CN116041785A - Modified liquid nitrile rubber and preparation method and application thereof - Google Patents
Modified liquid nitrile rubber and preparation method and application thereof Download PDFInfo
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- CN116041785A CN116041785A CN202310134752.6A CN202310134752A CN116041785A CN 116041785 A CN116041785 A CN 116041785A CN 202310134752 A CN202310134752 A CN 202310134752A CN 116041785 A CN116041785 A CN 116041785A
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- nitrile rubber
- liquid nitrile
- carboxyl
- diglycidyl ether
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Abstract
The invention discloses modified liquid nitrile rubber, which consists of 100 parts of carboxyl-terminated liquid nitrile rubber, 20-80 parts of diglycidyl ether compound and 0.3-1 part of antioxidant according to parts by weight. The invention also discloses a preparation method of the modified liquid nitrile rubber, which comprises the steps of mixing a diglycidyl ether compound and an antioxidant in a reaction kettle, heating to 90-110 ℃, taking 100 parts of carboxyl-terminated liquid nitrile rubber, putting into the reaction kettle for 1-3 times, controlling the temperature to 100-160 ℃, and carrying out heat preservation reaction for 0.5-2 hours. The invention also discloses application of the modified liquid nitrile rubber, wherein the modified liquid nitrile rubber is used as a toughening agent and applied to manufacturing epoxy resin adhesives and casting resins. The product prepared from the modified liquid nitrile rubber has the characteristics of good use toughness, good cold and heat cycle resistance and high bonding strength.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a modified liquid nitrile rubber and a preparation method and application thereof.
Background
Epoxy resins are often used for manufacturing epoxy resin adhesives and casting resins, but epoxy resins have the defect of high brittleness, so that the application of the epoxy resins is limited to a certain extent.
The epoxy resin is toughened, so that the defect of high brittleness of the epoxy resin can be overcome. The method for toughening the epoxy resin is mainly to add materials such as rubber elastomer, thermoplastic plastic, rigid filler and the like into the epoxy resin to form a two-phase structure, or to improve the epoxy resin by utilizing an interpenetrating network structure and change the net-shaped chemical structure of the epoxy resin. In the method of adding the rubber elastomer into the epoxy resin, adding the reactive liquid rubber is an important method for increasing the toughness of the epoxy resin, and the improvement of the toughness can increase the bonding force between the adhesive and the base material, thereby being beneficial to the application of the epoxy resin between the adhesive and the base material.
Carboxyl-terminated liquid nitrile rubber (CTBN) is one of reactive liquid rubbers, which is a telechelic high polymer, with reactive functional groups carboxyl groups at both ends of the molecular chain, but the epoxy groups of the epoxy resin or amine groups of the amine curing agent and carboxyl groups of the carboxyl-terminated liquid nitrile rubber generally cannot react at room temperature.
The problem is to be solved in the process of applying the carboxyl-terminated liquid nitrile rubber as a toughening agent to epoxy resin toughening.
Disclosure of Invention
In order to overcome the defect and the defect that carboxyl groups of the carboxyl-terminated liquid nitrile rubber and epoxy groups of epoxy resin or amine groups of amine curing agents cannot react at room temperature, the primary aim of the invention is to react excessive diglycidyl ether compound with the carboxyl-terminated liquid nitrile rubber at 100-160 ℃, and antioxidant is added to reduce oxidation and crosslinking reaction of the carboxyl-terminated liquid nitrile rubber at high temperature, so that the modified liquid nitrile rubber is prepared, and the modified liquid nitrile rubber has the characteristics of reacting with the amine curing agents of epoxy resin at room temperature, improving toughness of epoxy resin and increasing adhesion force between an epoxy resin adhesive and a base material. The specific technical scheme is as follows:
the modified liquid nitrile rubber consists of 100 parts of carboxyl-terminated liquid nitrile rubber, 20-80 parts of diglycidyl ether compound and 0.3-1 part of antioxidant in parts by weight.
Preferably, the mass percentage of acrylonitrile in the carboxyl-terminated liquid nitrile rubber is 20-30%, the mass percentage of carboxyl is 1-2%, and the viscosity of the carboxyl-terminated liquid nitrile rubber is 20-40 Pa.s at 23 ℃.
Preferably, the antioxidant is one of hindered phenol antioxidant 246, antioxidant 1010 and antioxidant 1076.
Preferably, the diglycidyl ether compound is one of ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, hexanediol diglycidyl ether, 1, 2-cyclohexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polyether polyol diglycidyl ether.
Preferably, the modified liquid nitrile rubber is a liquid nitrile rubber containing glycidyl ether groups.
The invention further aims to provide a preparation method of the modified liquid nitrile rubber, which comprises the steps of adding a diglycidyl ether compound and an antioxidant into a reaction kettle, stirring, heating to 90-110 ℃, taking 100 parts of carboxyl-terminated liquid nitrile rubber, adding the carboxyl-terminated liquid nitrile rubber into the reaction kettle for 1-3 times, wherein the time interval between the carboxyl-terminated liquid nitrile rubber and the reaction kettle is 5-15 min, and when the carboxyl-terminated liquid nitrile rubber is completely fed, controlling the temperature to 100-160 ℃, and carrying out heat preservation reaction for 0.5-2 h to obtain the modified liquid nitrile rubber.
It is a further object of the present invention to provide the use of the modified liquid nitrile rubber described above as a toughening agent for the manufacture of epoxy adhesives, casting resins.
The mechanism of the invention is as follows:
the carboxyl of the carboxyl-terminated liquid nitrile rubber and the epoxy group of the epoxy resin or the amine group of the amine curing agent cannot react at room temperature, so that the effect of chemical compatibility cannot be achieved. In order to overcome the defects and the shortcomings, the epoxy groups in the excessive diglycidyl ether compound and the carboxylic acid groups in the carboxyl-terminated liquid nitrile rubber are subjected to addition reaction at 100-160 ℃, and an antioxidant is added, so that the oxidation and crosslinking reactions of the carboxyl-terminated liquid nitrile rubber at high temperature can be reduced, and the purpose of preparing the glycidyl ether group-containing liquid nitrile rubber with controllable structure by using the carboxyl-terminated liquid nitrile rubber is achieved by the reaction mode.
The invention has the beneficial effects that:
the modified liquid nitrile rubber prepared by the invention, namely the liquid nitrile rubber containing the glycidyl ether group, has definite structure and composition, is used for toughening epoxy resin and casting resin, can react with anhydride curing agents under the heating condition, can react with amines of the epoxy resin curing agents at room temperature, and has the characteristics of high microphase separation degree, good impact property and low temperature resistance, and the liquid nitrile rubber molecules containing the glycidyl ether group are linked into the reticular molecular structure of the epoxy resin through the amino or carboxyl chemical bonds of the curing agents. The adhesive prepared from the modified liquid nitrile rubber has the characteristics of good use toughness, good cold and heat cycle resistance and high bonding strength.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to specific embodiments. It should be understood that the detailed description is presented by way of example only and is not intended to limit the invention.
Example 1
Adding 20 parts of ethylene glycol diglycidyl ether and 0.3 part of antioxidant 1010 into a reaction kettle, stirring, heating to 90 ℃, taking 100 parts of carboxyl-terminated liquid nitrile rubber, putting into the reaction kettle, controlling the temperature to 100 ℃ when the carboxyl-terminated liquid nitrile rubber is fed, and carrying out heat preservation reaction for 2 hours to obtain the ethylene glycol diglycidyl ether modified liquid nitrile rubber.
Wherein the mass percentage of acrylonitrile in the carboxyl-terminated liquid nitrile rubber is 20 percent, the mass percentage of carboxyl is 2 percent, and the viscosity of the carboxyl-terminated liquid nitrile rubber is 20 Pa.s at 23 ℃.
Example 2
Adding 40 parts of diethylene glycol diglycidyl ether and 0.5 part of antioxidant 1076 into a reaction kettle, stirring, heating to 95 ℃, taking 100 parts of carboxyl-terminated liquid nitrile rubber, adding the 100 parts of carboxyl-terminated liquid nitrile rubber into the reaction kettle for 2 times, wherein the time interval between each time of adding the carboxyl-terminated liquid nitrile rubber is 5min, and when the feeding of the carboxyl-terminated liquid nitrile rubber is completed, controlling the temperature to 110 ℃, and carrying out heat preservation reaction for 1.5h to obtain the diethylene glycol diglycidyl ether modified liquid nitrile rubber.
Wherein the mass percentage of acrylonitrile in the carboxyl-terminated liquid nitrile rubber is 25 percent, the mass percentage of carboxyl is 2 percent, and the viscosity of the carboxyl-terminated liquid nitrile rubber is 30 Pa.s at 23 ℃.
Example 3
Adding 30 parts of 1, 4-butanediol diglycidyl ether and 1 part of hindered phenol antioxidant 246 into a reaction kettle, stirring, heating to 100 ℃, taking 100 parts of carboxyl-terminated liquid nitrile rubber, adding into the reaction kettle for 3 times, wherein the time interval for adding the carboxyl-terminated liquid nitrile rubber each time is 10min, and when the carboxyl-terminated liquid nitrile rubber is completely added, controlling the temperature to 120 ℃, and carrying out heat preservation reaction for 2h to obtain the 1, 4-butanediol diglycidyl ether modified liquid nitrile rubber.
Wherein the mass percentage of acrylonitrile in the carboxyl-terminated liquid nitrile rubber is 30 percent, the mass percentage of carboxyl is 1.5 percent, and the viscosity of the carboxyl-terminated liquid nitrile rubber is 40 Pa.s at 23 ℃.
Example 4
Adding 40 parts of neopentyl glycol diglycidyl ether and 0.5 part of antioxidant 1010 into a reaction kettle, stirring, heating to 100 ℃, taking 100 parts of carboxyl-terminated liquid nitrile rubber, adding into the reaction kettle for 3 times, wherein the time interval between each time of adding of the carboxyl-terminated liquid nitrile rubber is 5min, and when the feeding of the carboxyl-terminated liquid nitrile rubber is completed, controlling the temperature to 130 ℃, and carrying out heat preservation reaction for 0.5h to obtain the neopentyl glycol diglycidyl ether modified liquid nitrile rubber.
Wherein the mass percentage of acrylonitrile in the carboxyl-terminated liquid nitrile rubber is 30 percent, the mass percentage of carboxyl is 1 percent, and the viscosity of the carboxyl-terminated liquid nitrile rubber is 40 Pa.s at 23 ℃.
Example 5
Adding 40 parts of 1, 2-cyclohexanediol diglycidyl ether and 0.5 part of antioxidant 1076 into a reaction kettle, stirring, heating to 110 ℃, taking 100 parts of carboxyl-terminated liquid nitrile rubber, putting the 100 parts of carboxyl-terminated liquid nitrile rubber into the reaction kettle for 2 times, and carrying out heat preservation reaction for 1h at a temperature of 140 ℃ when the carboxyl-terminated liquid nitrile rubber is fed completely, thereby obtaining the 1, 2-cyclohexanediol diglycidyl ether modified liquid nitrile rubber.
Wherein the mass percentage of acrylonitrile in the carboxyl-terminated liquid nitrile rubber is 30 percent, the mass percentage of carboxyl is 1 percent, and the viscosity of the carboxyl-terminated liquid nitrile rubber is 40 Pa.s at 23 ℃.
Example 6
Adding 80 parts of polyether polyol diglycidyl ether and 0.5 part of hindered phenol antioxidant 246 into a reaction kettle, stirring, heating to 100 ℃, taking 100 parts of carboxyl-terminated liquid nitrile rubber, adding into the reaction kettle for 3 times, wherein the time interval for adding the carboxyl-terminated liquid nitrile rubber each time is 10min, and when the carboxyl-terminated liquid nitrile rubber is completely added, controlling the temperature to 160 ℃, and carrying out heat preservation reaction for 2h to obtain the polyether polyol diglycidyl ether modified liquid nitrile rubber.
Wherein the mass percentage of acrylonitrile in the carboxyl-terminated liquid nitrile rubber is 30 percent, the mass percentage of carboxyl is 1 percent, and the viscosity of the carboxyl-terminated liquid nitrile rubber is 40 Pa.s at 23 ℃.
The products prepared in examples 1 to 6 can be used as toughening agents for manufacturing epoxy resin adhesives and casting resins.
It should be understood that the foregoing detailed description of the present invention is provided for illustration only and is not limited to the technical solutions described in the embodiments of the present invention, and those skilled in the art should understand that the present invention may be modified or substituted for the same technical effects; as long as the use requirement is met, the invention is within the protection scope of the invention.
Claims (7)
1. A modified liquid nitrile rubber is characterized in that: the modified liquid nitrile rubber consists of 100 parts of carboxyl-terminated liquid nitrile rubber, 20-80 parts of diglycidyl ether compound and 0.3-1 part of antioxidant according to parts by weight.
2. A modified liquid nitrile rubber according to claim 1, characterized in that: the mass percentage of acrylonitrile in the carboxyl-terminated liquid nitrile rubber is 20-30%, the mass percentage of carboxyl is 1-2%, and the viscosity of the carboxyl-terminated liquid nitrile rubber is 20-40 Pa.s at 23 ℃.
3. A modified liquid nitrile rubber according to claim 1, characterized in that: the antioxidant is one of hindered phenol antioxidants 264, antioxidants 1010 and antioxidants 1076.
4. A modified liquid nitrile rubber according to claim 1, characterized in that: the diglycidyl ether compound is one of ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, hexanediol diglycidyl ether, 1, 2-cyclohexanediol diglycidyl ether, neopentyl glycol diglycidyl ether and polyether polyol diglycidyl ether.
5. A modified liquid nitrile rubber according to claim 1, characterized in that: the modified liquid nitrile rubber is liquid nitrile rubber containing glycidyl ether groups.
6. The method for preparing the modified liquid nitrile rubber according to claim 1, wherein the method comprises the following steps: adding a diglycidyl ether compound and an antioxidant into a reaction kettle, stirring, heating to 90-110 ℃, taking 100 parts of carboxyl-terminated liquid nitrile rubber, adding the carboxyl-terminated liquid nitrile rubber into the reaction kettle for 1-3 times, wherein the time interval between the adding of the carboxyl-terminated liquid nitrile rubber is 5-15 min, and when the adding of the carboxyl-terminated liquid nitrile rubber is completed, controlling the temperature to 100-160 ℃, and carrying out heat preservation reaction for 0.5-2 h to obtain the modified liquid nitrile rubber.
7. Use of a modified liquid nitrile rubber as claimed in claim 1, characterized in that: the modified liquid nitrile rubber is used as a toughening agent for manufacturing epoxy resin adhesives and casting resins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310134752.6A CN116041785A (en) | 2023-02-20 | 2023-02-20 | Modified liquid nitrile rubber and preparation method and application thereof |
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| CN202310134752.6A CN116041785A (en) | 2023-02-20 | 2023-02-20 | Modified liquid nitrile rubber and preparation method and application thereof |
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| CN116041785A true CN116041785A (en) | 2023-05-02 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117603474A (en) * | 2023-12-20 | 2024-02-27 | 武汉中科先进材料科技有限公司 | Fiber-reinforced unsaturated polyester resin composite material for photovoltaic bracket and preparation method thereof |
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2023
- 2023-02-20 CN CN202310134752.6A patent/CN116041785A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117603474A (en) * | 2023-12-20 | 2024-02-27 | 武汉中科先进材料科技有限公司 | Fiber-reinforced unsaturated polyester resin composite material for photovoltaic bracket and preparation method thereof |
| CN117603474B (en) * | 2023-12-20 | 2024-05-31 | 武汉中科先进材料科技有限公司 | Fiber-reinforced unsaturated polyester resin composite material for photovoltaic bracket and preparation method thereof |
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