CN105330865B - A kind of synthetic method of catenne shape polysiloxanes - Google Patents
A kind of synthetic method of catenne shape polysiloxanes Download PDFInfo
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Abstract
The present invention relates to polysiloxanes synthesis technical field, to solve the problems, such as there is no practicable synthetic technology present in existing catenne shape polysiloxanes research, the present invention proposes a kind of synthetic method of catenne shape polysiloxanes, using small annular siloxane and water as raw material, and in the presence of metallic catalyst, reacted in organic solvent, pass through last handling process again, obtain catenne shape polysiloxanes, the present invention realizes efficiently synthesizing for catenne shape polysiloxanes, yield can reach 60~95%, product has heat endurance good, and reaction condition is gentle, it is applied widely, energy consumption is low, combined coefficient is high, raw material is cheap and easy to get, the advantages that product purification process is simple and easy.
Description
Technical field
The present invention relates to polysiloxanes synthesis technical field, more particularly to a kind of efficiently synthesizing for catenne shape polysiloxanes
Method.
Background technology
Catenne shape polysiloxanes has important use, is such as used for molecular recognition, synthesis of super branched gathers with special construction
Siloxanes, fire resistant polymer is prepared with developing novel silane coupler etc..So far, only document proposes catenne shape
The concept of polysiloxanes, not practicable synthetic method realize the synthesis of catenne shape polysiloxanes.
Nineteen fifty-three, Frisch, Martin and Mark speculate why high molecular weight silicone has liquid or wax-like
Outward appearance, be due in polysiloxanes contain catenne shape polysiloxanes caused by, these catenne shape polysiloxanes act as being plasticized
The effect (Monatsh.Chem.1953,84,250-256) of agent, but this hypothesis does not obtain experiment and confirmed.
Bannister and Semlyen proposes the big ring-like poly- silicon of heating in the heat endurance of the big ring-like polysiloxanes of research
Oxygen alkane may form catenne shape polysiloxanes (Polymer 1981,22,377-381), and same they simply propose one kind
Conjecture, data do not support them to obtain catenne shape polysiloxanes really.
The current report about catenne shape polysiloxanes is also merely resting on concept and the conjecture stage of proposing, unactual
Feasible synthetic method obtains catenne shape polysiloxanes.
The content of the invention
To solve the problems, such as there is no practicable synthetic technology, this hair present in existing catenne shape polysiloxanes research
It is bright to propose a kind of synthetic method of catenne shape polysiloxanes, with reaction condition is gentle, applied widely, energy consumption is low, synthesis
The advantages that efficiency high, raw material are cheap and easy to get, product purification process is simple and easy.
The present invention is achieved by the following technical solutions：A kind of synthetic method of catenne shape polysiloxanes is with small ring-type
Siloxanes and water are raw material, and in the presence of metallic catalyst, are reacted in organic solvent, then by post-processing
Journey, obtains catenne shape polysiloxanes, and the present invention realizes efficiently synthesizing for catenne shape polysiloxanes, and yield can reach 60~
95%, product has the advantages that heat endurance is good.
Course of reaction is as follows：
Wherein, R1、R2、R3、R4Separately selected from hydrogen, fluorine, alkyl, alkenyl, alkynyl, aromatic radical, epoxy radicals, ester group,
A kind of in sulfonic group, carboxyl, itrile group, haloalkyl, haloalkenyl group, halo alkynyl, hydroxyl, m, n, p, q are respectively to be more than or equal to 0
Integer, x is integer more than 0.
Described small annular siloxane is one or more of in cyclotrisiloxane, cyclotetrasiloxane, D5.It is small
The mass ratio of annular siloxane and water is 1: 0.001~1.
Described metallic catalyst is a kind of in metal simple-substance, metal oxide, metal salt, complex compound.Small ring silica
The mass ratio of alkane and metallic catalyst is 1: 0.0001~0.1.Preferably, metallic catalyst be selected from all metals simple substance or
The corresponding compound of person, more preferably from iron, cobalt, nickel, ruthenium, rhodium, platinum, palladium, gold, silver, copper, tin, titanium, pick, chromium, manganese, lanthanide series metal
A kind of simple substance of middle metal or corresponding compound.
Organic solvent is one or more of in alkane, aromatic hydrocarbon, ethers, cyclic ethers class, ketone.Amount used is to make solute
The amount of dissolving.Preferably, organic solvent is selected from hexane, hexamethylene, toluene, ether, butyl ether, tetrahydrofuran, dioxane, third
It is one or more of in ketone, methyl iso-butyl ketone (MIBK).
Reaction temperature is -75~140 DEG C, and the reaction time is 10 minutes~24 hours.
Last handling process is vacuum drying, absorption, precipitation or recrystallization.
The present invention using small annular siloxane (such as cyclotrisiloxane, cyclotetrasiloxane and D5), water as raw material,
In the presence of metallic catalyst, polymerisation occurs, realizes efficiently synthesizing for catenne shape polysiloxanes.Product structure passes through red
External spectrum, hydrogen spectrum nuclear magnetic resonance, silicon spectrum nuclear magnetic resonance, chemical method end-group analysis and rheology etc. have carried out structural characterization, pass through
Thermogravimetic analysis (TGA) have studied the heat endurance of product.Infrared spectrum, hydrogen spectrum nuclear magnetic resonance, silicon spectrum nuclear magnetic resonance, chemical method end group
Analysis etc. proves that product does not contain Si-OH, and rheological data shows that product contains long-chain branch.In summary characterize data can be demonstrate,proved
It is bright that we obtain is the catenne shape polysiloxanes with long branched chain structure.In addition, thermogravimetic analysis (TGA) as shown by data we obtain
Product there is excellent heat endurance.
The present invention proposes a kind of new method of catenne shape polysiloxanes synthesis, and its advantage is：With reaction condition
Gently, applied widely, the advantages that energy consumption is low, combined coefficient is high, raw material is cheap and easy to get, product purification process is simple and easy, production
Thing has the advantages that superior heat-stability.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of methyl ethylene catenne shape polysiloxanes in embodiment 1；
Fig. 2 is that the hydrogen of methyl ethylene catenne shape polysiloxanes in embodiment 1 composes nuclear magnetic resonance figures；
Fig. 3 is that the silicon of methyl ethylene catenne shape polysiloxanes in embodiment 1 composes nuclear magnetic resonance figures；
Fig. 4 is methyl ethylene catenne shape polysiloxanes and the gel infiltration color before methyl silicate reaction in embodiment 1
Spectrogram；
Fig. 5 is methyl ethylene catenne shape polysiloxanes and the reacted gel infiltration color of methyl silicate in embodiment 1
Spectrogram；
Fig. 6 is the Cole-Cole figures of methyl ethylene catenne shape polysiloxanes in embodiment 1；
Fig. 7 is the hot weightless picture of methyl ethylene catenne shape polysiloxanes in embodiment 1.
Embodiment
The present invention is described in further detail below by embodiment, it is raw materials used commercially available in embodiment.
Embodiment 1：The preparation of methyl ethylene catenne shape polysiloxanes
- 75 DEG C, 0.15 gram of water is added to equipped with 150 gram 1,3,5- trimethyls -1,3,5- trivinyls cyclotrisiloxane,
In 1000 milliliters of three-necked flasks of 0.015 gram of Raney Ni and 500 milliliters of ether, stirring reaction adds 300 grams of activity after 10 minutes
Charcoal, stir 30 minutes, adsorbed, filter and pass through vacuum drying, obtain colourless viscous liquid, i.e. methyl ethylene catenne shape
Polysiloxanes, yield 80%, the weight average molecular weight of product is 8 × 105Dalton, molecular weight distribution 1.5.
The infrared spectrogram of methyl ethylene catenne shape polysiloxanes is as shown in figure 1, the poly- silica of methyl ethylene catenne shape
The hydrogen spectrum nuclear magnetic resonance figures of alkane is as shown in Fig. 2 silicon spectrum nuclear magnetic resonance figures such as Fig. 3 institutes of methyl ethylene catenne shape polysiloxanes
Show, methyl ethylene catenne shape polysiloxanes is with the gel permeation chromatography figure before methyl silicate reaction as shown in figure 4, methyl second
Alkenyl catenne shape polysiloxanes is with the reacted gel permeation chromatography figure of methyl silicate as shown in figure 5, methyl ethylene catenne
The Cole-Cole of shape polysiloxanes is schemed as shown in fig. 6, the hot weightless picture of methyl ethylene catenne shape polysiloxanes is as shown in Figure 7.
Embodiment 2：The preparation of methyl catenne shape polysiloxanes
- 5 DEG C, 8 grams of water are added to equipped with 240 grams of octamethylcy-clotetrasiloxanes, 2 grams of di-iron trioxides and 600 milliliters of tetrahydrochysenes
In 1000 milliliters of three-necked flasks of furans, stirring reaction is adsorbed after 4 hours, is filtered and is passed through vacuum drying, obtains colourless
Thick liquid, i.e. methyl catenne shape polysiloxanes, yield 90%, the weight average molecular weight of product is 6 × 106Dalton, molecular weight
It is distributed as 1.2.
Embodiment 3：The preparation of methyl hydrogen catenne shape polysiloxanes
30 DEG C, 30 grams of water are added to equipped with 300 gram 1,3,5,7,9- pentamethyl D5s, 7 grams of ferrocene and 500 are in the least
In 1000 milliliters of three-necked flasks for rising hexamethylene, stirring reaction adds 30 grams of activated carbons after 8 hours, stirs 15 minutes, is inhaled
It is attached, filtering, methanol is poured into after reaction solution is concentrated, obtains colourless viscous liquid, i.e. methyl hydrogen catenne shape polysiloxanes, yield
75%, the weight average molecular weight of product is 5 × 104Dalton, molecular weight distribution 1.7.
Embodiment 4：The preparation of aminomethyl phenyl catenne shape polysiloxanes
70 DEG C, 5 grams of water are added to equipped with 25 gram 1,3,5,7,9- pentamethyls -1,3, the siloxanes of 5,7,9- five benzyl ring five,
In 300 milliliters of three-necked flasks of 1.3 grams of ferric trichlorides and 100 milliliters of ethyl acetate, stirring reaction adds 5 grams of work after 10 hours
Property charcoal, stir 10 minutes, filter simultaneously precipitated with ethanol, obtain white solid, i.e. aminomethyl phenyl catenne shape polysiloxanes, produce
Rate 60%, the weight average molecular weight of product is 3 × 105Dalton, molecular weight distribution 1.3.
Embodiment 5：The preparation of phenyl epoxy radicals catenne shape polysiloxanes
90 DEG C, 24 grams of water are added to equipped with 40 grams of octaphenylcyclotetrasiloxanes, 20 grams of octa-epoxy cyclotetrasiloxanes, 4.8
In 300 milliliters of three-necked flasks of gram palladium bichloride and 100 milliliters of methyl iso-butyl ketone (MIBK)s, stirring reaction adds 15 grams of work after 12 hours
Property charcoal, stir 50 minutes, adsorbed, filter and pass through vacuum drying, obtain white solid, be i.e. phenyl epoxy radicals catenne shape gathers
Siloxanes, yield 75%, the weight average molecular weight of product is 8 × 104Dalton, molecular weight distribution 1.2.
Embodiment 6：The preparation of vinyl epoxy base catenne shape polysiloxanes
110 DEG C, 60 grams of water are added to equipped with 100 gram 1,3,5,7- tetravinyls -1,3, the silica of 5,7- tetra- epoxy radicals ring four
In 500 milliliters of three-necked flasks of alkane, 10 gram of six hydration chloroplatinic acid and 300 milliliters of ethyl acetate, stirring reaction is carried out after 20 hours
Absorption, reaction solution is poured into 300 ml methanols, is filtered and is passed through vacuum drying, obtains white solid, i.e. vinyl epoxy base
Catenne shape polysiloxanes, yield 85%, the weight average molecular weight of product is 6 × 106Dalton, molecular weight distribution 1.9.
Embodiment 7：The preparation of pi-allyl p- chloromethyl phenyl catenne shape polysiloxanes
140 DEG C, 56 grams of water are added to equipped with 70 gram 1,3,5,7- tetraallyls -1,3,5,7- tetra- (p- chloromethyl phenyls) rings
In 500 milliliters of three-necked flasks of tetrasiloxane, 0.1 gram of nickel acetylacetonate and 300 milliliters of methyl iso-butyl ketone (MIBK)s, stirring reaction 24 is small
Shi Hou, adsorbed, reaction solution is poured into 600 ml methanols, filtered and pass through vacuum drying, obtain white solid, i.e. alkene
Propyl group p- chloromethyl phenyl catenne shape polysiloxanes, yield 83%, the weight average molecular weight of product is 7 × 105Dalton, molecular weight
It is distributed as 1.7.
Embodiment 8：The preparation of n-butyl ethoxycarbonyl catenne shape polysiloxanes
100 DEG C, 9 grams of water are added to equipped with 9 gram 1,3,5,7- tetra-n-butyls -1,3, the silicon of 5,7- tetrapropylene acetoacetic ester basic ring four
In 100 milliliters of three-necked flasks of oxygen alkane, 0.5 gram of di-iron trioxide and 50 milliliters of ether, stirring reaction adds 0.5 after 17 hours
Gram activated carbon, stir 30 minutes, adsorbed, filter and pass through vacuum drying, obtain colourless liquid, i.e. n-butyl second
Ester group catenne shape polysiloxanes, yield 78%, the weight average molecular weight of product is 4 × 104Dalton, molecular weight distribution 1.4.
Embodiment 9：The preparation of cyclohexylacrylic ethoxycarbonyl catenne shape polysiloxanes
10 DEG C, 0.018 gram of water is added to equipped with 2 gram of eight cyclohexyl ring tetrasiloxane, 2 gram of eight silicon of ethyl acrylate basic ring four
In 300 milliliters of three-necked flasks of oxygen alkane, 0.01 gram of rhodium sesquioxide and 100 milliliters of butanone, stirring reaction adds 5 after 13 hours
Gram activated carbon, stir 20 minutes, adsorbed, filter, and pass through vacuum drying, obtain white solid, i.e. cyclohexylacrylic
Ethoxycarbonyl catenne shape polysiloxanes, yield 81%, the weight average molecular weight of product is 7 × 106Dalton, molecular weight distribution 1.3.
Claims (9)
1. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：- 75 DEG C, by 0.15
Gram water is added to equipped with 150 gram 1,3,5- trimethyls -1,3,5- trivinyls cyclotrisiloxane, 0.015 gram of Raney Ni and 500 milliliters
In 1000 milliliters of three-necked flasks of ether, stirring reaction adds 300 grams of activated carbons after 10 minutes, stirs 30 minutes, is inhaled
It is attached, filter and pass through vacuum drying, obtain colourless viscous liquid, i.e. methyl ethylene catenne shape polysiloxanes.
2. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：- 5 DEG C, by 8 grams of water
It is added to 1000 milliliters of three mouthfuls of burnings equipped with 240 grams of octamethylcy-clotetrasiloxanes, 2 grams of di-iron trioxides and 600 milliliters of tetrahydrofurans
In bottle, stirring reaction is adsorbed after 4 hours, is filtered and is passed through vacuum drying, obtains colourless viscous liquid, i.e. methyl catenne
Shape polysiloxanes.
3. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：30 DEG C, by 30 grams
Water is added to equipped with 300 gram 1,3,5,7,9- pentamethyl D5s, 1000 milliliters of 7 grams of ferrocene and 500 milliliters of hexamethylenes
In three-necked flask, stirring reaction adds 30 grams of activated carbons after 8 hours, stirs 15 minutes, is adsorbed, and filters, and reaction solution is dense
Methanol is poured into after contracting, obtains colourless viscous liquid, i.e. methyl hydrogen catenne shape polysiloxanes.
4. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：70 DEG C, by 5 grams of water
It is added to equipped with 25 gram 1,3,5,7,9- pentamethyls -1,3, the siloxanes of 5,7,9- five benzyl ring five, 1.3 grams of ferric trichlorides and 100 are in the least
In 300 milliliters of three-necked flasks for rising ethyl acetate, stirring reaction adds 5 grams of activated carbons after 10 hours, stirs 10 minutes, filtering
And precipitated with ethanol, obtain white solid, i.e. aminomethyl phenyl catenne shape polysiloxanes.
5. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：90 DEG C, by 24 grams
Water is added to equipped with 40 grams of octaphenylcyclotetrasiloxanes, 20 grams of octa-epoxy cyclotetrasiloxanes, 4.8 grams of palladium bichlorides and 100 milliliters of first
In 300 milliliters of three-necked flasks of base isobutyl ketone, stirring reaction adds 15 grams of activated carbons after 12 hours, stirs 50 minutes, carries out
Absorption, filter and pass through vacuum drying, obtain white solid, i.e. phenyl epoxy radicals catenne shape polysiloxanes.
6. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：110 DEG C, by 60 grams
Water is added to equipped with 100 gram 1,3,5,7- tetravinyls -1,3,5,7- tetra- epoxy radicals cyclotetrasiloxanes, 10 gram of six hydration chloroplatinic acid with
In 500 milliliters of three-necked flasks of 300 milliliters of ethyl acetate, stirring reaction is adsorbed after 20 hours, and reaction solution is poured into 300
In ml methanol, filter and pass through vacuum drying, obtain white solid, i.e. vinyl epoxy base catenne shape polysiloxanes.
7. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：140 DEG C, by 56 grams
Water is added to equipped with 70 grams of 1,3,5,7- tetraallyls -1,3,5,7- four（p- chloromethyl phenyl）Cyclotetrasiloxane, 0.1 gram
In 500 milliliters of three-necked flasks of nickel acetylacetonate and 300 milliliters of methyl iso-butyl ketone (MIBK)s, stirring reaction is adsorbed after 24 hours,
Reaction solution is poured into 600 ml methanols, filters and passes through vacuum drying, obtain white solid, i.e. pi-allylp- chloromethylbenzene
Base catenne shape polysiloxanes.
8. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：100 DEG C, by 9 grams
Water be added to equipped with 9 grams of 1,3,5,7- tetra-n-butyl -1,3,5,7- tetrapropylene acetoacetic ester basic rings tetrasiloxanes, 0.5 gram three
In 100 milliliters of three-necked flasks for aoxidizing two iron and 50 milliliters of ether, stirring reaction adds 0.5 gram of activated carbon, stirring after 17 hours
30 minutes, adsorbed, filter and pass through vacuum drying, obtain colourless liquid, be i.e. n-butyl ethoxycarbonyl catenne shape gathers
Siloxanes.
9. a kind of synthetic method of catenne shape polysiloxanes, it is characterised in that described synthetic method is：10 DEG C, by 0.018
Gram water is added to equipped with 2 gram of eight cyclohexyl ring tetrasiloxane, 2 gram of eight ethyl acrylate basic ring tetrasiloxane, 0.01 gram of three oxidation two
In 300 milliliters of three-necked flasks of rhodium and 100 milliliters of butanone, stirring reaction adds 5 grams of activated carbons after 13 hours, stirs 20 minutes,
Adsorbed, filtered, and pass through vacuum drying, obtain white solid, i.e. cyclohexylacrylic ethoxycarbonyl catenne shape polysiloxanes.
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