CN118459765A - Hyperbranched vinyl end-capping agent and preparation method and application thereof - Google Patents
Hyperbranched vinyl end-capping agent and preparation method and application thereof Download PDFInfo
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- CN118459765A CN118459765A CN202410868778.8A CN202410868778A CN118459765A CN 118459765 A CN118459765 A CN 118459765A CN 202410868778 A CN202410868778 A CN 202410868778A CN 118459765 A CN118459765 A CN 118459765A
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- hyperbranched
- vinyl
- siloxane
- silicone oil
- capping agent
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 93
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229920002545 silicone oil Polymers 0.000 claims abstract description 78
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- -1 siloxane ring Chemical group 0.000 claims abstract description 37
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 125000005842 heteroatom Chemical group 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 239000002981 blocking agent Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000006837 decompression Effects 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000002210 silicon-based material Substances 0.000 description 6
- 229920002379 silicone rubber Polymers 0.000 description 6
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 125000004437 phosphorous atom Chemical group 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- JMVWCCOXRGFPJZ-UHFFFAOYSA-N propoxyboronic acid Chemical compound CCCOB(O)O JMVWCCOXRGFPJZ-UHFFFAOYSA-N 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to the field of preparation of organosilicon materials, in particular to a hyperbranched vinyl end-capping agent, a preparation method and application thereof, wherein the hyperbranched vinyl end-capping agent comprises a siloxane ring body and a linear siloxane chain segment connected with silicon atoms on the siloxane ring body; the number of silicon atoms in the siloxane ring is at least 3; the number of silicon atoms in the linear siloxane segment is at least 2; at least a portion of the end groups of the linear siloxane segments are vinyl groups. Compared with the prior hyperbranched structure of the organic siloxane, the molecular structure of the organic siloxane comprises a siloxane ring structure, and compared with the prior hyperbranched structure only comprising a linear structure, the addition of the siloxane ring structure can greatly improve the branching degree of the hyperbranched end-capping agent, so that the prepared hyperbranched silicone oil has higher thermal stability and lower glass transition temperature.
Description
Technical Field
The invention relates to the field of preparation of organic silicon materials, in particular to a hyperbranched vinyl end-capping agent and a preparation method and application thereof.
Background
Hyperbranched structures are special polymer structures which have a highly branched three-dimensional network structure. The structure has wide application prospect in the field of organic silicon. Hyperbranched structures can be used to improve the physical and mechanical properties of silicone rubber. Silicone rubber is a commonly used organic silicon material and has excellent weather resistance, high and low temperature resistance and electrical properties. By introducing the hyperbranched structure, the crosslinking density of the silicone rubber can be increased, the hardness and heat resistance of the silicone rubber can be improved, and meanwhile, the good elasticity and light transmittance can be kept.
Furthermore, hyperbranched structures can also be used to improve the stability of silicone oils. Silicone oil is a commonly used silicone material with excellent lubricity, water repellency, and weather resistance. By introducing the hyperbranched structure into the silicone oil, the viscosity and stability of the silicone oil can be increased, and the application effect and the service life of the silicone oil can be improved.
In addition, the hyperbranched structure can also be used for preparing organic silicon composite materials. The organic silicon composite material is a material formed by compounding an organic silicon material and other materials, and has excellent comprehensive performance. By introducing hyperbranched structures into the silicone composite, the toughness and heat resistance thereof can be improved while maintaining good electrical and mechanical properties. The hyperbranched structure has wide application prospect in the field of organic silicon, and can be used for improving the performances of silicon rubber, silicone oil and organic silicon composite materials and improving the stability and comprehensive performance of the silicon rubber, the silicone oil and the organic silicon composite materials. With the continuous progress of technology and the deep application research, the hyperbranched structure has wider application prospect in the field of organic silicon.
Vinyl methyl silicone oil is a common organic silicon material, has the characteristics of excellent thermal stability, electrical insulation, chemical inertness, hydrophobicity and the like, and is widely applied to various fields. However, the preparation technology of vinyl silicone oil with hyperbranched structure is relatively deficient, so that a novel preparation method of hyperbranched vinyl silicone oil is proposed and realized, and the preparation method has important significance for improving the product performance.
Disclosure of Invention
The invention provides a hyperbranched vinyl end-capping agent, a preparation method and application thereof to overcome the defects in the prior art, and aims to overcome the defects that a method for preparing a hyperbranched organic silicon material is complex and relatively deficient.
In order to achieve the aim of the invention, the invention is realized by the following technical scheme:
in a first aspect, the present invention provides a hyperbranched vinyl-capping agent,
A linear siloxane segment comprising a siloxane ring and attached to a silicon atom on the siloxane ring;
The number of silicon atoms in the siloxane ring is at least 3;
The number of silicon atoms in the linear siloxane segment is at least 2;
at least a portion of the end groups of the linear siloxane segments are vinyl groups.
Compared with the traditional linear blocking agents (such as hexamethyldisiloxane and long-chain polysiloxane), the hyperbranched vinyl blocking agent has a hyperbranched structure, so that after the hyperbranched vinyl blocking agent is added into a silicone oil preparation system, the hyperbranched vinyl blocking agent can block an originally linear polysiloxane linkage segment, so that the originally linear silicone oil is converted into the silicone oil with the hyperbranched structure.
Compared with the prior hyperbranched structure of the organic siloxane, the molecular structure of the organic siloxane comprises a siloxane ring structure, and compared with the prior hyperbranched structure only comprising a linear structure, the branching degree of the hyperbranched end-capping agent can be greatly improved by adding the siloxane ring structure. Meanwhile, on the premise of similar molecular weight, the blocking agent containing the siloxane ring structure has less entanglement among molecular chains, so that the viscosity of the blocking agent is obviously lower than that of the blocking agent only containing hyperbranched vinyl with linear structure, and the blocking agent is easier to participate in a silicone oil production system.
In addition, the preparation method of the silicone oil in the prior art is generally obtained by ring-opening polymerization of organic silicon rings (such as D3 and D4) in the presence of a catalyst, and the hyperbranched vinyl end-capping agent in the application has siloxane rings in the structure, so that the siloxane rings can also participate in the ring-opening polymerization of the organic silicon rings, thereby improving the molecular weight of the silicone oil in a short time and simultaneously rapidly improving the branching degree of the silicone oil.
Preferably, part or all of the siloxane ring bodies and/or linear siloxane segments are doped with heteroatoms other than silicon, oxygen, carbon.
The hyperbranched vinyl end-capping agent disclosed by the application can be doped with hetero atoms except silicon, oxygen and carbon in a siloxane ring body and/or a linear siloxane chain segment, and the properties of the end-capping agent and the silicone oil containing the end-capping agent are effectively regulated and controlled through the doped hetero atoms, for example, the high temperature resistance of silane can be effectively improved through doping nitrogen atoms in the hyperbranched vinyl end-capping agent, the transparency and flame retardance of the silicone oil can be improved through doping phosphorus atoms, and the viscosity and flame retardance of the silicone oil can be effectively improved through doping boron atoms.
Preferably, the heteroatom includes at least one of nitrogen, phosphorus, and boron atoms.
In a second aspect, the present invention also provides a process for preparing the hyperbranched vinyl-capping agent comprising the steps of: mixing hydrogen-containing cyclosiloxane and vinyl-containing linear siloxane, and carrying out hydrosilylation reaction under the condition of a catalyst to obtain the hyperbranched vinyl end-capping agent.
Preferably, the molar ratio of active hydrogen in the hydrogen-containing cyclosiloxane to vinyl in the vinyl-containing linear siloxane is 1:1.1-2.
Preferably, the method further comprises adding a heteroatom doped hyperbranched vinyl end-capping agent to the reactants.
In a third aspect, the invention also provides application of the hyperbranched vinyl end-capping agent in preparation of hyperbranched vinyl silicone oil.
In a fourth aspect, the invention also provides a preparation method of hyperbranched vinyl silicone oil, comprising the following steps:
(1) Mixing the hyperbranched vinyl end-capping agent and cyclosiloxane, and then carrying out polymerization reaction under the condition of a catalyst to obtain crude vinyl silicone oil;
(2) And removing the catalyst and low-boiling-point substances in the crude vinyl silicone oil to obtain the hyperbranched vinyl silicone oil.
Preferably, the polymerization temperature in the step (1) is 95-115 ℃ and the polymerization time is 2-4 hours.
In a fifth aspect, the present invention also provides a hyperbranched vinylmethylsilicone oil prepared by the method as described above.
Therefore, the invention has the following beneficial effects:
(1) The operation is simple and convenient: the hyperbranched vinyl end-capping agent with high branching degree is prepared at a lower temperature in a shorter time, and meanwhile, the preparation equipment is consistent with the traditional vinyl silicone oil, so that the sinking cost of the equipment caused by switching the hyperbranched silicone oil is avoided, and the production efficiency is improved;
(2) Cost: the raw materials are widely available and relatively safe;
(3) The product has excellent performance: the hyperbranched vinyl methyl silicone oil has the advantages of lower viscosity, higher refractive index, excellent thermal stability and the like, and can be widely applied to the fields of high polymer materials, electronic devices, cosmetics and the like;
(4) Environmental protection and safety: the preparation method does not use toxic and harmful substances, is environment-friendly, safe and reliable.
In conclusion, the preparation method of the hyperbranched vinyl methyl silicone oil has the advantages of simplicity and convenience in operation, low cost, excellent product performance and the like, and has important significance in improving the performance of the organic silicon material and reducing the production cost. Meanwhile, the method is environment-friendly and safe, and can be widely applied to actual production.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a phosphorus atom doped monomer in example 4.
FIG. 2 is a nuclear magnetic resonance spectrum of the hyperbranched vinyl-terminated agent D obtained in example 4.
FIG. 3 is a nuclear magnetic resonance spectrum of the boron atom-doped monomer obtained in example 5.
FIG. 4 is a nuclear magnetic resonance spectrum of a boron atom doped ring body in example 6.
FIG. 5 is a TGA test chart of the hyperbranched vinyl silicone oil prepared in example 7.
FIG. 6 is a TGA test chart of hyperbranched vinyl silicone oil prepared in example 8.
FIG. 7 is a TGA test chart of hyperbranched vinyl silicone oil prepared in example 8.
FIG. 8 is a TGA test chart of the hyperbranched vinyl silicone oil prepared in example 8.
FIG. 9 is a TGA test chart of the hyperbranched vinyl silicone oil prepared in example 8.
FIG. 10 is a TGA test chart of hyperbranched vinyl silicone oil prepared in example 8.
FIG. 11 is a TGA test chart of the linear vinyl silicone oil prepared in comparative example 1.
FIG. 12 is a DSC chart of hyperbranched vinyl silicone oil prepared in example 7.
FIG. 13 is a DSC chart of hyperbranched vinyl silicone oil prepared in example 10.
FIG. 14 is a DSC chart of hyperbranched vinyl silicone oil prepared in example 11.
FIG. 15 is a DSC chart of hyperbranched vinyl silicone oil prepared in example 12.
FIG. 16 is a DSC chart of the linear vinyl silicone oil prepared in comparative example 1.
Detailed Description
The invention is further described below in connection with specific embodiments. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
[ Preparation of hyperbranched vinyl-terminated agent ]
Example 1
2.4G (10 mmol) of tetramethyl cyclotetrasiloxane and 4.16g (22 mmol) of 1, 3-divinyl-1, 3-tetramethyl disiloxane (active hydrogen: vinyl molar ratio 1:1.1) were dissolved in 50ml of toluene under nitrogen protection, mixed, and 10mg of platinum catalyst (silica gel PL-56) was added thereto, followed by reflux reaction for 5 hours to obtain hyperbranched vinyl-terminated agent A.
Example 2
2.4G (10 mmol) of tetramethyl cyclotetrasiloxane and 5.58g (30 mmol) of 1, 3-divinyl-1, 3-tetramethyl disiloxane (active hydrogen: vinyl molar ratio 1:1.5) were dissolved in 50ml of toluene under nitrogen protection, mixed, and 10mg of platinum catalyst (silica gel PL-56) was added thereto, followed by reflux reaction for 5 hours to obtain hyperbranched vinyl-terminated agent B.
Example 3
2.4G (10 mmol) of tetramethyl cyclotetrasiloxane and 7.56g (40 mmol) of 1, 3-divinyl-1, 3-tetramethyl disiloxane (active hydrogen: vinyl molar ratio 1:2) were dissolved in 50ml of toluene under nitrogen protection, mixed, 10mg of platinum catalyst (silica gel PL-56) was added, and the mixture was refluxed for 5 hours to obtain hyperbranched vinyl-terminated agent C.
Example 4
(1) Under the protection of nitrogen, 2.22g (10 mmol) of bis (3-hydroxypropyl) isobutyl oxygen phosphorus and 2.02g (20 mol) of triethylamine are dissolved in 50ml of dichloromethane, then a mixed solution of 2.4g (20 mol) of dimethylvinylchlorosilane and 20ml of dichloromethane is dropwise added into the mixed solution at the temperature of minus 10 ℃ for 1 hour, the mixture is heated to room temperature for continuous reaction for 3 hours, the generated triethylamine hydrochloride is removed by filtration, the organic phase is washed by water, and then the dichloromethane is removed by evaporation to obtain a phosphorus atom doped monomer (the nuclear magnetic spectrum of which is shown as figure 1), and the preparation method is shown as the following formula (1):
(1)
(2) 2.4G (10 mmol) of tetramethyl cyclotetrasiloxane and 11.7g (30 mmol) of monomer doped with phosphorus atoms (active hydrogen: vinyl molar ratio 1:1.5) are dissolved in 50ml of toluene under the protection of nitrogen, mixed, 10mg of platinum catalyst (Sibao PL-56) is added, and reflux reaction is carried out for 5 hours to obtain the hyperbranched vinyl end-capping agent D (the nuclear magnetic spectrum of which is shown in figure 2).
Example 5
(1) Under the protection of nitrogen, 0.88g (10 mmol) of n-propyl boric acid and 2.02g (20 mol) of triethylamine are dissolved in 50ml of dichloromethane, then a mixed solution of 2.4g (20 mol) of dimethylvinylchlorosilane and 20ml of dichloromethane is dropwise added into the mixed solution at the temperature of minus 10 ℃ for 1 hour, the mixed solution is heated to room temperature for continuous reaction for 3 hours, the generated triethylamine hydrochloride is filtered and removed, the organic phase is washed by water, and then the dichloromethane is evaporated to obtain boron atom doped monomer (the nuclear magnetic spectrum of which is shown in figure 3), and the preparation method is shown as the following formula (2):
(2)
(2) 2.4G (10 mmol) of tetramethyl cyclotetrasiloxane and 7.68g (30 mmol) of boron atom doped monomer (active hydrogen: vinyl molar ratio 1:1.5) are dissolved in 50ml of toluene under the protection of nitrogen, mixed, 10mg of platinum catalyst (silica gel PL-56) is added, and reflux reaction is carried out for 5 hours to obtain the hyperbranched vinyl end-capping agent E.
Example 6
(1) Under the protection of nitrogen, dispersing 2.64g (30 mmol) of n-propyl boric acid and 8.4g (100 mmol) of zinc oxide in 500ml of ethyl acetate, stirring to form a suspension, then dropwise adding 10.2g (90 mmol) of methylhydrogen dichlorosilane into the suspension, continuing to react for 12 hours after the dropwise adding is finished, stopping reacting, filtering to remove insoluble zinc salt, washing filtrate, drying the filtrate with anhydrous sodium sulfate, filtering, removing ethyl acetate to obtain a crude product of borosiloxane, and performing vacuum fractionation to obtain a boron atom doped ring body (the nuclear magnetic spectrum of which is shown as figure 4), wherein the preparation method is shown as the following formula (3):
(3)
(2) 2.4G (10 mmol) of boron atom doped ring body and 4.25g (22.5 mmol) of 1, 3-divinyl-1, 3-tetramethyldisiloxane (active hydrogen: vinyl molar ratio 1:1.5) were dissolved in 50ml of toluene under the protection of nitrogen, mixed, and 10mg of platinum catalyst (silica gel PL-56) was added thereto, followed by reflux reaction for 5 hours to obtain hyperbranched vinyl-terminated agent F.
[ Preparation of hyperbranched vinyl Silicone oil ]
Example 7
The preparation method of the hyperbranched vinyl silicone oil comprises the following steps:
Mixing octamethyl cyclotetrasiloxane and a hyperbranched vinyl end-capping agent A according to a weight ratio of 100:2, adding tetramethyl ammonium hydroxide silicon alkoxide accounting for 0.01% of the total mass of octamethyl cyclotetrasiloxane as a catalyst, heating to 95-115 ℃ under the conditions of nitrogen introduction and decompression (about 8 kPa), carrying out polymerization reaction for 2-4 hours, releasing vacuum, heating to 160-180 ℃ and maintaining for 1 hour to destroy the catalyst, heating to 200 ℃ to obtain crude vinyl silicone oil, and removing low-boiling substances to obtain the hyperbranched vinyl silicone oil.
Example 8
The preparation method of the hyperbranched vinyl silicone oil comprises the following steps:
Mixing octamethyl cyclotetrasiloxane and a hyperbranched vinyl end-capping agent B according to a weight ratio of 100:2, adding tetramethyl ammonium hydroxide silicon alkoxide accounting for 0.01% of the total mass of octamethyl cyclotetrasiloxane as a catalyst, heating to 95 ℃ under the conditions of nitrogen introduction and decompression (about 8 kPa), carrying out polymerization reaction, reacting for 4 hours, releasing vacuum, heating to 160-180 ℃ and maintaining for 1 hour to destroy the catalyst, heating to 200 ℃ to obtain crude vinyl silicone oil, and removing low-boiling substances to obtain the hyperbranched vinyl silicone oil.
Example 9
The preparation method of the hyperbranched vinyl silicone oil comprises the following steps:
Mixing octamethyl cyclotetrasiloxane and a hyperbranched vinyl end-capping agent C according to a weight ratio of 100:2, adding tetramethyl ammonium hydroxide silicon alkoxide accounting for 0.01% of the total mass of octamethyl cyclotetrasiloxane as a catalyst, heating to 100 ℃ under the conditions of nitrogen introduction and decompression (about 8 kPa), carrying out polymerization reaction, reacting for 3 hours, releasing vacuum, heating to 160-180 ℃ and maintaining for 1 hour to destroy the catalyst, heating to 200 ℃ to obtain crude vinyl silicone oil, and removing low-boiling substances to obtain the hyperbranched vinyl silicone oil.
Example 10
The preparation method of the hyperbranched vinyl silicone oil comprises the following steps:
Mixing octamethyl cyclotetrasiloxane and a hyperbranched vinyl end-capping agent D according to a weight ratio of 100:2, adding tetramethyl ammonium hydroxide silicon alkoxide accounting for 0.01% of the total mass of octamethyl cyclotetrasiloxane as a catalyst, heating to 115 ℃ under the conditions of nitrogen introduction and decompression (about 8 kPa), carrying out polymerization reaction, reacting for 2 hours, releasing vacuum, heating to 160-180 ℃ and maintaining for 1 hour to destroy the catalyst, heating to 200 ℃ to obtain crude vinyl silicone oil, and removing low-boiling substances to obtain the hyperbranched vinyl silicone oil.
Example 11
The preparation method of the hyperbranched vinyl silicone oil comprises the following steps:
mixing octamethyl cyclotetrasiloxane and a hyperbranched vinyl end-capping agent E according to a weight ratio of 100:2, adding tetramethyl ammonium hydroxide silicon alkoxide accounting for 0.01% of the total mass of octamethyl cyclotetrasiloxane as a catalyst, heating to 110 ℃ under the conditions of nitrogen introduction and decompression (about 8 kPa), carrying out polymerization reaction for 3 hours, releasing vacuum, heating to 160-180 ℃ and maintaining for 1 hour to destroy the catalyst, heating to 200 ℃ to obtain crude vinyl silicone oil, and removing low-boiling substances to obtain hyperbranched vinyl silicone oil.
Example 12
The preparation method of the hyperbranched vinyl silicone oil comprises the following steps:
Mixing octamethyl cyclotetrasiloxane and a hyperbranched vinyl end-capping agent F according to a weight ratio of 100:2, adding tetramethyl ammonium hydroxide silicon alkoxide accounting for 0.01% of the total mass of octamethyl cyclotetrasiloxane as a catalyst, heating to 110 ℃ under the conditions of nitrogen introduction and decompression (about 8 kPa), carrying out polymerization reaction for 3 hours, releasing vacuum, heating to 160-180 ℃ and maintaining for 1 hour to destroy the catalyst, heating to 200 ℃ to obtain crude vinyl silicone oil, and removing low-boiling substances to obtain hyperbranched vinyl silicone oil.
Comparative example 1
A preparation method of linear vinyl silicone oil comprises the following steps:
Mixing octamethyl cyclotetrasiloxane and 1, 3-divinyl-1, 3-tetramethyl disiloxane according to a weight ratio of 100:2, adding tetramethyl ammonium hydroxide silicon alkoxide accounting for 0.01% of the total weight of the octamethyl cyclotetrasiloxane as a catalyst, heating to 110 ℃ under the conditions of nitrogen introduction and decompression (about 8 kPa), carrying out polymerization reaction for 3 hours, releasing vacuum, heating to 160-180 ℃ and maintaining for 1 hour to destroy the catalyst, heating to 200 ℃ to obtain crude vinyl silicone oil, and removing low-boiling substances to obtain linear vinyl silicone oil.
Performance test:
the hyperbranched vinyl silicone oil prepared in example 7 to example 12 and the linear vinyl silicone oil prepared in comparative example 1 were tested.
TGA analysis: the temperature rising rate is 10 ℃/min in the temperature range of 50 ℃ to 800 ℃ under the nitrogen atmosphere.
DSC analysis: the temperature was first lowered from room temperature to-100℃at a rate of 10℃per minute, and then raised to room temperature at a rate of 10℃per minute.
The test results are shown in table 1 below:
TABLE 1
| Project | Weight loss on heating 5% temperature/°c | Glass transition temperature/DEGC | Number average molecular weight |
| Example 7 | 251 | -58℃ | 65285 |
| Example 8 | 259 | -60℃ | 64786 |
| Example 9 | 257 | -59℃ | 67129 |
| Example 10 | 280 | -68℃ | 71685 |
| Example 11 | 312 | -37℃ | 48960 |
| Example 12 | 319 | -31℃ | 52845 |
| Comparative example 1 | 214 | -52℃ | 23560 |
Fig. 5 to 11 are TGA test charts of examples 7 to 12 and comparative example 1, and it is understood from the data of fig. 5 to 11 and table 1 that the thermal stability of silicone oil can be effectively improved by introducing a hyperbranched structure into the silicone oil. Meanwhile, hetero atoms are introduced into the hyperbranched silicone oil, so that the high temperature resistance of the hyperbranched silicone oil can be further improved.
Fig. 12 to 16 are DSC test charts of example 7, example 10, example 11, example 12 and comparative example 1, respectively, and the test results show that the introduction of the hyperbranched structure into the silicone oil can affect the glass transition temperature of the silicone oil, and the glass transition temperature of the silicone oil can be reduced to a certain extent without doping of hetero atoms. And after the hetero atoms are introduced into the silicone oil, different hetero atoms have different influences on the glass transition temperature of the silicone oil, and when the hetero atoms are phosphorus atoms, the glass transition temperature of the silicone oil can be greatly reduced. And when the heteroatom is a boron atom, the glass transition temperature is raised.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions, without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (10)
1. A hyperbranched vinyl end-capping agent is characterized in that,
A linear siloxane segment comprising a siloxane ring and attached to a silicon atom on the siloxane ring;
The number of silicon atoms in the siloxane ring is at least 3;
The number of silicon atoms in the linear siloxane segment is at least 2;
at least a portion of the end groups of the linear siloxane segments are vinyl groups.
2. The hyperbranched vinyl-terminated agent as claimed in claim 1, wherein,
Some or all of the siloxane rings and/or linear siloxane segments are doped with heteroatoms other than silicon, oxygen, carbon.
3. A hyperbranched vinyl-terminated agent according to claim 2, wherein,
The heteroatom includes at least one of nitrogen, phosphorus, and boron atoms.
4. A process for preparing the hyperbranched vinyl-terminated agents according to claim 1 to 3,
The method comprises the following steps: mixing hydrogen-containing cyclosiloxane and vinyl-containing linear siloxane, and carrying out hydrosilylation reaction under the condition of a catalyst to obtain the hyperbranched vinyl end-capping agent.
5. The method of claim 4, wherein the step of determining the position of the first electrode is performed,
The molar ratio of active hydrogen in the hydrogen-containing cyclosiloxane to vinyl in the vinyl-containing linear siloxane is 1:1.1-2.
6. The method according to claim 4 or 5, wherein,
Further comprising adding heteroatom doped siloxane rings and/or linear siloxanes to the reactants.
7. Use of a hyperbranched vinyl-terminated agent according to any one of claims 1 to 3 for the preparation of hyperbranched vinyl silicone oils.
8. The preparation method of the hyperbranched vinyl silicone oil is characterized by comprising the following steps of:
(1) Mixing the hyperbranched vinyl end-capping agent and cyclosiloxane according to any one of claims 1-3, and performing polymerization reaction under the condition of a catalyst to obtain crude vinyl silicone oil;
(2) And removing the catalyst and low-boiling-point substances in the crude vinyl silicone oil to obtain the hyperbranched vinyl silicone oil.
9. The method of claim 8, wherein the step of determining the position of the first electrode is performed,
The polymerization temperature in the step (1) is 95-115 ℃ and the polymerization time is 2-4 hours.
10. Hyperbranched vinylmethylsilicone oil, characterized in that it is prepared by the process described in claim 8 or 9.
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