CN113019456B - Titanium chelate catalyst, preparation method and application thereof in silicone rubber - Google Patents
Titanium chelate catalyst, preparation method and application thereof in silicone rubber Download PDFInfo
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- CN113019456B CN113019456B CN202110265652.8A CN202110265652A CN113019456B CN 113019456 B CN113019456 B CN 113019456B CN 202110265652 A CN202110265652 A CN 202110265652A CN 113019456 B CN113019456 B CN 113019456B
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- 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
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention discloses a titanium chelate catalyst and a preparation method and application thereof in silicone rubber, wherein under the inert atmosphere, titanate is heated to 90-110 ℃, compound A is added, and the reaction is carried out at the temperature of 80-100 ℃ to obtain the titanium chelate catalyst; wherein the compound A is N-ethoxycarbonylphthalimide or 1, 4-diacetylpiperazine-2, 5-diketone. The invention solves the technical problems of poor stability and the like of the titanium chelate catalyst, and the dealcoholized RTV-1 produced by using the titanium chelate prepared by the invention as the catalyst has greatly prolonged storage period and excellent high temperature resistance, aging resistance and other performances.
Description
Technical Field
The invention belongs to the technical field of preparation of organic silanol type rubber auxiliaries, and relates to a titanium chelate catalyst, a preparation method and application thereof in silicone rubber.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Single-component room temperature vulcanized silicone rubber (RTV-1) appears in the market from the sixties of the last century, is gradually widely accepted by the market, and is increasingly used at present. The vulcanization reaction of RTV-1 requires a crosslinking reaction with water in the air, and there are a deacetone type, a deamidation type, a dealcoholization type, a deacidification type, and the like depending on the crosslinking agent. RTV-1 is widely used in the fields of aerospace, electronics, optical instruments and buildings because of its excellent electrical and chemical inertness, heat resistance, natural aging resistance, fire resistance, moisture resistance, good air permeability and the like. Furthermore, the dealcoholization type RTV-1 is attracting more and more attention because methanol is removed during vulcanization and there is no corrosion to metal products. However, the dealcoholized RTV-1 has a relatively slow vulcanization rate and usually requires the addition of a catalyst to promote the vulcanization process. The catalysts usually used are organotin catalysts, but such catalysts cause a decrease in the storage stability of the alcohol-type silicone rubber, making it impossible to store it for a long period of time. The titanate catalyst is also a catalyst commonly used in the alcohol-type silicon rubber, and has the function of prolonging the storage stability of the alcohol-type silicon rubber. At present, titanate-based catalysts are often used as catalysts in alcohol-based silicone rubbers.
However, titanate catalysts can cause viscosity spikes in the preparation of alcohol-type silicone rubbers, resulting in increased energy consumption and increased equipment investment. Therefore, titanate-based catalysts with high activity and structural stability become the key to the alcohol-based silicone rubber. Patent CN103554172A describes the preparation of titanate chelate from isopropyl titanate, ethyl acetoacetate and 1, 3-propanediol, and has the advantages of simple and easily available raw materials, easily realized process, easy control of production process, and reduced or avoided occurrence of "viscosity peak". However, the inventor researches and discovers that the titanium chelate catalyst is not stable enough in structure and high in storage temperature requirement. In addition, the alcohol type glue may deteriorate during storage due to its high activity. In addition, if the chelating degree of titanate is increased, the stability of the structure of the titanate itself can be improved, but the activity is also reduced.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a titanium chelate catalyst, a preparation method and application thereof in silicone rubber.
In order to realize the purpose, the technical scheme of the invention is as follows:
on the one hand, the preparation method of the titanium chelate catalyst comprises the steps of heating titanate to 90-110 ℃ in an inert atmosphere, adding a compound A, and reacting at 80-100 ℃ to obtain the titanium chelate catalyst; wherein the compound A is N-ethoxycarbonylphthalimide or 1, 4-diacetylpiperazine-2, 5-diketone.
According to the invention, N-ethoxycarbonylphthalimide or 1, 4-diacetyl piperazine-2, 5-diketone is adopted as a modifier, wherein the modifier contains a plurality of carbonyl groups, and experiments show that under the above conditions, the plurality of carbonyl groups in the modifier can be bonded with titanium atoms to form a stable structure, so that the stability of the modifier is improved, and the occurrence of viscosity peak is avoided.
In another aspect, a titanium chelate catalyst obtained by the above preparation method.
In a third aspect, the titanium chelate catalyst is used in alcohol-type silicone rubber.
The invention has the beneficial effects that:
(1) The titanium chelate catalyst prepared by the invention has excellent performance, stable structure and long storage period.
(2) The dealcoholized RTV-1 prepared by using the titanium chelate prepared by the invention as a catalyst has excellent high temperature resistance, aging resistance and other properties. Solves the technical problems of short shelf life, poor stability, large viscosity peak and the like.
(3) The invention has convenient construction and no additional construction requirement.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The titanium acid ester is easy to hydrolyze into titanium dioxide, so that the structure is unstable, and the viscosity peak and the construction difficulty can be caused in the preparation process of the silicon rubber. The invention provides a titanium chelate catalyst, a preparation method and application thereof in silicone rubber.
The invention provides a typical embodiment of a preparation method of a titanium chelate catalyst, which comprises the steps of heating titanate to 90-110 ℃ in an inert atmosphere, adding a compound A, and reacting at 80-100 ℃ to obtain the titanium chelate catalyst; wherein the compound A is N-ethoxycarbonylphthalimide or 1, 4-diacetylpiperazine-2, 5-diketone.
The invention uses compounds containing dicarbonyl (N-ethoxycarbonylphthalimide and 1, 4-diacetyl piperazine-2, 5-diketone) as modifiers to perform ester exchange with titanate to replace alcohol compounds such as normal propyl alcohol, isopropyl alcohol, normal butyl alcohol, tertiary butyl alcohol and the like in the structure. The carbonyl group of the dicarbonyl compound is bonded with the titanium atom to form a stable structure, so that the stability of the dicarbonyl compound is improved, and the occurrence of a viscosity peak is avoided. The invention firstly heats up to 90-110 ℃, which can ensure that the compound A keeps liquid state and quickly disperses into the whole system, thereby avoiding the viscosity rise caused by the state change of the compound A.
In some examples of this embodiment, the titanate is any one of tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, and tetra-t-butyl titanate.
The inert atmosphere may be a nitrogen atmosphere, an argon atmosphere, or the like, and in some examples of this embodiment, the inert atmosphere is a nitrogen atmosphere. The production cost is reduced.
In some examples of this embodiment, the mass ratio of titanate to compound a is 1. When the mass ratio of the titanate to the compound A is 1.
In some examples of this embodiment, the titanate is heated to 95-100 ℃ and compound a is added.
In some examples of this embodiment, the reaction is carried out at 90 to 100 ℃ after addition of compound A.
In some examples of this embodiment, the reaction is followed by distillation under reduced pressure. Can remove the replaced structure and increase the purity of the titanium chelate catalyst.
In one or more embodiments, the distillation is performed under reduced pressure until the distillation stops.
In one or more embodiments, the vacuum of the reduced pressure distillation is between-0.1 and-0.09 MPa.
In one or more embodiments, the temperature of the reduced pressure distillation is from 105 to 115 ℃.
In another embodiment of the present invention, there is provided a titanium chelate catalyst obtained by the above preparation method.
In a third embodiment of the invention, the invention provides an application of the titanium chelate catalyst in alcohol-type silicone rubber.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
(1) 20g of tetraisopropyl titanate was placed in a flask, stirred under a nitrogen atmosphere, and heated to a temperature of 100 ℃.
(2) Under a nitrogen atmosphere, 20g of 1, 4-diacetylpiperazine-2, 5-dione was rapidly added and reacted at a temperature of 90 ℃ for 5 hours.
(3) Heating to 110 deg.C, vacuum distilling at-0.1 Mpa until no low-boiling-point substance is removed.
The product is collected and sealed and stored by using a plastic bottle, and is placed in the environment of 10 ℃ and 40 ℃ for 24 hours respectively, the crystallization and solidification phenomena are avoided, and the property is stable.
The catalyst is matched with a cross-linking agent (methyltrimethoxysilane), a coupling agent (KH-560), a tin catalyst (dibutyltin dilaurate), a water removing agent (vinyl trimethoxy silane) and triethyl citrate, and a compounded auxiliary agent can effectively catalyze the surface drying, viscosity breaking and curing of alcohol type glue (8 ten thousand viscosity 107 glue) and the surface drying, viscosity breaking and curing after 1 day of aging at 90 ℃.
Catalyst, 8 ten thousand viscosity 107 glue, methyl trimethoxy silane, KH-560, dibutyltin dilaurate, vinyl trimethoxy silane, fumed silica, 150 viscosity dimethyl silicone oil and triethyl citrate according to the mass ratio of 16:280:40:4:8:4:32:60:3 adding the mixture into a planetary dispersion machine, uniformly compounding, canning, putting into an aging oven at 90 ℃ for 24 hours, taking out, cooling to room temperature, taking out adhesive tapes, observing and recording the surface drying, tack-eliminating and curing time.
Surface drying for 5min, removing viscosity for 30min, and curing for 28h;
surface drying at 90 deg.C for 1 day for 20min, removing adhesive for 200min, and curing for 60h.
Example 2
As described in example 1, except that in step (2), the 1, 4-diacetylpiperazine-2, 5-dione was changed to N-ethoxycarbonylphthalimide (35 g).
The product is collected and sealed and stored by using a plastic bottle, and is placed in the environment of 10 ℃ and 40 ℃ for 24 hours respectively, the crystallization and solidification phenomena are avoided, and the property is stable.
Drying the surface for 20min, removing the adhesive for 40min, and curing for 30h;
surface drying at 90 deg.C for 1 day for 40min, removing stickiness for 160min, and curing for 70h.
Example 3
As described in example 1, except that tetra-t-butyl titanate was used instead of tetraisopropyl titanate in step (1);
the 1, 4-diacetylpiperazine-2, 5-dione in step (2) was changed to 25g of N-ethoxycarbonylphthalimide.
The product is collected, sealed and stored by using a plastic bottle, and placed in the environment of 10 ℃ and 40 ℃ for 24 hours respectively, and the product has no crystallization and solidification phenomena and stable property.
Drying the surface for 15min, removing the adhesive for 20min, and curing for 24h;
surface drying at 90 deg.C for 1 day for 40min, removing adhesive for 220min, and curing for 80 hr.
Example 4
As described in example 1, except that the amount of 1, 4-diacetylpiperazine-2, 5-dione used in step (2) was changed to 15g.
The product is collected, sealed and stored by using a plastic bottle, and placed in the environment of 10 ℃ and 40 ℃ for 24 hours respectively, and the product has no crystallization and solidification phenomena and stable property.
Drying the surface for 2min, removing the viscosity for 8min, and curing for 24h;
surface drying at 90 deg.C for 1 day for 20min, removing adhesive for 180min, and curing for 90h.
Comparative example 1
The S22 titanium catalyst of Guangzhou firm and resolute chemical engineering is used, matched with the same auxiliary agent and dosage as the embodiment, uniformly compounded in a planetary dispersion machine, canned, and then the adhesive tape is punched out for surface drying, tack-eliminating and curing.
The S22 titanium catalyst of Guangzhou firm and permanent chemical engineering is hermetically stored by a plastic bottle and is placed in the environment of 10 ℃ and 40 ℃ for 24 hours respectively, and the crystallization and solidification phenomena are avoided, and the property is stable.
The detection results for the strips were as follows:
surface drying for 16min, tack eliminating for 48min, and curing for 96h;
surface drying at 90 deg.C for 1 day for 29min, removing viscosity for 300min, and not curing.
Comparative example 2
D-60 titanium catalyst of New materials Co, new blue sky, hubei is used, auxiliary agents and dosage which are the same as those in the embodiment are matched, the mixture is uniformly compounded in a planet dispersion machine and then canned, and an adhesive tape is punched out to measure surface dryness, tack free and solidification.
The D-60 titanium catalyst of New materials Co, new blue sky, hubei is stored in plastic bottle in sealed mode, and is placed in 10 deg.C and 40 deg.C environment for 24h respectively, and has no crystallization and solidification phenomena, and stable property.
The detection results for the strips were as follows:
surface drying for 31min, tack removing for 100min, and curing for 96h;
surface drying at 90 deg.C for 1 day for 77min, removing adhesive for 180min, and curing for 120h.
Comparative example 3
The Tyzor726 titanium catalyst of Guangzhou firm and resolute chemical engineering is used, matched with the same auxiliary agent and dosage as the embodiment, uniformly compounded in a planetary dispersion machine, canned, and then the adhesive tape is punched out to measure the surface dryness, the tack free and the solidification.
The Tyzor726 titanium catalyst of Guangzhou firm chemical industry is stored in a plastic bottle in a sealing way, and is placed in the environment of 10 ℃ and 40 ℃ for 24 hours respectively, wherein the solid is completely crystallized after 24 hours at 10 ℃ and can be recovered by heating, but the problem that the glue cannot be solidified after repeated crystallization and melting processes is solved.
The detection results for the adhesive tape were as follows:
the surface drying time of the product is less than 1min, the surface is dried and viscosity is removed before canning, and the condition of direct use is not met.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a titanium chelate catalyst is characterized in that under the inert atmosphere, titanate is heated to 90-110 ℃, a compound A is added, and the reaction is carried out at the temperature of 80-100 ℃ to obtain the titanium chelate catalyst; wherein the compound A is N-ethoxycarbonylphthalimide or 1, 4-diacetylpiperazine-2, 5-dione; the mass ratio of the titanate to the compound A is 1.5-1.
2. The method of preparing a titanium chelate catalyst according to claim 1, wherein the titanate is any one of tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate and tetra-t-butyl titanate.
3. The method for preparing a titanium chelate catalyst according to claim 1, wherein the inert atmosphere is a nitrogen atmosphere.
4. The method for preparing a titanium chelate catalyst according to claim 1, wherein the mass ratio of the titanate to the compound A is 1.
5. The method for preparing a titanium chelate catalyst according to claim 1, wherein the titanate is heated to 95 to 100 ℃ and then the compound A is added.
6. The process for producing a titanium chelate catalyst according to claim 1, wherein the reaction is carried out at 90 to 100 ℃ after the compound A is added.
7. The process for producing a titanium chelate catalyst according to claim 1, wherein the reaction is followed by distillation under reduced pressure.
8. The process for producing a titanium chelate catalyst according to claim 7, wherein the distillation is carried out under reduced pressure until the distillation is stopped;
or the vacuum degree of the reduced pressure distillation is-0.1 to-0.09 MPa;
or the temperature of the reduced pressure distillation is 105-115 ℃.
9. A titanium chelate catalyst obtained by the production method according to any one of claims 1 to 8.
10. Use of the titanium chelate catalyst according to claim 9 in an alcohol-type silicone rubber.
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| CN114456601A (en) * | 2022-02-09 | 2022-05-10 | 江西晨光新材料股份有限公司 | Dealcoholized single-component room temperature vulcanized silicone rubber and preparation method thereof |
| CN115991875B (en) * | 2023-02-15 | 2023-12-15 | 杭州之江有机硅化工有限公司 | Titanate catalyst for dealcoholized room temperature vulcanized silicone rubber and preparation method thereof |
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| US6054552A (en) * | 1998-08-14 | 2000-04-25 | General Electric Company | Process for preparing ester amides and polyesteramides |
| CN102875591B (en) * | 2012-09-25 | 2015-03-04 | 湖北新蓝天新材料股份有限公司 | Method for preparing tetra-tert-butyl orthotitanate composite |
| CN103554172A (en) * | 2013-10-17 | 2014-02-05 | 深圳市红叶杰科技有限公司 | Titanate chelate for single-component dealcoholized room temperature vulcanized silicone rubber and preparation method thereof |
| CN109749453B (en) * | 2018-12-28 | 2021-06-22 | 广州市白云化工实业有限公司 | Titanate catalytic composition, preparation method and application thereof |
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