CN116284788A - Preparation method and application of end-ring carbonate modified polysiloxane - Google Patents
Preparation method and application of end-ring carbonate modified polysiloxane Download PDFInfo
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- CN116284788A CN116284788A CN202310248220.5A CN202310248220A CN116284788A CN 116284788 A CN116284788 A CN 116284788A CN 202310248220 A CN202310248220 A CN 202310248220A CN 116284788 A CN116284788 A CN 116284788A
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- modified polysiloxane
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- -1 polysiloxane Polymers 0.000 title claims abstract description 50
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 35
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920002545 silicone oil Polymers 0.000 claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007822 coupling agent Substances 0.000 claims abstract description 14
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 150000001336 alkenes Chemical class 0.000 claims abstract description 5
- 150000005690 diesters Chemical class 0.000 claims abstract description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims abstract description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000004945 silicone rubber Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000004650 carbonic acid diesters Chemical class 0.000 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 claims description 2
- UXGHWJFURBQKCJ-UHFFFAOYSA-N oct-7-ene-1,2-diol Chemical compound OCC(O)CCCCC=C UXGHWJFURBQKCJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007344 nucleophilic reaction Methods 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 229920002635 polyurethane Polymers 0.000 description 10
- 239000004814 polyurethane Substances 0.000 description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 7
- 239000000565 sealant Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001558 organosilicon polymer Polymers 0.000 description 2
- 239000004590 silicone sealant Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000196322 Marchantia Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance 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
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
- C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method and application of end-ring carbonate modified polysiloxane, and belongs to the technical field of organosilicon preparation. The technical scheme comprises the following steps: 1) Mixing hydrogen-containing silicone oil, alkene glycol and a platinum catalyst, heating, and reacting to obtain a product I; 2) Adding carbonic diester, mixing uniformly, adding catalyst, heating, and reacting to obtain the end-ring carbonic ester modified polysiloxane. The amino in the aminosilane coupling agent can carry out nucleophilic reaction with the carbonyl group in the cyclic carbonate, the synthesis avoids toxic isocyanate groups, and the invention accords with the green pollution-free theme in the new era, and has simple preparation process.
Description
Technical Field
The invention relates to the technical field of organosilicon preparation, in particular to a preparation method and application of end-ring carbonate modified polysiloxane.
Background
The organic silicon rubber has important application in the fields of construction, industry, electronic power, high-speed rail, aerospace and the like. Among them, the use as a sealant product has been of great interest. As one of the modern three sealants (polyurethane, organosilicon and acrylic acid), the organosilicon sealant has the advantages of weather resistance, corrosion resistance, no solvent, environmental protection and the like, and can realize the adhesion among a plurality of base materials. The organosilicon sealant is prepared by polymerizing hydroxy (or alkoxy) polydimethylsiloxane serving as a base adhesive, white carbon black or calcium carbonate serving as a filler through a crosslinking agent and a catalyst. However, because the adhesion of the siloxane to the substrate is poor, it is generally necessary to add a silane coupling agent as a tackifier to improve the adhesion strength to the substrate.
Since the adhesion strength of the polyurethane structure to the substrate is generally superior to that of the organosilicon, the material prepared by compounding the organosilicon with polyurethane generally has more excellent adhesion performance. The adhesive property is enhanced by adding isocyanate silane coupling agent, epoxy siloxane coupling agent and tackifier with polyurethane structure as tackifying components, for example, the invention patent (CN 107641494) discloses an alpha-isocyanate silane coupling agent modified sealant, and the modified silane coupling agent has the characteristics of high activity and easy synthesis, and can shorten the curing time. The organosilicon modified polyurethane or polyurethane modified organosilicon polymer is developed, and the polyurethane modified organosilicon polymer can also have the performances of increasing adhesion and improving deep curing, for example, the invention patent (CN 110358050A) discloses a preparation method of an aminosilane coupling agent modified polyurethane aqueous adhesive, which has the advantages of simple preparation, no toxicity, no environmental pollution and the like. However, the isocyanate material is highly reactive and environmentally unfriendly. At present, most polyurethane modified sealants are prepared by using isocyanate as a raw material, and few polyurethane modified organosilicon sealants are prepared by using non-isocyanate. The preparation of modified organic silicon rubber with self-adhesive function by adopting a non-isocyanate method becomes a difficulty of industry.
Disclosure of Invention
The invention aims to solve the technical problems that: the preparation method and the application of the end-ring carbonate modified polysiloxane are provided, wherein amino groups in the aminosilane coupling agent can carry out nucleophilic reaction with carbonyl groups in the end-ring carbonate, the synthesis avoids toxic isocyanate groups, and the preparation method and the application are more in line with the new green pollution-free theme and simple in preparation process.
The technical scheme of the invention is as follows:
in a first aspect, a method for preparing a cyclic carbonate modified polysiloxane is disclosed, comprising the steps of:
1) Mixing hydrogen-containing silicone oil, alkene glycol and a platinum catalyst, heating, and reacting to obtain a product I;
2) Adding carbonic diester, mixing uniformly, adding catalyst, heating, and reacting to obtain the end-ring carbonic ester modified polysiloxane.
Preferably, the reaction temperature in the step 1) is 110-130 ℃, and the reaction time is 2-5 h.
Preferably, the reaction temperature in the step 2) is 90-110 ℃, and the reaction time is 1-5 h.
Preferably, the hydrogen-containing silicone oil is hydrogen-containing silicone oil with hydrogen content of 0.10% -0.38%.
Preferably, the alkylene glycol is one or more of butylene glycol, hexadiene glycol and 7-octene-1, 2-diol.
Preferably, in the step (1), the molar ratio of the hydrogen-containing silicone oil to the alkene diol is 1: 1-1:1.3, wherein the addition amount of the platinum catalyst is 0.1-0.2 wt% of the total weight of the hydrogen-containing silicone oil and the alkene glycol.
Preferably, the carbonic acid diester is dimethyl carbonate or diethyl carbonate.
Preferably, the catalyst is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
Preferably, the mass ratio of the product mono-and carbonic acid diester in the step 2) is 100: 13.65-100:16.38, wherein the addition amount of the catalyst is 0.2-0.4 wt% of the total weight of the product I and the carbonic acid diester.
On the other hand, a method for preparing silicone rubber by utilizing end-ring carbonate modified polysiloxane is disclosed, wherein the end-ring carbonate modified polysiloxane, filler and aminosilane coupling agent are mixed according to a certain proportion to prepare the modified silicone rubber.
Firstly, preparing o-diol-containing siloxane through an addition reaction of hydrogen-containing silicone oil and o-olefin diol; the o-diol siloxane and the carbonic diester are mixed and reacted according to a certain proportion, and the cyclic carbonate siloxane is prepared through transesterification, and the cyclic carbonate siloxane and the amino coupling agent are combined to promote the adhesion to the surface of the substrate, so that the adhesion of the silicon rubber to the substrate is effectively improved, the modified siloxane is environment-friendly and pollution-free, conforms to the trend of the age, and conforms to the theme of environment protection and pollution free. Moreover, the silicone rubber with the novel structure overcomes the defects of the traditional organic silicone sealant that a cross-linking agent and a catalyst are used, can be directly mixed and sized, is convenient to use, can be directly used after being directly prepared into the silicone rubber, and does not need secondary mixing and re-sizing.
Compared with the prior art, the invention has the following beneficial effects:
(1) The prepared end-ring carbonate modified polysiloxane and the silicon rubber prepared by using the same have excellent adhesive force and bonding performance. The preparation process is simple, and the adhesive property is excellent;
(2) The end-ring carbonate modified polysiloxane and the silicon rubber prepared by using the end-ring carbonate modified polysiloxane have the advantages of wide raw material sources and low cost, avoid the use of a cross-linking agent and a catalyst of the traditional silicon rubber, are beneficial to deep solidification, are convenient to use, and are suitable for industrial production.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it is to be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not intended to limit the scope of the claims of the invention, which are commercially available as raw materials unless otherwise specifically indicated.
The hydrogen-containing silicone oil is terminal hydrogen-containing silicone oil with hydrogen content of 0.18% produced by Shanghai Sibao advanced materials Co.
The platinum catalyst is a carbote catalyst (5000 ppm platinum catalyst) produced by the pharmaceutical chemical company of marchantia white, ltd.
Example 1
The embodiment provides a preparation method of end-ring carbonate modified polysiloxane, which comprises the following steps:
1) 50g of 0.18% end hydrogen-containing silicone oil is added into a 100mL three-neck flask, the temperature is raised to 120 ℃, 7.93g of butylene glycol is added dropwise, the dropping speed is 2-3 s/d, after the dropping is finished, 0.09g of platinum catalyst is added, and the reaction is carried out for 3.5h, thus obtaining a product I.
2) 50g of the product I and 7.17g of dimethyl carbonate are uniformly mixed, the temperature is raised to 100 ℃, then 0.17g of potassium hydroxide is added for reaction for 3 hours, and the end-ring carbonate modified polysiloxane is obtained.
Example 2
The embodiment provides a preparation method of end-ring carbonate modified polysiloxane, which comprises the following steps:
1) 50g of 0.18% end hydrogen-containing silicone oil is added into a 100mL three-neck flask, the temperature is raised to 120 ℃, 9.52g of butylene glycol is added dropwise, the dropping speed is 2-3 s/d, after the dropping is finished, 0.09g of platinum catalyst is added, and the reaction is carried out for 3.5h, thus obtaining a product I.
2) 50g of the product I and 8.19g of dimethyl carbonate are uniformly mixed, the temperature is raised to 100 ℃, then 0.17g of potassium hydroxide is added for reaction for 3 hours, and the end-ring carbonate modified polysiloxane is obtained.
Example 3
The embodiment provides a preparation method of end-ring carbonate modified polysiloxane, which comprises the following steps:
1) 50g of 0.18% end hydrogen-containing silicone oil is added into a 100mL three-neck flask, the temperature is raised to 110 ℃, 9.52g of butylene glycol is added dropwise, the dropping speed is 2-3 s/d, after the dropping is finished, 0.09g of platinum catalyst is added, and the reaction is carried out for 3.5h, thus obtaining a product I.
2) 50g of the product I and 7.17g of dimethyl carbonate are uniformly mixed, the temperature is raised to 100 ℃, then 0.17g of potassium hydroxide is added for reaction for 3 hours, and the end-ring carbonate modified polysiloxane is obtained.
Example 4
The embodiment provides a method for preparing silicon rubber by using end-ring carbonate modified polysiloxane, which comprises the following steps: 30 parts of the end-ring carbonate-modified polydimethylsiloxane prepared in example 1, 10 parts of amino coupling agent (KH 550), 60 parts of CaCO 3 And (3) uniformly dispersing the filler at a high speed to prepare the modified silicone rubber.
Example 5
The embodiment provides a method for preparing silicon rubber by using end-ring carbonate modified polysiloxane, which comprises the following steps: 25 parts of the ends prepared in example 1Cyclocarbonate modified polydimethylsiloxane, 10 parts of amino coupling agent (KH 550), 65 parts of CaCO 3 And (3) uniformly dispersing the filler at a high speed to prepare the modified silicone rubber.
Example 6
The embodiment provides a method for preparing silicon rubber by using end-ring carbonate modified polysiloxane, which comprises the following steps: 40 parts of the end-ring carbonate-modified polydimethylsiloxane prepared in example 1, 10 parts of an amino coupling agent (KH 550), 50 parts of CaCO 3 And (3) uniformly dispersing the filler at a high speed to prepare the modified silicone rubber.
Comparative example 1
The comparative example provides a method for preparing silicone rubber by using end-ring carbonate modified polysiloxane, which comprises the following steps: 30 parts of hydroxy polydimethylsiloxane, 10 parts of amino coupling agent (KH 550) and 60 parts of CaCO 3 And (3) uniformly dispersing the filler at a high speed to prepare the silicone rubber.
The tack free time, and glass strength data for the glass of the silicone rubbers prepared in examples 4-6 and comparative example 1 are shown in Table 1. And (3) surface dry test: reference is made to GB/T13477.5-2002 peel strength test: 180℃glass test, see GB/T2790-1995.
TABLE 1
| Time of surface drying (min) | Tack free time (min) | Peel strength/N/mm | |
| Example 4 | 45 | 49 | 1.65 |
| Example 5 | 20 | 23 | 1.50 |
| Example 6 | 60 | 62 | 1.52 |
| Comparative example 1 | No surface dryness | Non-sticky | 0 |
The use amount of the carbonate modified polydimethylsiloxane and the amino coupling agent is a main reason for influencing the surface dryness, the viscosity breaking and the peeling strength of the silicon rubber, and when the ratio of the carbonate modified polydimethylsiloxane to the amino coupling agent to the CaCO3 filler is 3:1:6, the surface dryness and the viscosity breaking time are moderate, the peeling strength is better, and the bonding effect on a base material is better.
Firstly, preparing o-diol-containing siloxane through an addition reaction of hydrogen-containing silicone oil and o-olefin diol; the o-diol siloxane and the carbonic diester are mixed and reacted according to a certain proportion, and the cyclic carbonate siloxane is prepared through transesterification, and the cyclic carbonate siloxane and the amino coupling agent are combined to promote the adhesion to the surface of the substrate, so that the adhesion of the silicon rubber to the substrate is effectively improved, the modified siloxane is environment-friendly and pollution-free, conforms to the trend of the age, and conforms to the theme of environment protection and pollution free. Moreover, the silicone rubber with the novel structure overcomes the defects of the traditional organic silicone sealant that a cross-linking agent and a catalyst are used, can be directly mixed and sized, is convenient to use, can be directly used after being directly prepared into the silicone rubber, and does not need secondary mixing and re-sizing.
Although the present invention has been described in detail by way of the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications and substitutions for embodiments of the invention may be made by those skilled in the art without departing from the spirit and scope of the invention, and these modifications and substitutions are intended to be within the scope of the invention. Therefore, the protection scope of the invention is subject to the protection scope of the claims.
Claims (10)
1. A method for preparing a cyclic carbonate modified polysiloxane, comprising the steps of:
1) Mixing hydrogen-containing silicone oil, alkene glycol and a platinum catalyst, heating, and reacting to obtain a product I;
2) Adding carbonic diester, mixing uniformly, adding catalyst, heating, and reacting to obtain the end-ring carbonic ester modified polysiloxane.
2. The method for preparing a modified polysiloxane with a cyclic carbonate according to claim 1, wherein the reaction temperature in the step 1) is 110-130 ℃ and the reaction time is 2-5 h.
3. The method for preparing a modified polysiloxane with a cyclic carbonate according to claim 1, wherein the reaction temperature in the step 2) is 90-110 ℃ and the reaction time is 1-5 h.
4. The method for preparing a cyclic carbonate modified polysiloxane according to claim 1, wherein the hydrogen-containing silicone oil is hydrogen-containing silicone oil having a hydrogen content of 0.10% -0.38%.
5. The method of preparing a cyclic carbonate modified polysiloxane according to claim 1, wherein the alkylene glycol is one or more of butylene glycol, hexadiene glycol, and 7-octene-1, 2-diol.
6. The method for preparing a cyclic carbonate modified polysiloxane according to claim 1, wherein the molar ratio of hydrogen-containing silicone oil to alkylene glycol in the step (1) is 1: 1-1:1.3, wherein the addition amount of the platinum catalyst is 0.1-0.2 wt% of the total weight of the hydrogen-containing silicone oil and the alkene glycol.
7. The method for preparing a cyclic carbonate modified polysiloxane according to claim 1, wherein the carbonic acid diester is dimethyl carbonate or diethyl carbonate.
8. The method for preparing a cyclic carbonate modified polysiloxane according to claim 1, wherein the catalyst is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
9. The process for preparing a cyclic carbonate modified polysiloxane according to claim 1, wherein the mass ratio of product mono-and carbonic acid diester in step 2) is 100: 13.65-100:16.38, wherein the addition amount of the catalyst is 0.2-0.4 wt% of the total weight of the product I and the carbonic acid diester.
10. A method for preparing silicone rubber by using the end-ring carbonate modified polysiloxane prepared by the preparation method of claims 1-9, which is characterized in that the end-ring carbonate modified polysiloxane, filler and aminosilane coupling agent are mixed according to a certain proportion to prepare the modified silicone rubber.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06145636A (en) * | 1991-03-14 | 1994-05-27 | Asahi Chem Ind Co Ltd | Urethane acrylate adhesive |
| CN1133310A (en) * | 1995-03-02 | 1996-10-16 | 通用电气公司 | Preparation method for blocked copolymerized siloxanes carbonic ester |
| US5606077A (en) * | 1995-02-21 | 1997-02-25 | Th. Goldschmidt Ag | Method for the synthesis of organopolysiloxanes containing carbonate groups |
| JP2005068383A (en) * | 2003-08-28 | 2005-03-17 | Dow Corning Toray Silicone Co Ltd | Silicone rubber composition for metal mold-molding of unified molded product of organic resin with silicone rubber |
| KR20070030682A (en) * | 2005-09-13 | 2007-03-16 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Cyclic Carbonate-Modified Organosilicon Compound, Non-Aqueous Electrolytic Solution Comprising the Same, Secondary Battery and Capacitor |
| CN1931863A (en) * | 2005-09-13 | 2007-03-21 | 信越化学工业株式会社 | Cyclic carbonate-modified organosilicon compound, non-aqueous electrolytic solution comprising same, secondary battery, and capacitor |
| CN101003630A (en) * | 2005-09-14 | 2007-07-25 | 信越化学工业株式会社 | Cyclic carbonate-modified siloxane and method for producing the same, non-aqueous electrolyte solution, secondary cell and capacitor |
| CN103351467A (en) * | 2013-07-18 | 2013-10-16 | 东莞市贝特利新材料有限公司 | Addition type liquid silicone rubber bonding accelerant and preparation method and application thereof |
| CN107698756A (en) * | 2017-08-30 | 2018-02-16 | 万华化学集团股份有限公司 | A kind of silane-modified line style polyurea adhesive and its preparation and application |
| CN108164705A (en) * | 2017-12-18 | 2018-06-15 | 深圳市康利邦科技有限公司 | A kind of odorlessness add-on type liquid silicon rubber tackifier and its preparation method and application |
| CN108587548A (en) * | 2018-05-11 | 2018-09-28 | 万华化学集团股份有限公司 | A kind of Silante terminated modified polycarbonate polyurethane adhesive resin and its preparation method and application |
| CN109232882A (en) * | 2018-09-29 | 2019-01-18 | 中国林科院林产化工研究所南京科技开发总公司 | Organic-silicon-modified galla turcica acidic group non-isocyanate polyurethane and preparation method thereof |
| CN113265177A (en) * | 2021-06-25 | 2021-08-17 | 浙江纳美新材料股份有限公司 | Color paste for color filter |
| CN116284798A (en) * | 2023-03-15 | 2023-06-23 | 山东共聚有机硅技术研究院有限公司 | Preparation method of polyurethane modified organosilicon tackifier and application of polyurethane modified organosilicon tackifier in silicone rubber |
-
2023
- 2023-03-15 CN CN202310248220.5A patent/CN116284788A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06145636A (en) * | 1991-03-14 | 1994-05-27 | Asahi Chem Ind Co Ltd | Urethane acrylate adhesive |
| US5606077A (en) * | 1995-02-21 | 1997-02-25 | Th. Goldschmidt Ag | Method for the synthesis of organopolysiloxanes containing carbonate groups |
| CN1133310A (en) * | 1995-03-02 | 1996-10-16 | 通用电气公司 | Preparation method for blocked copolymerized siloxanes carbonic ester |
| JP2005068383A (en) * | 2003-08-28 | 2005-03-17 | Dow Corning Toray Silicone Co Ltd | Silicone rubber composition for metal mold-molding of unified molded product of organic resin with silicone rubber |
| KR20070030682A (en) * | 2005-09-13 | 2007-03-16 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Cyclic Carbonate-Modified Organosilicon Compound, Non-Aqueous Electrolytic Solution Comprising the Same, Secondary Battery and Capacitor |
| CN1931863A (en) * | 2005-09-13 | 2007-03-21 | 信越化学工业株式会社 | Cyclic carbonate-modified organosilicon compound, non-aqueous electrolytic solution comprising same, secondary battery, and capacitor |
| CN101003630A (en) * | 2005-09-14 | 2007-07-25 | 信越化学工业株式会社 | Cyclic carbonate-modified siloxane and method for producing the same, non-aqueous electrolyte solution, secondary cell and capacitor |
| CN103351467A (en) * | 2013-07-18 | 2013-10-16 | 东莞市贝特利新材料有限公司 | Addition type liquid silicone rubber bonding accelerant and preparation method and application thereof |
| CN107698756A (en) * | 2017-08-30 | 2018-02-16 | 万华化学集团股份有限公司 | A kind of silane-modified line style polyurea adhesive and its preparation and application |
| CN108164705A (en) * | 2017-12-18 | 2018-06-15 | 深圳市康利邦科技有限公司 | A kind of odorlessness add-on type liquid silicon rubber tackifier and its preparation method and application |
| CN108587548A (en) * | 2018-05-11 | 2018-09-28 | 万华化学集团股份有限公司 | A kind of Silante terminated modified polycarbonate polyurethane adhesive resin and its preparation method and application |
| CN109232882A (en) * | 2018-09-29 | 2019-01-18 | 中国林科院林产化工研究所南京科技开发总公司 | Organic-silicon-modified galla turcica acidic group non-isocyanate polyurethane and preparation method thereof |
| CN113265177A (en) * | 2021-06-25 | 2021-08-17 | 浙江纳美新材料股份有限公司 | Color paste for color filter |
| CN116284798A (en) * | 2023-03-15 | 2023-06-23 | 山东共聚有机硅技术研究院有限公司 | Preparation method of polyurethane modified organosilicon tackifier and application of polyurethane modified organosilicon tackifier in silicone rubber |
Non-Patent Citations (2)
| Title |
|---|
| 李广宇，等: "胶粘与密封新技术", vol. 1, 31 January 2006, 国防工业出版社, pages: 180 - 181 * |
| 潘科学;赖学军;李红强;曾幸荣;: "加成型液体硅橡胶的粘接性能研究进展", 有机硅材料, no. 01, 25 January 2016 (2016-01-25), pages 53 - 57 * |
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