CN113185546B - High-activity catalyst for dealcoholized silicone sealant and preparation method and application thereof - Google Patents
High-activity catalyst for dealcoholized silicone sealant and preparation method and application thereof Download PDFInfo
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- CN113185546B CN113185546B CN202110470377.3A CN202110470377A CN113185546B CN 113185546 B CN113185546 B CN 113185546B CN 202110470377 A CN202110470377 A CN 202110470377A CN 113185546 B CN113185546 B CN 113185546B
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- 239000004590 silicone sealant Substances 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 230000000694 effects Effects 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 21
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229920002545 silicone oil Polymers 0.000 claims abstract description 35
- 239000013522 chelant Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims 3
- 239000006229 carbon black Substances 0.000 claims 3
- 238000003860 storage Methods 0.000 abstract description 18
- 238000004383 yellowing Methods 0.000 abstract description 12
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 description 12
- 230000005494 condensation Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000565 sealant Substances 0.000 description 6
- KZOYXZJYXGPUCM-UHFFFAOYSA-N CCOC(=O)CC(C)=O.CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C Chemical compound CCOC(=O)CC(C)=O.CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C KZOYXZJYXGPUCM-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 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
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002631 room-temperature vulcanizate silicone Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention discloses a high-activity catalyst for dealcoholized silicone sealant, and a preparation method and application thereof. The high-activity catalyst is siloxane-tetraisopropoxytitanium chelate, the siloxane-tetraisopropoxytitanium chelate is obtained by reacting tetraisopropoxytitanium and MDT silicone oil, and the weight ratio of the tetraisopropoxytitanium to the MDT silicone oil is 100: 85-95. The catalyst is used for preparing dealcoholized silicone sealant, and has the advantages of high deep curing speed, long storage time, yellowing resistance, excellent bonding performance to various substrates, no viscosity peak generation in the process of preparing the silicone sealant and the like.
Description
Technical Field
The invention relates to the technical field of silicone sealants, in particular to a high-activity catalyst for dealcoholized silicone sealants, and a preparation method and application thereof.
Background
One-component room temperature vulcanizing silicone sealant (called as one-component RTV for short) starts to be vulcanized from the surface and the inside by means of trace moisture in the air, and the vulcanizing speed inside the sealant is mainly determined by the temperature and the humidity of the environment. Generally, the names are given according to the trace amount of small molecules released during vulcanization, and the most widely used products are the ketoxime-removed type, dealcoholization type, deacetylation type, deacetonization type, and dehydroxylamine type. The deacetylated single-component RTV has pungent smell and certain corrosivity to metal, but has very good adhesion to materials such as glass, and is mainly used as a building sealant for sealing joints of materials such as glass, ceramic tiles and aluminum sashes; the ketoxime-removed single-component RTV has low corrosivity, and the released butanone oxime has potential carcinogenic risk and can be used as an adhesive or a sealant in the fields of buildings, electronics and electric appliances; the dehydroxylamine type single-component RTV has low modulus of definite elongation, is mainly used as a building sealant, and has less domestic research; the acetone-removing type single-component RTV silicone rubber is non-corrosive and mainly used as an adhesive for electronics and electrical appliances, but has relatively high cost; the dealcoholized single-component RTV has the advantages of environmental friendliness, no corrosion, low production cost, easily obtained raw materials and the like, is mainly applied to bonding and weather-resistant sealants in the industries of buildings, electronics, electric appliances and the like, and is the main direction for developing room-temperature vulcanized silicone sealants in the future.
The dealcoholized one-component RTV is gradually cured from the surface and the inside by virtue of a trace amount of moisture in the air, if the traditional organic titanium such as titanium tetraisopropoxide is used as a catalyst, the titanium tetraisopropoxide has higher activity, poor stability and shorter storage period, is easy to generate colloid yellowing phenomenon, is easy to hydrolyze in the presence of moisture, and can directly remove isopropanol in the production process, so that the viscosity peak is obvious. In order to solve the problem of short storage period, ethyl acetoacetate-titanium tetraisopropoxide chelate is generally obtained by exchanging ethyl acetoacetate and titanium tetraisopropoxide through ester exchange reaction, so that the stability of the chelate can be improved to a certain extent, the storage period is prolonged, but the yellowing phenomenon and the viscosity peak still exist. In addition, under the conditions of low temperature and low humidity, the deep curing speed of common catalysts such as ethyl acetoacetate-titanium tetraisopropoxide chelate and the like is slow, so that the outdoor weather-resistant dealcoholized silicone weather-resistant sealant can cause surface bulging due to slow curing in winter every year, and the automatic operation of products such as electronic and electric appliances cannot be realized due to slow deep curing, so that the efficiency is influenced. The existing catalyst of the conventional single-component room temperature vulcanized silicone sealant can not solve the problems of short storage period and low curing speed at the same time.
Disclosure of Invention
Based on the high-activity catalyst for the dealcoholized silicone sealant, the catalyst is used for preparing the dealcoholized silicone sealant, and has the advantages of high deep curing speed, long storage time, yellowing resistance, excellent bonding performance to various base materials, no viscosity peak generation in the process of preparing the silicone sealant and the like.
The specific technical scheme is as follows:
a high-activity catalyst for dealcoholization type silicone sealant is a siloxane-tetraisopropoxytitanium chelate, wherein the siloxane-tetraisopropoxytitanium chelate is obtained by reacting tetraisopropoxytitanium and MDT silicone oil, and the weight ratio of the tetraisopropoxytitanium to the MDT silicone oil is 100: 85-95.
In some of these embodiments, the ratio of parts by weight of the titanium tetraisopropoxide and the MDT silicone oil is 100: 88-92.
In some of these embodiments, the ratio of parts by weight of the titanium tetraisopropoxide and the MDT silicone oil is 100: 90.
in some of these embodiments, the MDT silicone oil has a viscosity of 5 to 50mPa · s and a reactive group content of 0.5 to 1.5%.
In some of these embodiments, the MDT silicone oil has a viscosity of 15 to 35mPa · s and a reactive group content of 0.8 to 1%.
The invention also provides a preparation method of the high-activity catalyst for the dealcoholized silicone sealant.
The specific technical scheme is as follows:
the preparation method of the high-activity catalyst for the dealcoholized silicone sealant comprises the following steps:
and putting the tetraisopropoxytitanium and the MDT silicone oil into a reaction vessel, heating, stirring and reacting at the temperature of 90-120 ℃ and under a certain vacuum degree, distilling off isopropanol under reduced pressure, and cooling to obtain a siloxane-tetraisopropoxytitanium chelate, namely the high-activity catalyst for the dealcoholization type silicone sealant.
In some of these embodiments, the temperature of the reaction is 100-110 ℃.
In some of these embodiments, the reaction time is 2 to 6 hours.
In some of these embodiments, the reaction time is 3 to 5 hours.
In some of these embodiments, the reaction time is 4 hours.
In some of these embodiments, the vacuum is between-0.06 and-0.10 MPa.
In some of these embodiments, the vacuum is between-0.085 and-0.095 MPa.
In some of these embodiments, the vacuum is-0.09 MPa.
In some of these embodiments, the temperature of the reduced pressure distillation is 80-90 ℃.
In some of these embodiments, the temperature of the reduced pressure distillation is 84-86 ℃.
The invention also discloses a dealcoholized silicone sealant. The dealcoholized silicone sealant has the advantages of high deep curing speed, long storage time, yellowing resistance, excellent bonding performance to various base materials and the like.
The specific technical scheme is as follows:
the dealcoholized silicone sealant is prepared from the following raw materials in parts by weight:
the catalyst is the high-activity catalyst for the dealcoholized silicone sealant.
In some embodiments, the dealcoholized silicone sealant is prepared from the following raw materials in parts by weight:
in some embodiments, the dealcoholized silicone sealant is prepared from the following raw materials in parts by weight:
in some of these embodiments, the viscosity of the 107 glue is 1.5 to 2.5 ten thousand mPa-s.
In some of these embodiments, the silane coupling agent is KH-550.
The invention also provides a preparation method of the dealcoholized silicone sealant.
The specific technical scheme is as follows:
the preparation method of the dealcoholized silicone sealant comprises the following steps:
And adding the 107 glue, the nano activated calcium carbonate, the fumed silica, the methyltrimethoxysilane, the catalyst and the silane coupling agent into a high-speed dispersion stirrer or a planetary stirrer, and stirring for 45-75 minutes at the rotating speed of 15-25Hz under the protection of nitrogen to obtain the dealcoholized silicone sealant.
The synthesis principle of the high-activity catalyst for the dealcoholized silicone sealant disclosed by the invention is as follows: the MDT silicone oil is branched chain reaction type silicone oil, ester exchange reaction can be carried out between the MDT silicone oil and titanium tetraisopropoxide, hydroxyl in the MDT silicone oil replaces the isopropoxide, so that a siloxane-titanium tetraisopropoxide chelate can be formed, and then the exchanged isopropanol is distilled and removed, so that the high-activity catalyst can be obtained.
The high-activity catalyst for the dealcoholized silicone sealant has the following advantages:
1. the catalyst has good stability and long storage period, can accelerate the deep curing speed of the dealcoholized silicone sealant, improve the assembly speed of downstream household electrical appliances, and solve the problem of swelling of the adhesive surface of outdoor construction of buildings in winter.
2. The catalyst has excellent compatibility with high-viscosity hydroxyl silicone oil (commonly known as 107 glue), and can avoid the problem of product scrapping caused by high viscosity in the production process of dealcoholized silicone sealant when applied to the actual production process.
3. The dealcoholized silicone sealant prepared by the catalyst also has the advantages of good yellowing resistance, excellent bonding performance to various base materials and the like.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to only those steps or modules listed, but may alternatively include other steps not listed or inherent to such process, method, article, or device.
The "plurality" referred to in the present invention means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
The viscosity in the invention refers to the viscosity at 25 ℃.
The MDT silicone oils in the following examples were purchased from Wuhan Hongjingtai technologies, Inc.
The following are specific examples.
Example 1
The preparation method of the high activity catalyst for dealcoholization type silicone sealant provided by the embodiment is as follows:
100 parts of titanium tetraisopropoxide and 70 parts of MDT silicone oil with viscosity of 15 mPas and active group content of 1% are put into a reaction vessel with a condensation reflux device, the temperature is slowly raised, the mixture is stirred and reacted for 4 hours under the conditions that the temperature is 105 ℃ and the vacuum degree is-0.09 MPa, then isopropanol is distilled under reduced pressure at 85 ℃, and after cooling for 8 hours, siloxane-titanium tetraisopropoxide chelate, namely the high-activity catalyst for the dealcoholization type silicone sealant is obtained.
Example 2
The preparation method of the high activity catalyst for dealcoholization type silicone sealant provided by the embodiment is as follows:
100 parts of titanium tetraisopropoxide and 70 parts of MDT silicone oil with the viscosity of 35 mPas and the active group content of 0.8 percent are put into a reaction vessel with a condensation reflux device, the temperature is slowly increased, the mixture is stirred and reacted for 4 hours under the conditions that the temperature is 105 ℃ and the vacuum degree is-0.09 MPa, then isopropanol is distilled out under reduced pressure at 85 ℃, and after cooling for 8 hours, siloxane-titanium tetraisopropoxide chelate, namely the high-activity catalyst for the dealcoholization type silicone sealant is obtained.
Example 3
The preparation method of the high activity catalyst for dealcoholization type silicone sealant provided by the embodiment is as follows:
100 parts of titanium tetraisopropoxide and 80 parts of MDT silicone oil with viscosity of 15 mPas and active group content of 1% are put into a reaction vessel with a condensation reflux device, the temperature is slowly raised, the mixture is stirred and reacted for 4 hours under the conditions that the temperature is 105 ℃ and the vacuum degree is-0.09 MPa, then isopropanol is distilled under reduced pressure at 85 ℃, and after cooling for 8 hours, siloxane-titanium tetraisopropoxide chelate, namely the high-activity catalyst for the dealcoholization type silicone sealant is obtained.
Example 4
The preparation method of the high activity catalyst for dealcoholization type silicone sealant provided by the embodiment is as follows:
100 parts of titanium tetraisopropoxide and 80 parts of MDT silicone oil with the viscosity of 35 mPas and the active group content of 0.8 percent are put into a reaction vessel with a condensation reflux device, the temperature is slowly increased, the mixture is stirred and reacted for 4 hours under the conditions that the temperature is 105 ℃ and the vacuum degree is-0.09 MPa, then isopropanol is distilled out under reduced pressure at 85 ℃, and after cooling for 8 hours, siloxane-titanium tetraisopropoxide chelate, namely the high-activity catalyst for the dealcoholization type silicone sealant is obtained.
Example 5
The preparation method of the high activity catalyst for dealcoholization type silicone sealant provided by the embodiment is as follows:
100 parts of titanium tetraisopropoxide and 90 parts of MDT silicone oil with viscosity of 15 mPas and active group content of 1% are put into a reaction vessel with a condensation reflux device, the temperature is slowly raised, the mixture is stirred and reacted for 4 hours under the conditions that the temperature is 105 ℃ and the vacuum degree is-0.09 MPa, then isopropanol is distilled under reduced pressure at 85 ℃, and after cooling for 8 hours, siloxane-titanium tetraisopropoxide chelate, namely the high-activity catalyst for the dealcoholization type silicone sealant is obtained.
Example 6
The preparation method of the high activity catalyst for dealcoholization type silicone sealant provided by the embodiment is as follows:
100 parts of titanium tetraisopropoxide and 90 parts of MDT silicone oil with the viscosity of 35 mPas and the active group content of 0.8 percent are put into a reaction vessel with a condensation reflux device, the temperature is slowly increased, the mixture is stirred and reacted for 4 hours under the conditions that the temperature is 105 ℃ and the vacuum degree is-0.09 MPa, then isopropanol is distilled out under reduced pressure at 85 ℃, and after cooling for 8 hours, siloxane-titanium tetraisopropoxide chelate, namely the high-activity catalyst for the dealcoholization type silicone sealant is obtained.
Example 7
The preparation method of the high activity catalyst for dealcoholization type silicone sealant provided by the embodiment is as follows:
100 parts of titanium tetraisopropoxide and 100 parts of MDT silicone oil with viscosity of 15 mPas and active group content of 1% are put into a reaction vessel with a condensation reflux device, the temperature is slowly raised, the mixture is stirred and reacted for 4 hours under the conditions that the temperature is 105 ℃ and the vacuum degree is-0.09 MPa, then isopropanol is distilled under reduced pressure at 85 ℃, and after cooling for 8 hours, siloxane-titanium tetraisopropoxide chelate, namely the high-activity catalyst for the dealcoholization type silicone sealant is obtained.
Example 8
The preparation method of the high activity catalyst for dealcoholization type silicone sealant provided by the embodiment is as follows:
100 parts of titanium tetraisopropoxide and 100 parts of MDT silicone oil with the viscosity of 35 mPas and the active group content of 0.8 percent are put into a reaction vessel with a condensation reflux device, the temperature is slowly raised, the mixture is stirred and reacted for 4 hours under the conditions that the temperature is 105 ℃ and the vacuum degree is-0.09 MPa, then isopropanol is distilled out under reduced pressure at the temperature of 85 ℃, and after cooling for 8 hours, siloxane-titanium tetraisopropoxide chelate, namely the high-activity catalyst for dealcoholization type silicone sealant is obtained.
Comparative example 1
100 parts of tetraisopropoxytitanium and 90 parts of hydroxyl silicone oil (the hydroxyl value is 8.5%) with the viscosity of 15mPa & s are put into a reaction vessel with a condensation reflux device, the temperature is slowly increased, the mixture is stirred and reacted for 4 hours under the conditions that the temperature is 105 ℃ and the vacuum degree is-0.09 MPa, then isopropanol is distilled out under reduced pressure at 85 ℃, and the siloxane-tetraisopropoxytitanium chelate is obtained after cooling for 8 hours.
Comparative example 2
100 parts of tetraisopropoxytitanium and 90 parts of hydroxyl silicone oil (the hydroxyl value is 4.8%) with the viscosity of 35mPa & s are put into a reaction vessel with a condensation reflux device, the temperature is slowly increased, the mixture is stirred and reacted for 4 hours under the conditions that the temperature is 105 ℃ and the vacuum degree is-0.09 MPa, then isopropanol is distilled out under reduced pressure at 85 ℃, and the siloxane-tetraisopropoxytitanium chelate is obtained after cooling for 8 hours.
Comparative example 3
100 parts of titanium tetraisopropoxide and 90 parts of MDT silicone oil with viscosity of 15 mPas and active group content of 1% are put into a reaction vessel with a condensation reflux device, the temperature is slowly increased, the mixture is stirred and reacted for 4 hours under the conditions that the temperature is 55 ℃ and the vacuum degree is-0.09 MPa, then isopropanol is distilled out under reduced pressure at 85 ℃, and the siloxane-titanium tetraisopropoxide chelate is obtained after cooling for 8 hours.
Comparative example 4
100 parts of titanium tetraisopropoxide and 90 parts of ethyl acetoacetate are put into a reaction vessel with a condensation reflux device, the temperature is slowly increased, the reaction is stirred for 4 hours under the conditions that the temperature is 105 ℃ and the vacuum degree is-0.09 MPa, then isopropanol is distilled under reduced pressure at 85 ℃, and the chelate of ethyl acetoacetate-titanium tetraisopropoxide is obtained after cooling for 8 hours.
Example 9 preparation of a dealcoholized Silicone sealant
Dealcoholized silicone sealants (in parts by weight) were prepared according to the following formulation composition using as catalysts the high activity catalysts prepared in examples 1 to 8, the siloxane-titanium tetraisopropoxide chelate prepared in comparative examples 1 to 3, the ethyl acetoacetate-titanium tetraisopropoxide chelate prepared in comparative example 4, unmodified titanium tetraisopropoxide, a mixture of unmodified titanium tetraisopropoxide and MDT silicone oil, respectively:
the preparation method comprises the following steps:
and (2) sequentially adding the raw materials into a high-speed dispersion stirrer or a planetary stirrer at room temperature, and stirring at the rotating speed of 20Hz for 60 minutes under the protection of nitrogen to obtain the dealcoholized silicone sealant.
Dealcoholized silicone sealants were prepared using the products prepared in examples and comparative examples as catalysts and were subjected to the performance tests shown in Table 1, in which the tack-free time and adhesion properties (test materials were common adhesion substrates such as aluminum, glass, ABS, PVC) were tested in accordance with GB/T13477-; the curing depth was tested according to method 3 in GB/T32369-; the yellowing resistance is tested according to a yellowing resistance test method of GB/T23983-2009 woodware coating; accelerated storage days at 70 ℃: the test is carried out after the accelerated storage for a certain number of days at 70 ℃, the surface drying is qualified within 24 hours, and the curing judgment refers to GB/T13477.5. The test results are shown in table 1.
TABLE 1 basic Properties of dealcoholized Silicone sealants
CF for cohesive failure and AF for adhesive failure;
titanium tetraisopropoxide (1) represents: the catalyst is titanium tetraisopropoxide, and other preparation raw materials and methods are the same as those of example 9;
titanium tetraisopropoxide (2) represents: the catalyst was prepared by physically mixing 100 parts of titanium tetraisopropoxide and 90 parts of MDT silicone oil having a viscosity of 15 mPas and an active group content of 1%, and other preparation raw materials and methods were the same as in example 9.
From the results in table 1, it can be seen that: the dealcoholized silicone sealant prepared in the embodiment 1-2 has the characteristics of fast deep curing and good bonding effect, but the storage period is relatively short, which is not beneficial to practical use; the dealcoholized silicone sealants prepared in the examples 3 to 4 have the characteristics of fast deep curing and good storage life, but the adhesive property is not wide enough and is not beneficial to practical use; the dealcoholized silicone sealants prepared in examples 7 to 8 have the characteristic of excellent storage performance, but the deep curing is slow, the adhesion is not wide enough, and the practical use is not facilitated; the dealcoholized silicone sealants prepared in examples 5 to 6 had short surface drying time, high curing speed, stable storage life, long storage time, good yellowing resistance, no viscosity peak generated during the preparation of the silicone sealants, and excellent adhesion to various substrates, so that the dealcoholized silicone sealants prepared in examples 5 to 6 had excellent comprehensive properties.
The dealcoholized silicone sealant prepared in the comparative examples 1-2 has the characteristics of stable adhesion, good adhesion universality and long storage period, but has long surface drying time and slow deep curing.
In the comparative example 3, because the reaction temperature is relatively low, the isopropanol of the siloxane-titanium tetraisopropoxide chelate is not completely removed, the prepared dealcoholized silicone sealant has the characteristics of stable bonding performance and fast deep curing, but has the defects of unsatisfactory storage period, poor yellowing resistance, obvious viscosity peak in the production process and the like.
The dealcoholized silicone sealant prepared in the comparative example 4 has the characteristics of stable adhesion and good adhesion universality, but has the defects of long surface drying time, slow deep curing, unsatisfactory yellowing resistance effect, high viscosity peak generation in the production process and the like.
The dealcoholized silicone sealant prepared by taking the titanium tetraisopropoxide (1) and the titanium tetraisopropoxide (2) as catalysts has the characteristics of stable bonding performance and quick deep curing, but has the defects of unsatisfactory storage period, poor yellowing resistance, obvious viscosity peak in the production process and the like.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (13)
1. The high-activity catalyst for the dealcoholization type silicone sealant is characterized by being siloxane-tetraisopropoxytitanium chelate, wherein the siloxane-tetraisopropoxytitanium chelate is obtained by reacting tetraisopropoxytitanium and MDT silicone oil at the temperature of 90-120 ℃ and under a certain vacuum degree, and the weight ratio of the tetraisopropoxytitanium to the MDT silicone oil is 100: 85-95;
the viscosity of the MDT silicone oil is 5-50 mPa.s, and the content of active groups is 0.5-1.5%;
the reaction time is 2-6 hours;
the vacuum degree is-0.06 to-0.10 MPa.
2. The high activity catalyst for a dealcoholization type silicone sealant according to claim 1, wherein the weight ratio of the titanium tetraisopropoxide to the MDT silicone oil is 100: 88-92.
3. The high activity catalyst for a dealcoholization type silicone sealant according to claim 2, wherein the weight ratio of the titanium tetraisopropoxide to the MDT silicone oil is 100: 90.
4. the highly active catalyst for a dealcoholization type silicone sealant according to claim 1, wherein the viscosity of said MDT silicone oil is 15 to 35 mPa-s, and the active group content is 0.8 to 1%.
5. A method for preparing a high activity catalyst for a dealcoholized silicone sealant according to any one of claims 1 to 4, comprising the steps of:
putting the tetraisopropoxytitanium and the MDT silicone oil into a reaction container, heating, stirring and reacting at 90-120 ℃ and a certain vacuum degree, distilling off isopropanol under reduced pressure, and cooling to obtain a siloxane-tetraisopropoxytitanium chelate, namely the high-activity catalyst for the dealcoholization type silicone sealant; the reaction time is 2-6 hours; the vacuum degree is-0.06 to-0.10 MPa.
6. The method for preparing the high-activity catalyst for the dealcoholized silicone sealant according to claim 5, wherein the reaction temperature is 100-110 ℃.
7. The method for preparing a high activity catalyst for a dealcoholized silicone sealant according to claim 5 or 6, wherein the temperature of the reduced pressure distillation is 80-90 ℃.
8. The method for preparing a high activity catalyst for a dealcoholized silicone sealant according to claim 7, wherein the reaction time is 3 to 5 hours; and/or the presence of a gas in the gas,
the vacuum degree is-0.085 to-0.095 MPa; and/or the presence of a gas in the gas,
the temperature of the reduced pressure distillation is 84-86 ℃.
9. The dealcoholized silicone sealant is characterized by being prepared from the following raw materials in parts by weight:
107 of 100 parts of glue, and the adhesive is prepared,
90-110 parts of nano active calcium carbonate,
2-8 parts of white carbon black by a gas phase method,
2-8 parts of methyltrimethoxysilane,
1-7 parts of a catalyst, namely,
0.1-1.0 part of silane coupling agent;
the catalyst is the high activity catalyst for a dealcoholized silicone sealant according to any one of claims 1 to 4.
10. The dealcoholized silicone sealant according to claim 9, which is prepared from the following raw materials in parts by weight:
107 of 100 parts of glue, and the adhesive is prepared,
95-105 parts of nano active calcium carbonate,
4-6 parts of white carbon black by a gas phase method,
4-6 parts of methyl trimethoxy silane,
3-5 parts of a catalyst, namely,
0.4-0.6 part of silane coupling agent.
11. The dealcoholized silicone sealant according to claim 10, wherein the dealcoholized silicone sealant is prepared from the following raw materials in parts by weight:
107 of 100 parts of glue, and the adhesive is prepared,
100 parts of nano-active calcium carbonate, namely,
5 parts of white carbon black by a gas phase method,
5 parts of methyl trimethoxy silane, namely methyl trimethoxy silane,
4 parts of a catalyst, namely adding 4 parts of,
and 0.5 part of silane coupling agent.
12. The dealcoholized silicone sealant according to any one of claims 9 to 11, wherein the viscosity of said 107 glue is from 1.5 to 2.5 ten thousand mPa-s; and/or the presence of a gas in the gas,
the silane coupling agent is KH-550.
13. A method of preparing a dealcoholized silicone sealant according to any one of claims 9 to 12 comprising the steps of:
and adding the 107 glue, the nano activated calcium carbonate, the fumed silica, the methyltrimethoxysilane, the catalyst and the silane coupling agent into a high-speed dispersion stirrer or a planetary stirrer, and stirring for 45-75 minutes at the rotating speed of 15-25Hz under the protection of nitrogen to obtain the dealcoholized silicone sealant.
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