CN105330865A - Synthesis method of catenane-like polysiloxane - Google Patents
Synthesis method of catenane-like polysiloxane Download PDFInfo
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Abstract
The invention relates to the technical field of polysiloxane synthesis, aims to solve the problem that conventional catenane-like polysiloxane has no feasible synthesis technology, and provides a synthesis method of catenane-like polysiloxane; with small ring-like siloxane and water as raw materials, and under the action of a metal catalyst, a reaction is carried out in an organic solvent, then a post-treatment process is carried out, and the catenane-like polysiloxane is obtained; the catenane-like polysiloxane is synthesized with high efficiency, the productive rate can reach 60-95%, the product has good thermal stability, and the synthesis method has the advantages of mild reaction conditions, wide applicable range, low energy consumption, high synthesis efficiency, cheap and easily available raw materials, simple and feasible product purification process and the like.
Description
Technical field
The present invention relates to polysiloxane synthesis technical field, particularly relate to a kind of high-efficiency synthesis method of catenne shape polysiloxane.
Background technology
Catenne shape polysiloxane has important use, as having special construction polysiloxane for molecular recognition, synthesis of super branched etc., preparing the aspect such as fire resistant polymer and development of new silane coupling agent.So far, only have document to propose the concept of catenne shape polysiloxane, practicable synthetic method does not realize the synthesis of catenne shape polysiloxane.
Nineteen fifty-three, Frisch, Martin and Mark infers why high molecular weight silicone has liquid or wax-like outward appearance, owing to causing containing catenne shape polysiloxane in polysiloxane, these catenne shape polysiloxane act as the effect (Monatsh.Chem.1953 of softening agent, 84,250-256), but this hypothesis does not obtain experiment to be confirmed.
Bannister and Semlyen proposes the large ring-like polysiloxane of heating when studying the thermostability of large ring-like polysiloxane may form catenne shape polysiloxane (Polymer1981,22,377-381), they just propose a kind of conjecture equally, and they obtain catenne shape polysiloxane really not have Data support.
At present about the report of catenne shape polysiloxane also just rests on proposition concept and conjecture stage, practicable synthetic method does not obtain catenne shape polysiloxane.
Summary of the invention
For solving the problem not having practicable synthetic technology existed in the research of existing catenne shape polysiloxane, the present invention proposes a kind of synthetic method of catenne shape polysiloxane, advantages such as there is reaction conditions gentleness, applied widely, energy consumption is low, combined coefficient is high, raw material is cheap and easy to get, product purification process is simple.
The present invention is achieved by the following technical solutions: a kind of synthetic method of catenne shape polysiloxane is for raw material with little annular siloxane and water, and under the effect of metal catalyst, react in organic solvent, again through last handling process, obtain catenne shape polysiloxane, the present invention realizes the efficient synthesis of catenne shape polysiloxane, and productive rate can reach 60 ~ 95%, and product has the advantages such as Heat stability is good.
Reaction process is as follows:
Wherein, R
1, R
2, R
3, R
4separately be selected from hydrogen, fluorine, alkyl, thiazolinyl, alkynyl, aromatic base, epoxy group(ing), ester group, sulfonic group, carboxyl, itrile group, haloalkyl, haloalkenyl group, halo alkynyl, hydroxyl a kind of, m, n, p, q are respectively the integer being more than or equal to 0, x be greater than 0 integer.
Described little annular siloxane is selected from one or more in cyclotrisiloxane, cyclotetrasiloxane, D5.The mass ratio of little annular siloxane and water is 1: 0.001 ~ 1.
Described metal catalyst is selected from metal simple-substance, metal oxide, metal-salt, complex compound a kind of.The mass ratio of little cyclosiloxane and metal catalyst is 1: 0.0001 ~ 0.1.As preferably, metal catalyst is selected from the simple substance of all metals or corresponding compound, more preferably a kind of simple substance of metal or corresponding compound in iron, cobalt, nickel, ruthenium, rhodium, platinum, palladium, gold and silver, copper, tin, titanium, pick, chromium, manganese, lanthanide series metal.
Organic solvent is selected from one or more in alkane, aromatic hydrocarbon, ethers, cyclic ethers class, ketone.Amount used is for making the amount of solute dissolves.As preferably, organic solvent is selected from one or more in hexane, hexanaphthene, toluene, ether, butyl ether, tetrahydrofuran (THF), dioxane, acetone, methyl iso-butyl ketone (MIBK).
Temperature of reaction is-75 ~ 140 DEG C, and the reaction times is 10 minutes ~ 24 hours.
Last handling process is vacuum drying, absorption, precipitation or recrystallization.
The present invention is with little annular siloxane (as cyclotrisiloxane, cyclotetrasiloxane and D5 etc.), water for raw material, and under the existence of metal catalyst, polymerization reaction take place, realizes the efficient synthesis of catenne shape polysiloxane.Product structure has carried out structural characterization by infrared spectra, hydrogen spectrum nucleus magnetic resonance, silicon spectrum nucleus magnetic resonance, chemical method end group analysis and rheology etc., be have studied the thermostability of product by thermogravimetic analysis (TGA).Infrared spectra, hydrogen spectrum nucleus magnetic resonance, silicon spectrum nucleus magnetic resonance, chemical method end group analysis etc. prove product not containing Si-OH, and rheological data shows that product contains long-chain branch.The catenne shape polysiloxane that what comprehensive above characterization data can prove that we obtain is with long branched chain structure.In addition, thermogravimetic analysis (TGA) data show that the product that we obtain has excellent thermostability.
The present invention proposes the novel method of a kind of catenne shape polysiloxane synthesis, its beneficial effect is: advantages such as having reaction conditions gentleness, applied widely, energy consumption is low, combined coefficient is high, raw material is cheap and easy to get, product purification process is simple, product has the advantages such as superior heat-stability.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of methyl ethylene catenne shape polysiloxane in embodiment 1;
Fig. 2 is the hydrogen spectrum nucleus magnetic resonance figure of methyl ethylene catenne shape polysiloxane in embodiment 1;
Fig. 3 is the silicon spectrum nucleus magnetic resonance figure of methyl ethylene catenne shape polysiloxane in embodiment 1;
Fig. 4 be in embodiment 1 methyl ethylene catenne shape polysiloxane and methyl silicate react before gel permeation chromatography figure;
Fig. 5 is methyl ethylene catenne shape polysiloxane and the reacted gel permeation chromatography figure of methyl silicate in embodiment 1;
Fig. 6 is the Cole-Cole figure of methyl ethylene catenne shape polysiloxane in embodiment 1;
Fig. 7 is the hot weightless picture of methyl ethylene catenne shape polysiloxane in embodiment 1.
Embodiment
Below by embodiment, the present invention is described in further detail, raw materials used all commercially available in embodiment.
Embodiment 1: the preparation of methyl ethylene catenne shape polysiloxane
-75 DEG C, 0.15 gram of water is added to and is equipped with 150 gram 1,3, in 1000 milliliters of there-necked flasks of 5-trimethylammonium-1,3,5-trivinyl cyclotrisiloxane, 0.015 gram of Raney Ni and 500 milliliters of ether, stirring reaction, after 10 minutes, adds 300 grams of gacs, stirs 30 minutes, adsorb, filter and through vacuum drying, obtain colourless viscous liquid, i.e. methyl ethylene catenne shape polysiloxane, productive rate 80%, the weight-average molecular weight of product is 8 × 10
5dalton, molecular weight distribution is 1.5.
The infrared spectrogram of methyl ethylene catenne shape polysiloxane as shown in Figure 1, the hydrogen spectrum nucleus magnetic resonance figure of methyl ethylene catenne shape polysiloxane as shown in Figure 2, the silicon spectrum nucleus magnetic resonance figure of methyl ethylene catenne shape polysiloxane as shown in Figure 3, gel permeation chromatography figure before methyl ethylene catenne shape polysiloxane and methyl silicate react as shown in Figure 4, methyl ethylene catenne shape polysiloxane and the reacted gel permeation chromatography figure of methyl silicate are as shown in Figure 5, the Cole-Cole figure of methyl ethylene catenne shape polysiloxane as shown in Figure 6, the hot weightless picture of methyl ethylene catenne shape polysiloxane as shown in Figure 7.
Embodiment 2: the preparation of methyl catenne shape polysiloxane
-5 DEG C, 8 grams of water are added in 1000 milliliters of there-necked flasks that 240 grams of octamethylcyclotetrasiloxanes, 2 grams of ferric oxide and 600 milliliters of tetrahydrofuran (THF)s are housed, stirring reaction is after 4 hours, adsorb, filter and through vacuum drying, obtain colourless viscous liquid, i.e. methyl catenne shape polysiloxane, productive rate 90%, the weight-average molecular weight of product is 6 × 10
6dalton, molecular weight distribution is 1.2.
Embodiment 3: the preparation of methyl hydrogen catenne shape polysiloxane
30 DEG C, 30 grams of water are added to and are equipped with 300 gram 1,3, in 1000 milliliters of there-necked flasks of 5,7,9-pentamethyl-D5,7 grams of ferrocene and 500 milliliters of hexanaphthenes, stirring reaction, after 8 hours, adds 30 grams of gacs, stirs 15 minutes, adsorb, filter, impouring methyl alcohol after reaction solution is concentrated, obtain colourless viscous liquid, i.e. methyl hydrogen catenne shape polysiloxane, productive rate 75%, the weight-average molecular weight of product is 5 × 10
4dalton, molecular weight distribution is 1.7.
Embodiment 4: the preparation of aminomethyl phenyl catenne shape polysiloxane
70 DEG C, 5 grams of water are added to and are equipped with 25 gram 1,3,5,7,9-pentamethyl--1,3,5,7, in 300 milliliters of there-necked flasks of 9-pentapheneyl D5,1.3 grams of iron trichlorides and 100 milliliters of ethyl acetate, stirring reaction, after 10 hours, adds 5 grams of gacs, stir 10 minutes, filter and precipitate with ethanol, obtaining white solid, i.e. aminomethyl phenyl catenne shape polysiloxane, productive rate 60%, the weight-average molecular weight of product is 3 × 10
5dalton, molecular weight distribution is 1.3.
Embodiment 5: the preparation of phenyl epoxy group(ing) catenne shape polysiloxane
90 DEG C, 24 grams of water are added in 300 milliliters of there-necked flasks that 40 grams of octaphenylcyclotetrasiloxanes, 20 grams of octa-epoxy cyclotetrasiloxanes, 4.8 grams of Palladous chlorides and 100 milliliters of methyl iso-butyl ketone (MIBK) are housed, stirring reaction, after 12 hours, adds 15 grams of gacs, stirs 50 minutes, adsorb, filter and through vacuum drying, obtain white solid, i.e. phenyl epoxy group(ing) catenne shape polysiloxane, productive rate 75%, the weight-average molecular weight of product is 8 × 10
4dalton, molecular weight distribution is 1.2.
Embodiment 6: the preparation of vinyl epoxy base catenne shape polysiloxane
110 DEG C, 60 grams of water are added to and are equipped with 100 gram 1,3,5,7-tetravinyl-1,3, in 500 milliliters of there-necked flasks of 5,7-tetra-epoxy basic ring tetrasiloxane, 10 gram of six hydration Platinic chloride and 300 milliliters of ethyl acetate, stirring reaction is after 20 hours, adsorb, by reaction solution impouring 300 ml methanol, filter and through vacuum drying, obtain white solid, i.e. vinyl epoxy base catenne shape polysiloxane, productive rate 85%, the weight-average molecular weight of product is 6 × 10
6dalton, molecular weight distribution is 1.9.
Embodiment 7: the preparation of allyl group p-chloromethyl phenyl catenne shape polysiloxane
140 DEG C, 56 grams of water are added to and are equipped with 70 gram 1,3,5,7-tetraallyl-1,3, in 500 milliliters of there-necked flasks of 5,7-tetra-(p-chloromethyl phenyl) cyclotetrasiloxane, 0.1 gram of acetylacetonate nickel and 300 milliliters of methyl iso-butyl ketone (MIBK), stirring reaction is after 24 hours, adsorb, by reaction solution impouring 600 ml methanol, filter and through vacuum drying, obtain white solid, i.e. allyl group p-chloromethyl phenyl catenne shape polysiloxane, productive rate 83%, the weight-average molecular weight of product is 7 × 10
5dalton, molecular weight distribution is 1.7.
Embodiment 8: the preparation of n-butyl ethoxycarbonyl catenne shape polysiloxane
100 DEG C, 9 grams of water are added to and are equipped with 9 gram 1,3,5,7-tetra-n-butyl-1,3, in 100 milliliters of there-necked flasks of 5,7-tetrapropylene acetoacetic ester basic ring tetrasiloxane, 0.5 gram of ferric oxide and 50 milliliters of ether, stirring reaction is after 17 hours, add 0.5 gram of gac, stir 30 minutes, adsorb, filter and through vacuum drying, obtain colourless liquid, i.e. n-butyl ethoxycarbonyl catenne shape polysiloxane, productive rate 78%, the weight-average molecular weight of product is 4 × 10
4dalton, molecular weight distribution is 1.4.
Embodiment 9: the preparation of cyclohexylacrylic ethoxycarbonyl catenne shape polysiloxane
10 DEG C, be added to by 0.018 gram of water in 300 milliliters of there-necked flasks that 2 gram of eight cyclohexyl ring tetrasiloxane, 2 gram of eight ethyl propenoate basic ring tetrasiloxane, 0.01 gram of rhodium sesquioxide and 100 milliliters of butanone are housed, stirring reaction, after 13 hours, adds 5 grams of gacs, stir 20 minutes, adsorb, filter, and through vacuum drying, obtain white solid, i.e. cyclohexylacrylic ethoxycarbonyl catenne shape polysiloxane, productive rate 81%, the weight-average molecular weight of product is 7 × 10
6dalton, molecular weight distribution is 1.3.
Claims (9)
1. the synthetic method of a catenne shape polysiloxane, it is characterized in that, described synthetic method is for raw material with little annular siloxane and water, and under the effect of metal catalyst, react in organic solvent, again through last handling process, obtain catenne shape polysiloxane, reaction process is as follows:
Wherein, R
1, R
2, R
3, R
4separately be selected from hydrogen, fluorine, alkyl, thiazolinyl, alkynyl, aromatic base, epoxy group(ing), ester group, sulfonic group, carboxyl, itrile group, haloalkyl, haloalkenyl group, halo alkynyl, hydroxyl a kind of, m, n, p, q are respectively the integer being more than or equal to 0, x be greater than 0 integer.
2. the synthetic method of a kind of catenne shape polysiloxane according to claim 1, it is characterized in that, described little annular siloxane is selected from one or more in cyclotrisiloxane, cyclotetrasiloxane, D5.
3. the synthetic method of a kind of catenne shape polysiloxane according to claim 1 and 2, is characterized in that, the mass ratio of little annular siloxane and water is 1: 0.001 ~ 1.
4. the synthetic method of a kind of catenne shape polysiloxane according to claim 1 and 2, it is characterized in that, described metal catalyst is selected from metal simple-substance, metal oxide, metal-salt, complex compound a kind of, and the mass ratio of little annular siloxane and metal catalyst is 1: 0.0001 ~ 0.1.
5. the synthetic method of a kind of catenne shape polysiloxane according to claim 4, it is characterized in that, a kind of simple substance of metal or corresponding compound in metal catalyst chosen from Fe, cobalt, nickel, ruthenium, rhodium, platinum, palladium, gold and silver, copper, tin, titanium, pick, chromium, manganese, lanthanide series metal.
6. the synthetic method of a kind of catenne shape polysiloxane according to claim 1, is characterized in that, organic solvent is selected from one or more in alkane, aromatic hydrocarbon, ethers, cyclic ethers class, ketone.
7. the synthetic method of a kind of catenne shape polysiloxane according to claim 6, it is characterized in that, organic solvent is selected from one or more in hexane, hexanaphthene, toluene, ether, butyl ether, tetrahydrofuran (THF), dioxane, acetone, methyl iso-butyl ketone (MIBK).
8. the synthetic method of a kind of catenne shape polysiloxane according to claim 1, is characterized in that, temperature of reaction is-75 DEG C ~ 140 DEG C, and the reaction times is 10 minutes ~ 24 hours.
9. the synthetic method of a kind of catenne shape polysiloxane according to claim 1, it is characterized in that, last handling process is vacuum drying, absorption, precipitation or recrystallization.
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