7%.
Polysiloxanes of the invention has excellent optical property, and the P7 is higher than 92% in visible light wave range transmitance, Refractive index is 1.539.
Polysiloxanes of the invention has excellent heat resistance simultaneously, according to TGA the results show that the P7 is in nitrogen atmosphere Enclosing lower weightless 5% temperature is 474 DEG C.
Embodiment 8
Caged and trapezoidal is prepared by vinyltrimethoxysilane, phenyltrimethoxysila,e and diisopropyl silicon diol From terminated polysiloxane.
(1) under dry nitrogen protection, in the more neck bottles for being mounted with condenser pipe and dropping funel, 14.8 grams are placed in (0.10 mole) vinyltrimethoxysilane and 19.8 grams of (0.10 mole) phenyltrimethoxysila,e mixing, will at 40 DEG C The mixed liquor of 80 grams of tetrahydrofurans and dioxane and 19.8 grams of (0.10 mole) diisopropyl silicon diols is added drop-wise in more neck bottles, Add 0.002 gram (8 × 10 simultaneously-4Mole) enter tetrabutylammonium hydroxide；After being added dropwise 5 hours, stop reaction, be washed to neutrality, does After dry filtering, distill to remove tetrahydrofuran, dioxane, methanol, unreacted vinyltrimethoxysilane and unreacted Phenyltrimethoxysila,e obtain pure intermediate；
(2) intermediate and the tetrahydrofuran mixing obtained step (1), it is molten to obtain the intermediate that concentration is about 0.5wt% Liquid；At 25 DEG C, by midbody solution and 36.0 grams of (2.00 moles) water and 0.96 gram (5.00 × 10-3Mole) lemon acid-mixed It closes, is reacted 1.5 hours at 25 DEG C；Reaction gained mixture is removed water, is separated by filtration to obtain the presoma from end-cap product；
(3) triethanolamine of 6.7 grams (0.05 mole) is added in the presoma obtained to step (2), it is anti-at 70 DEG C 75 DEG C, which are warming up to, after answering 30 minutes distills out tetrahydrofuran and water；Will reaction gained mixture it is neutralized, remove water, be separated by filtration and Purification is obtained from terminated polysiloxane (being denoted as P8), and the P8 includes caged shown in logical formula (II) from terminated polysiloxane and leads to It is trapezoidal from terminated polysiloxane shown in formula (I), wherein R=vinyl, R '=phenyl, A=A '=isopropyl, m=1.Gained P8 Yield be 90%.
By FTIR spectrogram it is found that in 1012cm-1, 1072cm-1, 1129cm-1, 1429cm-1, 1595cm-1And 3080cm-1Out Existing absorption peak.By its molecular weight of VPO (vapour-pressure osmometer) test analysis, the average value for obtaining n is 9.Dissolve in hexamethylene In.Condensation degree is 98.2%.
Polysiloxanes of the invention has excellent optical property, and the P8 is higher than 90% in visible light wave range transmitance. Refractive index is 1.521.
Polysiloxanes of the invention has excellent heat resistance simultaneously, according to TGA the results show that the P8 is in nitrogen atmosphere Enclosing lower weightless 5% temperature is 470 DEG C.
Embodiment 9
Pass through mercaptopropyl trimethoxysilane, phenyltrimethoxysila,e and HO (Ph2SiO)2H prepare caged and it is trapezoidal from Terminated polysiloxane.
(1) under dry nitrogen protection, in the more neck bottles for being mounted with condenser pipe and dropping funel, 19.6 grams are placed in (0.10 mole) mercapto propyl base trimethoxy silane and 19.8 grams of (0.10 mole) phenyltrimethoxysila,e mixing, at -20 DEG C It is lower by 65 grams of toluene and 41.4 grams of (0.10 mole) HO (Ph2SiO)2The mixed liquor of H is added drop-wise in more neck bottles, while being passed through ammonia； After being added dropwise 10 hours, stop logical ammonia, be gradually warming up to 70 DEG C of reactions 2 hours to remove ammonia, distillation with remove toluene, methanol, Unreacted mercaptopropyl trimethoxysilane and unreacted phenyltrimethoxysila,e obtain pure intermediate；
(2) intermediate and the trichloroethanes mixing obtained step (1), it is molten to obtain the intermediate that concentration is about 50wt% Liquid；At 60 DEG C, by midbody solution and 18.0 grams of (1.00 moles) water and 0.05 gram (5.00 × 10-4Mole) sulfuric acid mixing, It is reacted 45 minutes at 60 DEG C；Reaction gained mixture is removed water, is separated by filtration to obtain the presoma from end-cap product；
(3) 3.68 grams of tetraethyl ammonium hydroxide (0.025 mole) is added in the presoma obtained to step (2), 60 130 DEG C, which are warming up to, after reacting 2 hours at DEG C distills out trichloroethanes and water；Neutralized gained mixture, water removal, filtering will be reacted Separation and purification are obtained from terminated polysiloxane (being denoted as P9), and the P9 includes that caged shown in logical formula (II) blocks poly- silicon oxygen certainly It is trapezoidal from terminated polysiloxane shown in alkane and logical formula (I), wherein R=mercapto propyl, R '=phenyl, A=A '=phenyl, m=2.Institute The yield for obtaining P9 is 73%.
By FTIR spectrogram it is found that in 1070cm-1, 1131cm-1, 1430cm-1, 1599cm-1And 3074cm-1It absorbs Peak.Condensation degree is 95.5%.By XRD spectra it is found that thering is obvious peak to occur in the position that 2 θ are 8.8 ° and 18.3 °.Pass through VPO Its molecular weight of (vapour-pressure osmometer) test analysis, the average value for obtaining n is 5.It dissolves in dichloroethanes.Condensation degree is 91.3%.
Polysiloxanes of the invention has excellent optical property, and the P9 is higher than 92% in visible light wave range transmitance, Refractive index is 1.549.
Polysiloxanes of the invention has excellent heat resistance simultaneously, according to TGA the results show that the P9 is in nitrogen atmosphere Enclosing lower weightless 5% temperature is 488 DEG C.
Embodiment 10
Pass through vinyl trichlorosilane, methyl trichlorosilane and HO (Ph2SiO)3H prepares caged and the trapezoidal poly- silicon of sealing end certainly Oxygen alkane.
(1) under dry nitrogen protection, in the more neck bottles for being mounted with condenser pipe and dropping funel, 12.9 grams are placed in (0.08 mole) vinyl trichlorosilane and 14.9 grams of (0.10 mole) methyltrimethoxysilane mixing, by 160 at -20 DEG C Gram tetrahydrofuran and 55.8 grams of (0.09 mole) HO (Ph2SiO)3The mixed liquor of H is added drop-wise in more neck bottles, while being added 109 grams (1.1 moles) triethylamine；After being added dropwise 30 hours, stop reaction, be washed to neutrality, after dry filter, distills to remove tetrahydro furan It mutters, unreacted vinyl trichlorosilane and unreacted methyl trichlorosilane obtain pure intermediate；
(2) intermediate and the tetrahydrofuran mixing obtained step (1), it is molten to obtain the intermediate that concentration is about 65wt% Liquid；At -20 DEG C, midbody solution is mixed with 28.8 grams of (1.60 moles) water and 4.9 grams of (0.05 mole) phosphoric acid, -20 It is reacted 9 hours at DEG C；Reaction gained mixture is removed water, is separated by filtration to obtain the presoma from end-cap product；
(3) sodium hydroxide of 0.2 gram (0.005 mole) is added in the presoma obtained to step (2), is reacted at 55 DEG C It is warming up to 80 DEG C after 1 hour and distills out tetrahydrofuran and water；Mixture will be neutralized obtained by reacting, removes water, is separated by filtration and mentions It is pure, it obtains from terminated polysiloxane (being denoted as P10), the P10 includes caged shown in logical formula (II) from terminated polysiloxane and leads to It is trapezoidal from terminated polysiloxane shown in formula (I), wherein R=vinyl, R '=methyl, A=A '=phenyl, m=3.Gained P10's Yield is 70%.
By XRD spectra it is found that thering is obvious peak to occur in the position that 2 θ are 8.3 ° and 19.3 °.By29Si-NMR spectrogram it is found that There is peak in 47.4ppm, 65.4ppm and 80.9ppm.By its molecular weight of VPO (vapour-pressure osmometer) test analysis, n is obtained Average value be 8.It dissolves in dioxane.Condensation degree is 97.6%.
Polysiloxanes of the invention has excellent optical property, and the P10 is higher than 90% in visible light wave range transmitance, Refractive index is 1.529.
Polysiloxanes of the invention has excellent heat resistance simultaneously, according to TGA the results show that the P10 is in nitrogen The temperature of weightlessness 5% is 477 DEG C under atmosphere.
Embodiment 11
P1 obtained in embodiment 1 is added in the product 6630A and 6630B of DOW CORNING organic siliconresin, enhancing has The performance of machine silicone resin
After the P1 of 1 gram of embodiment 1,1 gram of 6630A and 8 gram of 6630B are sufficiently mixed, the Karstedt that 400ppm is added is urged Agent is uniformly mixed again, is poured into mold, after vacuum drying oven deaeration processing, is warming up to 150 DEG C, is reacted 6 hours, obtain Modified organosilicon material.
The refractive index for measuring material is 1.564.Transmitance is 92.1% in the wave-length coverage of visible light.Thermal weight loss point Analysis, weightlessness 5% when temperature be 483 DEG C, be warming up to 750 DEG C residual volume be 76%.And made from uncapped polysiloxanes Temperature when modified organosilicon material weightlessness 5% is 426 DEG C, and the residual volume for being warming up to 750 DEG C is 54%.
Embodiment 12
P2 obtained in embodiment 2 is added in commercially available end hydroxyl silicone oil, the performance of end hydroxyl silicone oil is enhanced
50 grams of commercially available 107# end hydroxyl silicone oil is added in kneader, is removed by high temperature (100 DEG C) high pressure (1kPa) After 4 hours of water, it is down to room temperature, P2 and 0.003 gram obtained in 3 grams of embodiments 2 of chloroplatinic acid catalyst is added, it is small to mediate 2 When, mixture is taken out, modified end hydroxyl silicone oil is obtained.
According to GB/T14683-2003 method detect mechanical property, modulus 0.83MPa, tensile strength 1.54MPa, Elongation at break is 339%.TGA as the result is shown weightlessness 5% when temperature be 474 DEG C, the residual volume for being warming up to 750 DEG C is 74%.And the temperature when end hydroxyl silicone oil weightlessness 5% of modification made from uncapped polysiloxanes is 421 DEG C, is warming up to 750 DEG C residual volume be 49%.

Claims (59)

1. a kind of ladder polysiloxane from sealing end, which is characterized in that the polysiloxanes has structure shown in lower formula (I):
In formula (I), R, R ', A, A ' are identical or different, are independently from each other alkyl, alkenyl, aryl, aryloxy group or arylalkoxy Base；The alkyl be it is substituted or unsubstituted, the aryl be it is substituted or unsubstituted；The substituent group is-NR1R2、-SR3、- OR4, halogen or alkenyl；The R1、R2And R3It is identical or different, it is independently from each other H, C1-10Alkyl or amino replace C1-10Alkane Base；The R4Selected from glycidyl ether, acryloyl group or α-C1-4 alkyl acyl group；
M is 0 or z independently of one another, but is not all 0；The z is the integer of 1-10；
N is the integer of 1-500.
2. the ladder polysiloxane according to claim 1 from sealing end, which is characterized in that the alkyl is C1-10Alkyl.
3. the ladder polysiloxane according to claim 2 from sealing end, which is characterized in that the alkyl is C1-6Alkyl.
4. the ladder polysiloxane according to claim 3 from sealing end, which is characterized in that the alkyl is C1-4Alkyl.
5. it is according to claim 4 from sealing end ladder polysiloxane, which is characterized in that the alkyl be methyl, ethyl, N-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl.
6. the ladder polysiloxane according to claim 1 from sealing end, which is characterized in that the alkenyl is C2-10Alkenyl.
7. the ladder polysiloxane according to claim 6 from sealing end, which is characterized in that the alkenyl is C2-6Alkenyl.
8. the ladder polysiloxane according to claim 7 from sealing end, which is characterized in that the alkenyl is vinyl, 1- Acrylic, 1- cyclobutenyl.
9. the ladder polysiloxane according to claim 1 from sealing end, which is characterized in that the aryl is C6-20Aryl.
10. the ladder polysiloxane according to claim 9 from sealing end, which is characterized in that the aryl is C6-10Aryl.
11. the ladder polysiloxane according to claim 10 from sealing end, which is characterized in that the aryl is phenyl, naphthalene Base.
12. the ladder polysiloxane according to claim 1 from sealing end, which is characterized in that the aryloxy group or aryl alkane " aryl " or " alkyl " in oxygroup is as defined in any one of claim 2-5,9-11.
13. the ladder polysiloxane according to claim 1 from sealing end, which is characterized in that the substituent group is-NH2、-NH (CH2CH2NH2) ,-SH ,-OH or-Cl.
14. the ladder polysiloxane according to claim 1 from sealing end, which is characterized in that described R, the R ', A, A ' it is identical Or it is different, it is independently from each other methyl, ethyl, isopropyl, isobutyl group, vinyl, allyl, phenyl, glycidyl ether oxygen Base propyl, methacryloxypropyl, acryloxypropyl, aminopropyl, 3- (2- aminoethyl)-aminopropyl, chloropropyl, mercapto Propyl, chlorophenyl, phenylol or benzyl alcohol base.
15. the ladder polysiloxane according to claim 1 from sealing end, which is characterized in that the ratio for the repetitive unit that m is 0 Example is less than 50%.
16. the ladder polysiloxane according to claim 15 from sealing end, which is characterized in that the ratio for the repetitive unit that m is 0 Example is less than or equal to 10%.
17. the ladder polysiloxane according to claim 1 from sealing end, which is characterized in that n 2-100.
18. the ladder polysiloxane according to claim 17 from sealing end, which is characterized in that n 3-50.
19. the ladder polysiloxane according to claim 18 from sealing end, which is characterized in that n 4-20.
20. a kind of cage type polysiloxanes from sealing end, which is characterized in that the polysiloxanes has structure shown in lower formula (II):
The definition of in formula (II), R, R ', A, A ', m, n are the same as the definition in claim any one of 1-19.
21. a kind of polysiloxanes from sealing end, which is characterized in that the polysiloxanes includes described in claim any one of 1-19 The ladder polysiloxane (a) and claim 20 from sealing end described in from the cage type polysiloxanes (b) of sealing end, and polysiloxanes (a) and the molar content of polysiloxanes (b) is more than or equal to 50mol%.
22. the polysiloxanes according to claim 21 from sealing end, which is characterized in that polysiloxanes (a) and polysiloxanes (b) molar content is more than or equal to 70mol%.
23. the polysiloxanes according to claim 22 from sealing end, which is characterized in that polysiloxanes (a) and polysiloxanes (b) molar content is more than or equal to 80mol%.
24. the polysiloxanes according to claim 23 from sealing end, which is characterized in that polysiloxanes (a) and polysiloxanes (b) molar content is more than or equal to 90mol%.
25. the polysiloxanes according to claim 21 from sealing end, which is characterized in that polysiloxanes (a) accounts for polysiloxanes It (a) is greater than 0 with the molar content of the sum of polysiloxanes (b) to less than 100mol%.
26. the polysiloxanes according to claim 25 from sealing end, which is characterized in that polysiloxanes (a) accounts for polysiloxanes It (a) is 1~99mol% with the molar content of the sum of polysiloxanes (b).
27. a kind of preparation method of the described in any item polysiloxanes from sealing end of claim 21-26, which is characterized in that institute The method of stating includes the following steps:
(1) siloxanes abutment intermediate is synthesized, includes RSiX in raw material3And/or R ' SiX3And HO (AA ' SiO)zH；Its In, R, R ', A, A ', z are defined as above；X is identical or different, is independently from each other one of OH, Cl, alkoxy；
(2) intermediate is hydrolyzed；
(3) it is condensed in the presence of basic catalyst, obtains the polysiloxanes from sealing end.
28. preparation method according to claim 27, wherein X is identical or different, is independently from each other C1-10Alkoxy.
29. preparation method according to claim 28, wherein X is identical or different, is independently from each other methoxyl group, second Oxygroup, isopropoxy or isobutoxy.
30. preparation method according to claim 27, which is characterized in that step (1) specifically: in the reactor, be added RSiX3And/or R ' SiX3, add HO (AA ' SiO)zH, the first organic solvent and the first catalyst；Reaction, obtains silane oxygen bridge Base intermediate.
31. preparation method according to claim 30, in step (1), temperature when reaction is -20 DEG C to 60 DEG C；Reaction Time is 30 minutes to 10 hours.
32. preparation method according to claim 30, further include post-processing step after reaction in step (1), that is, passes through With filtering and/or distillation, silane oxygen bridge base midbody solution is obtained.
33. preparation method according to claim 30, in step (1), RSiX3With R ' SiX3Molar ratio be (0~1): 1, Alternatively, R ' SiX3With RSiX3Molar ratio be (0~1): 1.
34. preparation method according to claim 30, in step (1), RSiX3And/or R ' SiX3With HO (AA ' SiO)zH's Molar ratio is (1.8~20): 1.
35. preparation method according to claim 30, in step (1), the dosage of the first catalyst is HO (AA ' SiO)zH's 0.0001 to 10 times of molal quantity.
36. preparation method according to claim 30, in step (1), first catalyst be selected from ammonia, pyridine, hydrochloric acid, One of sulfuric acid, nitric acid, phosphoric acid, organic amine (ammonium), organic acid, metallo-organic compound, ion exchange resin are a variety of.
37. preparation method according to claim 36, in step (1), first catalyst is selected from ammonia, organic amine (ammonium) One of.
38. preparation method according to claim 30, in step (1), the first organic solvent in step (1) is selected from: benzene, Toluene, dimethylbenzene, methanol, ethyl alcohol, isopropanol, isobutanol, hexane, hexamethylene, acetone, butanone, tetrahydrofuran, cyclohexanone, two Six ring of oxygen, ether, petroleum ether, acetonitrile, methylene chloride, dichloroethanes, tetrachloromethane, chloroform, ethyl acetate, dimethyl are sub- One of sulfone, dimethylformamide are a variety of.
39. preparation method according to claim 27, which is characterized in that step (2) specifically: obtained to step (1) Water, the second catalyst and the second organic solvent are added in intermediate, alternatively, alcohol, the second catalyst and the second organic solvent is added； Hydrolysis obtains hydrolysate.
40. preparation method according to claim 39, in step (2), the amount of the water or alcohol that are added is institute in step (1) The HO (AA ' SiO) of additionz0~20 times of the molal quantity of H, but be not 0.
41. preparation method according to claim 40, in step (2), the amount of the water or alcohol that are added is institute in step (1) The HO (AA ' SiO) of additionz0.0001~20 times of the molal quantity of H.
42. preparation method according to claim 39, in step (2), the dosage of the second catalyst is added in step (1) The HO (AA ' SiO) enteredz0.0001 to 10 times of molal quantity.
43. preparation method according to claim 39, the temperature of the hydrolysis in step (2) is 0 DEG C to 150 DEG C, instead It is 30 minutes to 10 hours between seasonable.
44. preparation method according to claim 39, step (2) hydrolysis further includes after the completion post-processing step, i.e., Reaction gained mixture is removed water, is separated by filtration, hydrolysising product solution is obtained.
45. preparation method according to claim 39, in step (2), second catalyst be selected from ammonia, pyridine, hydrochloric acid, One of sulfuric acid, nitric acid, sulfonic acid, phosphoric acid, organic amine (ammonium), organic acid, metallo-organic compound, ion exchange resin are more Kind.
46. preparation method according to claim 45, in step (2), second catalyst is selected from hydrochloric acid, sulfuric acid, nitre One of acid, phosphoric acid, organic acid.
47. preparation method according to claim 39, in step (2), second organic solvent is selected from: benzene, toluene, two Toluene, ether, methyl phenyl ethers anisole, phenetole, ethyl acetate, tetrahydrofuran, dioxane, chloroform, dichloroethanes one kind or It is a variety of.
It is total by solvent in the presence of basic catalyst in step (3) 48. preparation method according to claim 27 Boil dehydrating condensation.
49. preparation method according to claim 48, the step (3) specifically: the hydrolysate obtained to step (2) Basic catalyst is added in solution, carries out condensation reaction, the water of condensation reaction generation is constantly steamed in reaction process；It obtains described From the polysiloxanes of sealing end.
50. preparation method according to claim 49, in step (3), the dosage of the basic catalyst is in step (1) The HO (AA ' SiO) being addedz0.0001~10 times of molal quantity.
51. preparation method according to claim 49, in step (3), the basic catalyst is selected from the hydroxide of metal One of object or its hydrate, metallo-organic compound, organic amine (ammonium) are a variety of.
52. preparation method according to claim 49, in step (3), the temperature of condensation reaction is total more than solvent and water 0~40 DEG C of boiling point, the reaction time is 30 minutes to 48 hours.
It further include post-processing step after condensation reaction in step (3) 53. preparation method according to claim 49, I.e. by mixture obtained by condensation reaction it is neutralized, remove water, be separated by filtration and purify, obtain the polysiloxanes from sealing end.
54. polysiloxanes (b) or right described in the described in any item polysiloxanes (a) of claim 1-19, claim 20 It is required that the purposes of the described in any item polysiloxanes from sealing end of 21-26, which is characterized in that the polysiloxanes is used for organic painting Expect the improvement of high molecular heatproof, radiation hardness and weather-resistant performance；Alternatively, for improving High Power LED (LED) heat resistance of packaging plastic and organic pressure-sensitive gel, index of refraction, caking property, air-tightness and mechanical property.
55. purposes according to claim 54, wherein the organic coating macromolecule be end hydroxyl silicone oil, hydroxy resin, Pass through one of the cured resin of Si―H addition reaction, polyurethane resin, epoxy resin, acrylic resin, alkyd resin.
56. purposes according to claim 54, wherein include organosilicon tree in the packaging plastic or organic pressure-sensitive gel Rouge.
57. a kind of coating high molecular material of modification, which is characterized in that wanted in the raw material of the high molecular material including right Ask polysiloxanes (b) described in the described in any item polysiloxanes (a) of 1-19, claim 20 or claim 21-26 any The polysiloxanes from sealing end described in.
58. the coating high molecular material of modification according to claim 57, wherein the high molecular material is terminal hydroxy group Silicone oil, can pass through the cured resin of Si―H addition reaction, polyurethane resin, epoxy resin, acrylic resin, alkyd tree at hydroxy resin One of rouge.
59. a kind of packaging plastic or organic pressure-sensitive gel, which is characterized in that the glue includes modified organic siliconresin, described to change Property organic siliconresin raw material in include the described in any item polysiloxanes (a) of claim 1-19, described in claim 20 Polysiloxanes (b) or claim 21-26 it is described in any item from sealing end polysiloxanes.
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