CN113528081A - Hot vulcanized silicone rubber base coat binder and preparation method thereof - Google Patents
Hot vulcanized silicone rubber base coat binder and preparation method thereof Download PDFInfo
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- CN113528081A CN113528081A CN202010294202.7A CN202010294202A CN113528081A CN 113528081 A CN113528081 A CN 113528081A CN 202010294202 A CN202010294202 A CN 202010294202A CN 113528081 A CN113528081 A CN 113528081A
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- silicone rubber
- adhesive
- heat
- vulcanized silicone
- base coat
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- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a heat-vulcanized silicone rubber base coat binder and a preparation method thereof, 11-27 parts of titanate and 5.5-31 parts of ethyl acetoacetate are mixed for 0.5-3 h at the temperature of 50-110 ℃, then 50-80 parts of vinyl silane are added at normal temperature and mixed uniformly to obtain the heat-vulcanized silicone rubber base coat binder, the base coat is mainly applied to the bonding of heat-vulcanized silicone rubber or high-temperature silicone rubber and heterogeneous workpieces, has good bonding performance, simultaneously has the bonding strength of up to 5.00MPa, can be stored in the air for a long time of up to 14h, and is also a binder with simple components, good stability and low toxicity.
Description
Technical Field
The invention relates to a heat-vulcanized silicone rubber base coat binder and a preparation method thereof, in particular to a heat-vulcanized silicone rubber base coat binder with low toxicity and good stability and a preparation method thereof, belonging to the technical field of silicone rubber.
Background
The silicon rubber is a special rubber material which takes a silicon-oxygen bond as a main chain of a molecular structure and is linked with other chemical structures by silicon elements, and is generally prepared by ring-opening polymerization of cyclic polysiloxane. The silicone rubber has a plurality of special properties such as weather resistance, physical and mechanical properties, excellent high and low temperature properties and the like due to the unique chemical structure. In the application process, the rubber material is usually taken as a product part and is combined with other heterogeneous parts to form a product. Because the surface free energy of the silicon rubber is low, interaction force is difficult to generate between the silicon rubber and other heterogeneous products, and the adhesive is mainly used for providing bonding effect between heterogeneous materials in the industry at present. Such adhesives are commonly referred to in the rubber industry as "primers". So that the base coat plays an important role in the rubber industry.
The main silicon rubber base coat in the market at present has complex components, and because a large amount of silane coupling agent and titanate coupling agent are added, the reaction activity is high, the long-term storage is not facilitated, and the operation time of the base coat in the use process is limited because the titanate activity is high. For example, patents CN109054725A and CN103214946A all use titanate as their effective components, but because the activity of titanate is high, the operation time in the air is short, especially in the area with high air humidity, which increases the operation difficulty and is difficult to store for a long time.
In addition, there are patents showing that toxic and harmful substances such as polyisocyanate and benzene-based solvent are used as one of the components of the primer, which seriously affect the safety and health of the constructors. For example, patent CN104830225A discloses a primer for bonding silicone rubber and polypropylene material and a preparation method thereof, wherein the primer is prepared from a silane coupling agent, a titanic acid compound, a benzene solvent, a low-boiling-point substance solvent, a polyisocyanate and an organosilicon compound, and can effectively provide interaction between silicone rubber and polypropylene. The benzene solvent and the polyisocyanate are used as components simultaneously, and are both harmful substances, and the benzene solvent has a large taste and has the defect of influencing the harm of constructors and the environment.
In addition, patent CN106280983A discloses an addition type tackifying primer and a preparation method thereof, which is prepared by using an organic solvent, polymethyltriethoxysilane, a silane coupling agent, titanate and an organic silicon resin, wherein the primer uses a peroxide vulcanization system of polymethyltriethoxysilane in large amount besides the silane coupling agent, so that the tackifying effect is good, and the tackifying effect can be maintained for a long time after construction.
Disclosure of Invention
The invention aims to provide a hot vulcanized silicone rubber base coat binder which is mainly applied to the bonding of hot vulcanized silicone rubber or high-temperature silicone rubber and heterogeneous workpieces, has good bonding performance, has the bonding strength of up to 5.00MPa, and is simple in component, good in stability and low in toxicity.
In order to ensure the long-term stability of the adhesive in the construction process, the invention also aims to provide a preparation method of the heat-vulcanized silicone rubber base coating adhesive, and the adhesive prepared by the method can be stored in the air for a long time of up to 14 hours.
The invention is realized by the following technical scheme: the heat-vulcanized silicone rubber base coat binder is prepared from the following raw materials in parts by weight:
vinyl silane: 50-80 parts;
titanate ester: 11-27 parts;
ethyl acetoacetate: 5.5 to 31 parts.
The vinyl silane is selected from vinyl triethoxysilane or vinyl trimethoxy siloxane.
The titanate is selected from tetraesters of titanic acid, such as tetrabutyl titanate, tetraisobutyl titanate, tetraethyl titanate, tetrapropyl titanate, or the like.
According to the proportion, titanate and ethyl acetoacetate are mixed for 0.5-3 hours at the temperature of 50-110 ℃, then vinyl silane is added at the normal temperature, and the mixture is uniformly mixed, so that the heat-vulcanized silicone rubber base coat binder is obtained.
The adhesive strength of the heat vulcanized silicone rubber priming adhesive is more than 2.0 MPa.
After the heat vulcanized silicone rubber priming adhesive is placed in the air for 14 hours, the adhesive strength is more than 1.4 MPa.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the invention, the primer with good adhesion property to the silicone rubber is obtained through selection of a specific raw material formula and limitation of component ratio, so that a solvent system of the primer is simplified, the use of toxic and harmful solvents is reduced on the premise of meeting performance requirements, and the toxicity of the primer is reduced.
(2) The invention can overcome the defect of high activity of titanate, adopts a stabilization in-situ treatment technology to stabilize the phthalate with higher reaction activity in the air, namely, the ethyl acetoacetate and the phthalate generate chelation reaction under certain conditions, realizes the improvement of the stability and the reverse movement of the phthalate, does not reduce the bonding effect of the phthalate, and further reduces the defect of bonding failure of the primer caused by hydrolysis in the construction process of the phthalate in the primer.
(3) The performance indexes of the primer provided by the invention meet the following requirements: the bonding strength is more than 2.0 MPa; and the adhesive can be stored in the air for a long time of 14h in the construction process, the adhesive strength is still more than 1.4MPa after the adhesive is placed for 14h, and the cohesive failure is kept.
(4) The primer disclosed by the invention also has the characteristic of high efficiency, and can be diluted by using an alcohol solvent, so that the maximum dilution ratio can reach 6 times.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
the embodiment relates to a heat-vulcanized silicone rubber prime coat adhesive with high viscosity, good stability, low toxicity and high efficiency.
The preparation process comprises the following steps:
firstly, 14.6g of tetrabutyl titanate and 5.5g of ethyl acetoacetate are taken to be put in a round-bottom flask, the mechanical stirring is carried out for 0.5h at the temperature of 80 ℃, then the round-bottom flask is placed to the normal temperature, 80.0g of vinyltriethoxysilane is added, and the mixture is uniformly mixed, thus obtaining the heat vulcanized silicone rubber prime coat adhesive.
Examples 2 to 5 and comparative examples 1 to 2:
referring to the production process described in example 1, examples 2 to 5 and comparative examples 1 to 2 were carried out, and the primer was prepared with the specific parameters shown in table 1 below.
TABLE 1
Comparative example 3:
firstly, 18.2g of tetrabutyl titanate and 13.8g of ethyl acetoacetate are uniformly mixed in a round-bottom flask, and then 68.0g of vinyl triethoxysilane is added and uniformly mixed to obtain the primer.
The binders prepared in the examples 1 to 6 and the comparative examples 1 to 3 were tested, and the test method was as follows:
the test was immediately carried out:
the primer prepared in examples 1 to 6 and comparative examples 1 to 3 was mixed with absolute ethanol at a dilution ratio for at least 5min, and after mixing, the mixture was applied to one end (about 20% area) of a galvanized sheet, and after drying naturally in the air for 0.5h, silicone rubber (GX-562, produced by Zhonglan Cheng light chemical research and design institute Co., Ltd.) was placed on the coated surface of one galvanized sheet, and then the other galvanized sheet coated with the primer was vulcanized for 10min at 165 ℃, and then the leftover materials were removed. Shear strength was tested according to GB/T2790-1995 standard.
Test after 14 h:
the primer prepared in examples 1 to 6 and comparative examples 1 to 3 was mixed with absolute ethanol at a dilution ratio for at least 5min, and after mixing, the mixture was applied to one end (about 20% area) of a galvanized sheet, and after 14.5h in the air, silicone rubber (GX-562, produced by Zhonglan Cheng light chemical research design institute Co., Ltd.) was applied to the coated surface of one galvanized sheet, and then the other sheet of galvanized sheet coated with primer was vulcanized on the reverse defense silicone rubber at 165 ℃ for 10min, and after taking out, leftover materials were removed. Shear strength was tested according to GB/T2790-1995 standard.
The properties of the primer after testing are shown in table 2 below.
TABLE 2
The test method can verify that the primer disclosed by the invention has good adhesive property, for example, the shear strength can reach 5.0 MPa in the immediate test of example 4, the adhesive property can be tested after the primer is placed for 14h, the shear strength is at least greater than 1.4MPa, particularly the shear strength in example 3 can even reach 3.15 MPa, and the cohesive failure is maintained, so that the primer disclosed by the invention can meet the long-term stability in the construction process and is more beneficial to the application of the primer in industrial production. In addition to this, the primer of the present invention is characterized by high efficacy, see example 6, when 1: the primer properties were measured at a dilution ratio of 6 and still met the shear strength 3.82MPa (tested immediately) and 2.43 MPa (left for 14 h).
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (6)
1. The heat-vulcanized silicone rubber base coat adhesive is characterized in that: the composition is prepared from the following raw materials in parts by weight:
vinyl silane: 50-80 parts;
titanate ester: 11-27 parts;
ethyl acetoacetate: 5.5 to 31 parts.
2. The thermally-curable silicone rubber primer adhesive of claim 1, wherein: the vinyl silane is selected from vinyl triethoxysilane or vinyl trimethoxy siloxane.
3. The thermally-curable silicone rubber primer adhesive of claim 1, wherein: the titanate is selected from tetrakistitanate.
4. A preparation method of a heat-vulcanized silicone rubber base coat adhesive is characterized by comprising the following steps: according to the proportion of claim 1, titanate and ethyl acetoacetate are mixed for 0.5-3 h at the temperature of 50-110 ℃, then vinyl silane is added at normal temperature, and the mixture is uniformly mixed, so that the hot vulcanized silicone rubber primer adhesive is obtained.
5. The method for preparing a heat-curable silicone rubber primer adhesive according to claim 4, wherein: the adhesive strength of the heat vulcanized silicone rubber priming adhesive is more than 2.0 MPa.
6. The method for preparing a heat-curable silicone rubber primer adhesive according to claim 4, wherein: after the heat vulcanized silicone rubber priming adhesive is placed in the air for 14 hours, the adhesive strength is more than 1.4 MPa.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010294202.7A CN113528081B (en) | 2020-04-15 | 2020-04-15 | Hot vulcanized silicone rubber primer adhesive and preparation method thereof |
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| CN202010294202.7A CN113528081B (en) | 2020-04-15 | 2020-04-15 | Hot vulcanized silicone rubber primer adhesive and preparation method thereof |
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| Publication Number | Publication Date |
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| CN113528081A true CN113528081A (en) | 2021-10-22 |
| CN113528081B CN113528081B (en) | 2023-07-04 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59152961A (en) * | 1983-02-18 | 1984-08-31 | Sunstar Giken Kk | Primer composition |
| EP0798344A2 (en) * | 1996-03-29 | 1997-10-01 | Dow Corning Toray Silicone Company, Limited | Fluorosilicone rubber composition and method of adhering it to a substrate |
| CN103214946A (en) * | 2013-04-28 | 2013-07-24 | 深圳市新亚新材料有限公司 | Primer coating for single-component room-temperature vulcanized silicone rubber and preparation method thereof |
| 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 |
| CN104830225A (en) * | 2015-01-27 | 2015-08-12 | 杭州师范大学 | Bottom sizing agent enhancing bonding strength between silicone rubber and polypropylene material and preparation method thereof |
| CN109233625A (en) * | 2018-09-28 | 2019-01-18 | 深圳市康利邦科技有限公司 | A kind of silicon rubber silane coupling agent resistant to high temperature and preparation method thereof |
-
2020
- 2020-04-15 CN CN202010294202.7A patent/CN113528081B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59152961A (en) * | 1983-02-18 | 1984-08-31 | Sunstar Giken Kk | Primer composition |
| EP0798344A2 (en) * | 1996-03-29 | 1997-10-01 | Dow Corning Toray Silicone Company, Limited | Fluorosilicone rubber composition and method of adhering it to a substrate |
| CN103214946A (en) * | 2013-04-28 | 2013-07-24 | 深圳市新亚新材料有限公司 | Primer coating for single-component room-temperature vulcanized silicone rubber and preparation method thereof |
| 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 |
| CN104830225A (en) * | 2015-01-27 | 2015-08-12 | 杭州师范大学 | Bottom sizing agent enhancing bonding strength between silicone rubber and polypropylene material and preparation method thereof |
| CN109233625A (en) * | 2018-09-28 | 2019-01-18 | 深圳市康利邦科技有限公司 | A kind of silicon rubber silane coupling agent resistant to high temperature and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 山下晋三 等编，纪奎江 等译: "《交联剂手册》", 31 July 1990, 化学工业出版社 * |
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