CN114591506A - Modified diene rubber and preparation method thereof - Google Patents
Modified diene rubber and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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Abstract
The invention relates to a modified diene rubber and a preparation method thereof, wherein the method comprises the following steps: (1) in the presence of a first initiator, carrying out a first contact reaction on a diene rubber solution and a polar reagent to obtain a diene rubber with functionalized side groups; and carrying out a second contact reaction on the polar monomer and the chain transfer agent in the presence of a first organic solvent and a second initiator to obtain a polar polymer; (2) and carrying out third contact reaction on the side group functionalized diene rubber and the polar polymer in the presence of a second organic solvent, a dehydrating agent and a catalyst. The method provided by the invention has mild reaction conditions, can be implemented at room temperature, has few side reactions, realizes effective regulation and control of diene rubber modification, can graft different polar side chains on butadiene rubber, and has a grafting rate as high as 62%.
Description
Technical Field
The invention relates to the technical field of rubber, in particular to modified diene rubber and a preparation method thereof.
Background
The introduction of polar functional groups or polar graft chains into elastomer macromolecules can solve many special problems, such as the improvement of cold resistance, heat resistance and solvent solubility resistance of rubber, the improvement of fatigue resistance, ozone resistance and weather resistance, and more importantly, the improvement of adhesion and bonding properties with reinforcing materials. Chemical graft modification is one of important modification methods for diene rubbers or elastomers.
The properties of rubber graft copolymers are closely related to the chemical composition, length and graft site density of the branches. It is common in the art to use free radical and other initiators (or catalysts) to initiate the monomer or modifier in a rubber blend containing a graft modifier to graft the modifier to the rubber. In the graft polymerization using a radical initiator, a part of the polar chains can be attached to the rubber macromolecule main chain, i.e., chemical bonds are formed with the rubber macromolecule, and a certain amount of the polar chains are mixed in the copolymer in the form of a homopolymer, i.e., the grafting efficiency is often not high. In addition, the traditional free radical polymerization method is difficult to accurately control the length of the grafted chain, and side reactions such as crosslinking, chain breakage and the like can be generated in the grafting polymerization process.
The prior art (synthetic rubber industry, 1997-03-15, 20(2):117) reports a method for preparing graft copolymers of chloroprene rubber and ethylene propylene diene rubber by an atom transfer radical polymerization method, wherein the length of a graft chain can be controlled by the atom transfer radical polymerization, but a metal catalyst is used in the atom transfer radical polymerization, the reaction temperature is higher, and the high temperature is between 90 and 130 ℃, so that the maintenance of the rubber structure and the performance is not favorable.
In addition, in the prior art (Polymer. adv. Technol.2004; 15:606-611), a styrene-butadiene rubber main chain is grafted with a stable free radical containing nitrogen and oxygen, a polystyrene branch chain is grafted by a controllable polymerization technology, the route design is very complex, and the stable free radical containing nitrogen and oxygen can only regulate and control the polymerization of styrene monomers and cannot be used for the polymerization of polar monomers such as acrylic ester, methacrylic ester and the like. In addition, the temperature of nitroxide-stable free radical polymerization is high, above 100 ℃, which is also disadvantageous for the modification of diene rubbers.
In summary, the rubber grafting in the prior art has the following disadvantages: (1) the grafting rate of modification is low, the length of a grafted chain is difficult to accurately control, and side reactions such as crosslinking and chain scission can be generated in the grafting polymerization process; (2) the temperature of the controlled polymerization, which is relatively high and generally between 90 ℃ and 130 ℃, is detrimental to the structure and properties of the rubber.
Disclosure of Invention
The invention aims to overcome the defects of high temperature and low grafting rate of rubber graft modification in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a method for modifying a diene rubber, comprising the steps of:
(1) in the presence of a first initiator, carrying out a first contact reaction on a diene rubber solution and a polar reagent at 40-80 ℃ to obtain a diene rubber with functionalized side groups; and
carrying out a second contact reaction on the polar monomer and the chain transfer agent in the presence of a first organic solvent and a second initiator to obtain a polar polymer;
(2) performing a third contact reaction on the side group functionalized diene rubber and the polar polymer in the presence of a second organic solvent, a dehydrating agent and a catalyst;
wherein the polar reagent is at least one selected from 1-thioglycerol, mercaptopropionic acid, thioglycolic acid, mercaptooxalic acid, 1-mercapto-2-propanol, 3-mercapto-1-propanol and 2, 3-dimercapto-1-propanol.
The second aspect of the present invention provides a modified diene rubber prepared according to the method.
Through the technical scheme, the invention at least has the following technical effects:
firstly, introducing polar groups to a main chain of diene rubber to obtain rubber macromolecules with functionalized side groups, and preparing a polar polymer with functional groups at the tail end by adopting controllable polymerization; the end group of the polar polymer reacts with the rubber macromolecule with functionalized lateral group through high-efficiency catalytic reaction, and the polar branched chain is grafted to the nonpolar rubber macromolecule, so that the modification of the rubber is realized.
The method provided by the invention has mild reaction conditions, can be implemented at room temperature, has few side reactions, realizes effective regulation and control of diene rubber modification, can graft different polar side chains on butadiene rubber, and has a grafting rate as high as 62%.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a method for modifying a diene rubber, comprising the steps of:
(1) in the presence of a first initiator, carrying out a first contact reaction on a diene rubber solution and a polar reagent at 40-80 ℃ to obtain a diene rubber with functionalized side groups;
carrying out a second contact reaction on the polar monomer and the chain transfer agent in the presence of a first organic solvent and a second initiator to obtain a polar polymer;
(2) performing a third contact reaction on the side group functionalized diene rubber and the polar polymer in the presence of a second organic solvent, a dehydrating agent and a catalyst;
wherein the polar reagent is at least one selected from 1-thioglycerol, mercaptopropionic acid, thioglycolic acid, mercaptooxalic acid, 1-mercapto-2-propanol, 3-mercapto-1-propanol and 2, 3-dimercapto-1-propanol.
Preferably, in step (1), the reaction conditions of the first contact reaction at least satisfy: the temperature is 50-70 ℃ and the time is 2-8 h.
According to the invention, firstly, a diene rubber solution reacts with a polar reagent, and a polar group (such as carboxyl, hydroxyl and the like) is introduced to a main chain of diene rubber to obtain a rubber macromolecule with a functionalized side group, so that the rubber macromolecule can be activated, and the reaction activity of the rubber macromolecule is improved, thereby reducing the reaction condition of subsequent grafting reaction, avoiding the generation of homopolymer, and improving the grafting efficiency; the quantity of active sites in the rubber macromolecules can be efficiently and accurately controlled, and the main microstructure of the rubber macromolecules is ensured not to be changed; in addition, the reaction conditions are mild, the reaction can be carried out at room temperature, and the structure and the performance of the rubber are not damaged.
In the present invention, the diene rubber and the polar agent are capable of reacting with the initiator to introduce a polar group (carboxyl group or hydroxyl group) into the main chain of the diene rubber, thereby increasing the activity of the diene rubber, and in order to effectively control the number of active sites in the diene rubber, it is preferable that in step (1), the diene rubber, the polar agent and the first initiator are used in a molar ratio of 1 (0.2-1.72) to (0.03-0.08), for example, 1:0.2:0.03, 1:0.5:0.05, 1:0.8:0.05, 1:1.2:0.08, 1:1.5:0.08 or any value therebetween, more preferably 1 (0.5-1) to (0.04-0.06), based on the carbon-carbon double bond contained therein.
In the present invention, the polar graft chain can be obtained by reacting a polar monomer with a chain transfer agent, and in order to control the length of the polar graft chain, it is preferable that in step (1), the reaction conditions of the second contact reaction at least satisfy: the temperature is 50-80 ℃, for example, 50 ℃, 60 ℃, 75 ℃, 80 ℃ or any value between the above values, more preferably 55-75 ℃; the time is 2 to 10 hours, for example 2 hours, 3 hours, 5 hours, 8 hours, 10 hours or any value between the above values, more preferably 3 to 6 hours.
In the present invention, in order to further control the length of the polar graft chain, it is preferable that the polar monomer, the chain transfer agent and the second initiator are used in the step (1) at a molar ratio of (10 to 100):1, (0.2 to 0.5), for example, 10:1:0.2, 20:1:0.3, 50:1:0.3, 80:1:0.4, 100:1:0.5 or any value therebetween, and more preferably (20 to 80):1, (0.2 to 0.5).
In the present invention, by subjecting the side group-functionalized diene-based rubber to the third contact reaction with the polar polymer, a polar branch can be introduced into the main chain of the diene-based rubber. Preferably, in step (2), the reaction conditions of the third contact reaction at least satisfy: the temperature is 20-50 deg.C, such as 20 deg.C, 25 deg.C, 30 deg.C or any value therebetween, and the time is 3-6h, such as 3h, 4h, 5h, 6h or any value therebetween.
In order to further improve the performance of the modified diene rubber, the weight ratio of the pendant-functionalized diene rubber to the polar polymer in step (2) is preferably 1 (0.1-2), for example, 1:0.1, 1:0.3, 1:0.5, 1:1, 1:1.5, 1:2 or any value therebetween, preferably 1 (0.3-1).
In order to further improve the properties of the modified diene rubber, the amount of the catalyst to be used in the step (2) is preferably 10 to 30:100 by weight, for example, 10:100, 15:100, 20:100, 25:100, 30:100 or any value therebetween.
In the present invention, in order to improve the modification efficiency of the diene-based rubber, it is preferable that in the step (1), the concentration of the diene-based rubber in the diene-based rubber solution is 4 wt% to 20 wt%, and for example, may be 4 wt%, 8 wt%, 12 wt%, 15 wt%, 20 wt%, or any value therebetween; preferably 6 wt% to 10 wt%.
Preferably, the solvent in the diene rubber solution is n-hexane and/or cyclohexane, and is preferably a mixed solvent of n-hexane and cyclohexane. More preferably, the content weight ratio of the n-hexane and the cyclohexane in the mixed solvent of the n-hexane and the cyclohexane is 1 (0.5-1.5), for example, 1:0.5, 1:0.8, 1:1, 1:1.5 or any value therebetween, and more preferably 1 (0.8-1.2).
In the present invention, in a preferred embodiment of the present invention, in the step (1), the diene-based rubber in the diene-based rubber solution is at least one selected from the group consisting of butadiene rubber, isoprene rubber, ethylene-propylene-diene rubber, styrene-butadiene rubber and nitrile-butadiene rubber.
In the present invention, in order to regulate the activity of the diene-based rubber, preferably, in step (1), the first initiator is at least one selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, and dibenzoyl peroxide.
In the present invention, in order to further optimize the performance of the polar polymer, preferably, in step (1), the polar monomer is selected from at least one of methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, N-dimethylacrylamide and hydroxyethyl methacrylate, more preferably one of N, N-dimethylacrylamide, methyl methacrylate and ethyl acrylate.
In the present invention, preferably, the first organic solvent is at least one selected from the group consisting of ethanol, methanol, tetrahydrofuran, toluene, and anisole. More preferably, the second initiator is azobisisobutyronitrile and/or azobisisoheptonitrile.
In the present invention, preferably, the chain transfer agent is selected from at least one of S-acetic acid-S '- (α, α' -dimethyl- α "-acetic acid-2-hydroxyethyl) trithiocarbonate, S-propionic acid-S '- (α -methyl- α' -acetic acid) -trithiocarbonate, 4-cyano-4- (((ethylthio) thiocarbonyl) thio) pentanoic acid, S '-bis (α, α' -methyl- α" -acetic acid) trithiocarbonate, and S-1-dodecyl-S '(α - α' -dimethyl- α "acetic acid) -trithiocarbonate.
In the invention, in order to further improve the performance of the modified diene rubber, under the preferable conditions, in the step (2), the dehydrating agent is N, N-dicyclohexylcarbodiimide; more preferably, the catalyst is 4-dimethylaminopyridine; more preferably, the second organic solvent is selected from at least one of dichloromethane, tetrahydrofuran, n-hexane, and cyclohexane.
As described above, the second aspect of the present invention also provides a modified diene rubber produced by the method.
The present invention is described in detail below by way of examples.
Chain transfer agent: S-1-dodecyl-S ' (α - α ' -dimethyl- α ' acetic acid) -trithiocarbonate (hereinafter chain transfer agent-1) synthesized according to the reference (Macromolecules,2002,35, 6754-6756.); 4-cyano-4- (((ethylthio) thiocarbonyl) thio) pentanoic acid (hereinafter chain transfer agent-2), available from Allantin reagent Inc.; s-acetic acid-S '- (α, α' -dimethyl- α "-acetic acid-2-hydroxyethyl) trithiocarbonate (hereinafter chain transfer agent-3), available from Inokay reagents;
the butadiene rubber is purchased from Yanshan petrochemical company and has the product model number of LCBR 130.
In the following examples, the diene-based rubber solution was a n-hexane/cyclohexane solution of butadiene rubber in which the mass ratio of n-hexane to cyclohexane was 1:1 and the mass fraction of butadiene rubber was 8 wt%.
In the following examples, the room temperature is 25. + -. 1 ℃.
Example 1
(1) Adding 15g of butadiene rubber solution, 0.3g of Azobisisobutyronitrile (AIBN), 3g of 1-thioglycerol and 15g of tetrahydrofuran into a 100mL round-bottom flask, reacting at 60 ℃ for 4 hours, adding the product into ethanol for precipitation, and drying to obtain butadiene rubber BR-1 containing hydroxyl;
adding 3g of N, N-dimethylacrylamide (NNDMA), 0.1g of Azobisisobutyronitrile (AIBN), 0.7g of chain transfer agent-1 and 8.62g of absolute ethyl alcohol into a reaction bottle, introducing argon for 10min, pumping for 7 times, removing oxygen in a system, then placing the system in a constant-temperature oil bath kettle at 70 ℃ for reaction for 5 hours to obtain a mixed product; then precipitating the mixed product in ether, and drying the mixed product under the vacuum condition at room temperature to obtain carboxyl-containing poly N, N-dimethylacrylamide NNDMA-1;
(2) in a 50mL flask, 1g of BR-1 was dissolved in 30g of Dichloromethane (DCM), and then 0.3g of NNDMA-1, 0.4g of N, N-Dicyclohexylcarbodiimide (DCC) and 0.09g of 4-dimethylaminopyridine were added to the flask, and the reaction was stopped at room temperature for 4 hours, and the reaction product was precipitated in ethanol to obtain a side chain-grafted polar monomer-modified butadiene rubber NNDMA-BR-1.
Example 2
(1) Adding 15g of butadiene rubber solution, 0.3g of Azobisisobutyronitrile (AIBN), 3g of 1-thioglycerol and 15g of tetrahydrofuran into a 100mL round-bottom flask, reacting at 60 ℃ for 4 hours, adding the product into ethanol for precipitation, and drying to obtain butadiene rubber BR-1 containing hydroxyl;
adding 3g of N, N-dimethylacrylamide (NNDMA), 0.1g of Azobisisobutyronitrile (AIBN), 0.7g of chain transfer agent-1 and 8.62g of absolute ethyl alcohol into a reaction bottle, introducing argon for bubbling for 10min, pumping for 7 times, removing oxygen in the system, placing the system in a constant-temperature oil bath kettle at 70 ℃, and reacting for 5 hours to obtain a mixed product; then precipitating the mixed product in ether, and drying the mixed product under the vacuum condition at room temperature to obtain carboxyl-containing poly N, N-dimethylacrylamide NNDMA-1;
(2) in a 50mL flask, 1g of BR-1 was dissolved in 30g of Dichloromethane (DCM), and then 1g of NNDMA-1, 0.4g of N, N-Dicyclohexylcarbodiimide (DCC), 0.15g of 4-dimethylaminopyridine and the reaction were added to the flask, and the reaction was stopped at room temperature for 4 hours, and the reaction product was precipitated in ethanol to obtain a side chain-grafted polar monomer-modified butadiene rubber NNDMA-BR-2.
Example 3
(1) Adding 15g of butadiene rubber solution, 0.3g of Azobisisobutyronitrile (AIBN), 3g of 1-thioglycerol and 15g of tetrahydrofuran into a 100mL round-bottom flask, reacting at 60 ℃ for 2 hours, adding the product into ethanol for precipitation, and drying to obtain butadiene rubber BR-2 containing hydroxyl;
adding 3g of Methyl Methacrylate (MMA), 0.1g of Azobisisobutyronitrile (AIBN), 0.7g of chain transfer agent-2 and 8.62g of tetrahydrofuran into a reaction bottle, introducing argon for bubbling for 10min, pumping for 7 times, removing oxygen in the system, placing the system in a constant-temperature oil bath kettle at 70 ℃, reacting for 6h to obtain a mixed product, then precipitating the mixed product in n-hexane, and drying at room temperature under vacuum condition to obtain the carboxyl-containing polymethyl methacrylate PMMA-1.
(2) In a 50mL flask, 1g of BR-2 was dissolved in 30g of Dichloromethane (DCM), and then 1g of PMMA-1, 0.4g of N, N-Dicyclohexylcarbodiimide (DCC), 0.3g of 4-dimethylaminopyridine and the reaction were added to the flask, and the reaction was stopped at room temperature for 4 hours, and the reaction product was precipitated in ethanol to obtain a modified butadiene rubber PMMA-BR-2 having a side chain grafted with a polar monomer.
Example 4
(1) Adding 15g of butadiene rubber solution, 0.3g of Azobisisobutyronitrile (AIBN), 4g of mercaptopropionic acid and 15g of tetrahydrofuran into a 100mL round-bottom flask, reacting at 60 ℃ for 2 hours, adding the product into ethanol for precipitation, and drying to obtain butadiene rubber BR-3 containing carboxyl;
adding 3g of Ethyl Acrylate (EA), 0.1g of Azobisisobutyronitrile (AIBN), 0.6g of chain transfer agent-1 and 7.5g of tetrahydrofuran into a reaction bottle, introducing argon for bubbling for 10min, pumping for 7 times, removing oxygen in a system, placing the system in a constant-temperature oil bath kettle at 70 ℃, reacting for 6h to obtain a mixed product, then precipitating the mixed product in n-hexane, and drying the mixed product under the vacuum condition at room temperature to obtain the hydroxyl-containing polyethylacrylate EA-1;
(2) in a 50mL flask, 1g of BR-3 was dissolved in 30g of Dichloromethane (DCM), and then 0.6g of EA-1, 0.4g of N, N-Dicyclohexylcarbodiimide (DCC) and 0.2g of 4-dimethylaminopyridine were added to the flask, and the reaction was stopped at room temperature for 4 hours, and the reaction product was precipitated in ethanol to obtain a modified butadiene rubber EA-BR-3 having a side chain grafted with a polar monomer.
Example 5
The process of example 1 was followed except that: in the step of(1) The amount of the carbon-carbon double bond in the diene rubber in terms of the carbon-carbon double bond contained therein, the mercapto group in the polar agent in terms of the mercapto group contained therein and the first initiator are used in a molar ratio (R)1) Is 1: 0.3: 0.03.
example 6
The process of example 1 was followed except that: in the step (1), the amount of the carbon-carbon double bond in the diene rubber in terms of the carbon-carbon double bond contained therein, the mercapto group in the polar agent in terms of the mercapto group contained therein and the first initiator are used in a molar ratio (R)1) Is 1: 1: 0.08.
example 7
The process of example 4 was followed except that: in the step (1), the polar monomer, the chain transfer agent and the second initiator are used in a molar ratio (R)2) Is 10:1: 0.2.
example 8
The process of example 4 was followed except that: in the step (1), the polar monomer, the chain transfer agent and the second initiator are used in a molar ratio (R)2) Is 100:1: 0.2.
example 9
The process of example 1 was followed except that: in the step (1), the reaction temperature of the rubber solution is 40 ℃, and the reaction lasts for 8 hours; in the step (2), the reaction temperature is 50 ℃, the reaction time is 10h, and the specific steps are as follows:
(1) adding 15g of butadiene rubber solution, 0.3g of Azobisisobutyronitrile (AIBN), 3g of 1-thioglycerol and 15g of tetrahydrofuran into a 100mL round-bottom flask, reacting at 40 ℃ for 8 hours, adding the product into ethanol for precipitation, and drying to obtain butadiene rubber BR-8 containing hydroxyl;
adding 3g of N, N-dimethylacrylamide (NNDMA), 0.1g of Azobisisobutyronitrile (AIBN), 0.7g of chain transfer agent-1 and 8.62g of absolute ethyl alcohol into a reaction bottle, introducing argon for 10min, pumping for 7 times, removing oxygen in a system, then placing the system in a constant-temperature oil bath kettle at 70 ℃ for reaction for 5 hours to obtain a mixed product; then precipitating the mixed product in ether, and drying the mixed product under the vacuum condition at room temperature to obtain carboxyl-containing poly N, N-dimethylacrylamide NNDMA-1;
(2) in a 50mL flask, 1g of BR-8 was dissolved in 30g of Dichloromethane (DCM), and then 0.3g of NNDMA-1, 0.4g of N, N-Dicyclohexylcarbodiimide (DCC), 0.09g of 4-dimethylaminopyridine were added to the flask, reacted at 50 ℃ for 10 hours, and the reaction product was precipitated in ethanol to obtain a side chain-grafted polar monomer-modified butadiene rubber NNDMA-BR-8.
Comparative example 1
The process of example 1 was followed except that: glycerol was used instead of 1-thioglycerol.
Comparative example 2
The process of example 1 was followed except that: in the step (1), the reaction conditions of the first contact reaction are as follows: the temperature is 100 ℃ and the time is 10 h.
Comparative example 3
The process of example 1 was followed except that: the diene-based rubber is not side-group functionalized, i.e., does not comprise a first contact reaction.
Comparative example 4
The process of example 1 was followed except that: in the step (1), the reaction temperature of the rubber solution is 80 ℃, and the reaction lasts for 2 hours; in the step (2), the reaction temperature is 80 ℃, the reaction time is 2h, and the specific steps are as follows:
(1) adding 15g of butadiene rubber solution, 0.3g of Azobisisobutyronitrile (AIBN), 3g of 1-thioglycerol and 15g of tetrahydrofuran into a 100mL round-bottom flask, reacting at 80 ℃ for 2 hours, adding the product into ethanol for precipitation, and drying to obtain butadiene rubber BR-11 containing hydroxyl;
adding 3g of N, N-dimethylacrylamide (NNDMA), 0.1g of Azobisisobutyronitrile (AIBN), 0.7g of chain transfer agent-1 and 8.62g of absolute ethyl alcohol into a reaction bottle, introducing argon for 10min, pumping for 7 times, removing oxygen in a system, then placing the system in a constant-temperature oil bath kettle at 70 ℃ for reaction for 5 hours to obtain a mixed product; then precipitating the mixed product in ether, and drying the mixed product under the vacuum condition at room temperature to obtain carboxyl-containing poly N, N-dimethylacrylamide NNDMA-1;
(2) in a 50mL flask, 1g of BR-11 was dissolved in 30g of Dichloromethane (DCM), and then 0.3g of NNDMA-1, 0.4g of N, N-Dicyclohexylcarbodiimide (DCC), 0.09g of 4-dimethylaminopyridine were added to the flask, reacted at 80 ℃ for 2 hours, and the reaction product was precipitated in ethanol to obtain a modified butadiene rubber NNDMA-BR-11 having a side chain grafted with a polar monomer.
The charge amounts of the respective materials and the reaction conditions in examples 1 to 9 and comparative examples 1 to 4 are shown in table 1;
the properties of the modified diene rubbers obtained in examples 1 to 9 and comparative examples 1 to 4 are shown in Table 2.
TABLE 1
TABLE 1 continuation
Wherein R is1The amount of the carbon-carbon double bond in the diene rubber calculated by the carbon-carbon double bond contained in the diene rubber, the mercapto group in the polar agent calculated by the mercapto group contained in the diene rubber and the first initiator are used in a molar ratio in the step (1);
R2the polar monomer, the chain transfer agent and the second initiator are used in a molar ratio in the step (1).
Test example
1. And (3) testing the grafting ratio: performing hydrogen spectrum test and calculation by a nuclear magnetic resonance spectrometer, dissolving the obtained copolymer in n-hexane/tetrahydrofuran solution-diethyl ether, precipitating, refining for three times, and dissolving in deuterated chloroform (CDCl)3) The test results are shown in table 2.
2. Contact angle test: and (3) measuring by using a water contact angle measuring instrument, pressing the sample into a film, controlling the volume of water drops to be 2uL, testing three different positions of each sample, and taking the average value of the tests, wherein the test results are shown in table 2.
TABLE 2
| Percent of grafting% | Contact Angle/° | |
| Example 1 | 52 | 8 |
| Example 2 | 60 | 6 |
| Example 3 | 62 | 30 |
| Example 4 | 57 | 45 |
| Example 5 | 25 | 32 |
| Example 6 | 50 | 9 |
| Example 7 | 61 | 42 |
| Example 8 | 62 | 41 |
| Example 9 | 55 | 8 |
| Comparative example 1 | 0.2 | 90 |
| Comparative example 2 | Cross-linking | - |
| Comparative example 3 | 0 | 92 |
| Comparative example 4 | 48 | 20 |
As can be seen from table 2: by the method provided by the embodiment of the invention, different polar side chains can be grafted on the butadiene rubber, and the grafting rate is as high as 62%; as the grafting rate increases, the contact angle with water gradually decreases.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A method for modifying diene rubber is characterized by comprising the following steps:
(1) in the presence of a first initiator, carrying out a first contact reaction on a diene rubber solution and a polar reagent at 40-80 ℃ to obtain a diene rubber with functionalized side groups; and
carrying out a second contact reaction on the polar monomer and the chain transfer agent in the presence of a first organic solvent and a second initiator to obtain a polar polymer;
(2) performing a third contact reaction on the side group functionalized diene rubber and the polar polymer in the presence of a second organic solvent, a dehydrating agent and a catalyst;
wherein the polar reagent is at least one selected from 1-thioglycerol, mercaptopropionic acid, thioglycolic acid, mercaptooxalic acid, 1-mercapto-2-propanol, 3-mercapto-1-propanol and 2, 3-dimercapto-1-propanol.
2. The modification method according to claim 1, wherein in step (1), the reaction conditions of the first contact reaction at least satisfy: the temperature is 50-70 ℃ and the time is 2-8 h.
3. A modification method as defined in claim 1 or 2, wherein in the step (1), the diene-based rubber, the polar agent and the first initiator are used in a molar ratio of 1 (0.2-1.72) to (0.03-0.08) in terms of the carbon-carbon double bond contained therein.
4. The modification method according to any one of claims 1 to 3, wherein in step (1), the reaction conditions of the second contact reaction at least satisfy: the temperature is 50-80 ℃ and the time is 2-10 h.
5. The modification method according to any one of claims 1 to 4, wherein in step (1), the polar monomer, the chain transfer agent and the second initiator are used in a molar ratio of (10-100) to 1 (0.2-0.5).
6. The modification method according to any one of claims 1 to 5, wherein in step (2), the reaction conditions of the third contact reaction at least satisfy: the temperature is 20-50 ℃ and the time is 3-6 h.
7. The modification method according to any one of claims 1 to 6, wherein in the step (2), the weight ratio of the amount of the pendant-functionalized diene-based rubber to the amount of the polar polymer is 1 (0.1 to 2), preferably 1 (0.3 to 1);
preferably, in step (2), the weight ratio of the catalyst to the polar polymer is 10-30: 100.
8. The modification method according to any one of claims 1 to 7, wherein in step (1), the concentration of the diene rubber in the diene rubber solution is 4% by weight to 20% by weight; preferably 6 wt% to 10 wt%;
preferably, the solvent in the diene rubber solution is n-hexane and/or cyclohexane, preferably a mixed solvent of n-hexane and cyclohexane;
preferably, the content weight ratio of the n-hexane and the cyclohexane in the mixed solvent formed by the n-hexane and the cyclohexane is 1 (0.5-1.5), preferably 1 (0.8-1.2).
9. The modification method according to any one of claims 1 to 8, wherein in step (1), the diene-based rubber in the diene-based rubber solution is at least one selected from the group consisting of butadiene rubber, isoprene rubber, ethylene propylene diene rubber, styrene butadiene rubber and nitrile butadiene rubber.
10. The modification method according to any one of claims 1 to 9, wherein, in step (1), the first initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptonitrile, and dibenzoyl peroxide.
11. The modification method according to any one of claims 1 to 10, wherein, in the step (1), the polar monomer is selected from at least one of methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, N-dimethylacrylamide and hydroxyethyl methacrylate;
preferably, the first organic solvent is selected from at least one of ethanol, methanol, tetrahydrofuran, toluene, and anisole; and/or
Preferably, the second initiator is azobisisobutyronitrile and/or azobisisoheptonitrile;
preferably, the chain transfer agent is selected from at least one of S-acetic acid-S '- (α, α' -dimethyl- α "-acetic acid-2-hydroxyethyl) trithiocarbonate, S-propionic acid-S '- (α -methyl- α' -acetic acid) -trithiocarbonate, 4-cyano-4- (((ethylthio) thiocarbonyl) thio) pentanoic acid, S '-bis (α, α' -methyl- α" -acetic acid) trithiocarbonate, and S-1-dodecyl-S '(α - α' -dimethyl- α "acetic acid) -trithiocarbonate.
12. The modification method according to any one of claims 1 to 11, wherein, in step (2), the dehydrating agent is N, N-dicyclohexylcarbodiimide;
preferably, the catalyst is 4-dimethylaminopyridine;
preferably, the second organic solvent is selected from at least one of dichloromethane, tetrahydrofuran, n-hexane, and cyclohexane.
13. A modified diene rubber produced by the process of any one of claims 1 to 12.
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| CN115710413A (en) * | 2023-01-09 | 2023-02-24 | 广东品凡派塑胶实业有限公司 | Chemical-resistant injection-molding-grade super-tough PET make-up package material and dynamic variable-mold-temperature injection molding method thereof |
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