CN116023591B - Maleic monoester salt modified natural rubber composite material and preparation method thereof - Google Patents
Maleic monoester salt modified natural rubber composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a maleic monoester salt modified natural rubber composite material and a preparation method thereof, belonging to the field of chemical modification of natural polymers. The modified natural rubber comprises the following preparation raw materials in parts by mass: 100 parts of natural latex based on dry rubber; 0.5 to 25 parts of maleic monoester salt; 0-20 parts of toenail latex based on dry adhesive; 1.0 to 6.0 portions of stabilizer; 0.1-5 parts of initiator; 0.01 to 0.5 part of activating agent; 100-200 parts of water. The maleic acid monoester salt maintains the structure of unsaturated carboxylate and simultaneously introduces the structure of unsaturated carboxylate, so that the compatibility with natural rubber is improved. When the smallpox latex is used as the interface modifier, the compatibility of the maleic monoester salt and the natural rubber can be further increased. After modification, the heat resistance, ageing resistance and mechanical properties of the natural rubber are obviously improved.
Description
Technical Field
The invention belongs to the technical field of natural polymer modification, and particularly relates to a maleic monoester salt modified natural rubber composite material and a preparation method thereof.
Background
Reinforcement of natural rubber has been an important research topic. Carbon black and white carbon black reinforcement have been dominant. However, carbon black and white carbon black have been difficult to obtain higher performance rubber products, so the search for new reinforcing agents with high reinforcing ability has been the focus of research in the rubber industry. Research has shown that the formation of interpenetrating network reinforced modified rubbers by "in situ polymerization" is an important direction to solve this problem. By "in situ polymerization" reinforcement is meant the "formation" of a reinforcing agent in a rubber, typically by mixing into the rubber some monomer species having reactive functional groups that are compatible with the base rubber, and then "in situ" polymerizing it into finely dispersed particles by appropriate conditions and forming a network structure in the rubber, thereby producing the reinforcement.
Unsaturated carboxylic acid metal salt reinforced rubber is a typical example of "in situ polymerization" reinforcement, and in the crosslinking process, the unsaturated carboxylic acid metal salt generates nanoparticles (poly unsaturated carboxylic acid metal salt) in situ in the rubber, thereby producing excellent reinforcing effect on the rubber, and having properties of low strain, high modulus, high elasticity and high elongation at the same time. However, the unsaturated carboxylic acid metal salt has poor compatibility with natural rubber, so that the unsaturated carboxylic acid metal salt reinforced rubber has poor ageing resistance and mechanical property.
Disclosure of Invention
The invention aims to provide a maleic monoester salt modified natural rubber composite material and a preparation method thereof.
The invention provides a maleic monoester salt modified natural rubber composite material, which comprises the following preparation raw materials in parts by mass:
preferably, the initiator comprises one or more of benzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile, sulfur, cumene hydroperoxide, potassium persulfate and N, N-methylenebisacrylamide.
Preferably, the activator comprises tetraethylenepentamine.
Preferably, the maleate monoester salt includes one of maleate monoester sodium salt, maleate monoester potassium salt, maleate monoester magnesium salt, maleate monoester calcium salt, maleate monoester zinc salt, maleate monoester iron salt and maleate monoester rare earth metal salt.
The invention also provides a preparation method of the maleic monoester salt modified natural rubber composite material, which comprises the following steps:
and mixing the preparation raw materials, and performing polymerization reaction to obtain the maleic monoester salt modified natural rubber composite material.
Preferably, the maleic monoester salt, the initiator and water are first mixed to obtain a first mixture; the first mixture is mixed with natural latex and smallpox latex for the second time to obtain a second mixture; and thirdly mixing the second mixture with the stabilizer and then mixing with the activator.
Preferably, the temperature of the third mixing is 60-80 ℃, and the third mixing comprises stirring and standing; the stirring time is 2h, and the parking time is 24h.
Preferably, the temperature of the polymerization reaction is 60-100 ℃ and the time is 2-24 h.
The invention provides a maleic monoester salt modified natural rubber composite material, which comprises the following preparation raw materials in parts by mass: 100 parts of natural latex based on dry rubber; 0.5 to 25 parts of maleic monoester salt; 0-20 parts of toenail latex based on dry adhesive; 1-6 parts of stabilizer; 0.1-5 parts of initiator; 0.01 to 0.5 part of activating agent; 100-200 parts of water. The maleic acid monoester salt maintains the structure of unsaturated carboxylate, and simultaneously introduces the structure of unsaturated carboxylate, so that the compatibility with natural rubber is improved, and the ageing resistance and mechanical property of the modified natural rubber are further improved; when the heavenly stems and earthly branches latex is added, the compatibility of the maleic monoester salt and the natural rubber can be further increased by taking the heavenly stems and earthly branches latex as an interface compatilizer, and the ageing resistance and the mechanical property of the maleic monoester salt modified natural rubber composite material can be further improved. The results of the examples show that the tensile strength of the maleic monoester salt modified natural rubber composite material is 35Mpa, the elongation at break is 632%, the heat-resistant temperature is improved by 110 ℃, and the phase separation phenomenon does not exist.
Detailed Description
The invention provides a maleic monoester salt modified natural rubber composite material, which comprises the following preparation raw materials:
the raw materials for preparing the maleic monoester salt modified natural rubber composite material comprise 100 parts of natural latex calculated by dry rubber. In the present invention, the natural latex preferably has a solid content of 60%.
The raw materials for preparing the maleic monoester salt modified natural rubber composite material comprise 0-20 parts by weight, preferably 5-15 parts by weight, and more preferably 8-12 parts by weight of the toenail latex based on dry rubber based on the mass parts of the natural latex based on dry rubber. In the present invention, the solid content of the toenail latex is preferably 25%. The tencel as the interfacial compatilizer can further improve the compatibility of the maleic monoester salt and the natural rubber, and the ageing resistance and the mechanical property of the maleic monoester salt modified natural rubber composite material.
The raw materials for preparing the maleic acid monoester salt modified natural rubber composite material comprise 1-6 parts of stabilizer, preferably 2-4 parts, and more preferably 2.5-3 parts, based on the mass parts of the natural latex based on dry rubber. In the present invention, the stabilizer preferably includes a nonionic surfactant and/or an ionic surfactant, and the nonionic surfactant preferably includes the nonionic surfactant peregal "O"; the ionic surfactant preferably comprises sodium dodecyl sulfonate.
The raw materials for preparing the maleic monoester salt modified natural rubber composite material comprise 0.1-5 parts of initiator, preferably 0.5-3 parts, and more preferably 0.5-2.5 parts by mass of natural latex based on dry rubber. In the present invention, the initiator preferably includes one or more of benzoyl peroxide, t-butyl hydroperoxide, azobisisobutyronitrile, sulfur, cumene hydroperoxide, potassium persulfate and N, N-methylenebisacrylamide. The initiator may initiate polymerization of the natural rubber with the maleate salt, the maleate monoester salt, and the maleate monoester salt.
The raw materials for preparing the maleic acid monoester salt modified natural rubber composite material comprise 0.01-0.5 part, preferably 0.05-0.4 part, more preferably 0.1-0.2 part of activating agent based on the mass parts of the natural latex based on dry rubber. In the present invention, the activator preferably comprises tetraethylenepentamine. The activator can increase the branching and crosslinking degree of the natural rubber.
The raw materials for preparing the maleic acid monoester salt modified natural rubber composite material comprise 100-200 parts of water, preferably 150-180 parts, based on the mass parts of the natural latex based on dry rubber.
The raw materials for preparing the maleic acid monoester salt modified natural rubber composite material comprise 0.5-25 parts of maleic acid monoester salt, preferably 5-15 parts, and more preferably 8-12 parts, based on the mass parts of the natural latex based on dry rubber. The maleate monoester salt preferably comprises one of sodium maleate monoester salt, potassium maleate monoester salt, magnesium maleate monoester salt, calcium maleate monoester salt, zinc maleate monoester salt, iron maleate monoester salt and rare earth maleate monoester metal salt.
In the present invention, the method for preparing the maleic acid monoester salt preferably comprises the steps of:
and (3) carrying out neutralization reaction on the maleic monoester, water and an alkaline compound of a corresponding metal element in the maleic monoester salt to obtain the maleic monoester salt.
In the present invention, the method for producing a maleic monoester preferably comprises: and (3) carrying out esterification reaction on maleic anhydride and monohydric alcohol to obtain the maleic monoester. In the present invention, the monohydric alcohol preferably includes one of methanol, ethanol, propanol and butanol. In the present invention, the molar ratio of maleic anhydride to monohydric alcohol is preferably 1:1. In the present invention, the temperature of the esterification reaction is preferably 50 to 65 ℃, more preferably 55 to 60 ℃; the time is preferably 2 to 8 hours, more preferably 4 to 6 hours. In the present invention, the esterification reaction is preferably carried out under reflux condensation conditions. The maleic acid contains 2 carboxyl groups, and in the esterification reaction process, one carboxyl group of the maleic acid is subjected to esterification reaction.
In the present invention, when the monohydric alcohol is ethanol, the reaction equation of the esterification reaction is:
after the esterification reaction, the present invention preferably subjects the esterification reaction product to reduced pressure distillation to obtain the maleic acid monoester. The reduced pressure distillation is not particularly limited in the present invention, and unreacted monohydric alcohol may be removed by a scheme well known to those skilled in the art. When the monohydric alcohol is methanol, the maleic monoester is monomethyl maleate; when the monohydric alcohol is ethanol, the maleic monoester is monoethyl maleate; when the monohydric alcohol is propanol, the maleic monoester is monopropyl maleate; when the monohydric alcohol is butanol, the maleic monoester is monobutyl maleate.
In the present invention, the basic compound preferably includes one of carbonate, metal oxide and metal hydroxide. In the present invention, the carbonate preferably includes one or more of gadolinium carbonate, samarium carbonate, cerium carbonate, zinc carbonate, cadmium carbonate, magnesium carbonate and calcium carbonate; the metal oxide preferably comprises zinc oxide.
In the present invention, the mass ratio of the basic compound to the maleic monoester is preferably 2:1. In the present invention, when the maleic monoester is monoethyl maleate and the basic compound is cadmium carbonate, the reaction equation of the neutralization reaction is:
the amount of the water used in the present invention is not particularly limited, and the maleic acid monoester may be dissolved. In the present invention, the temperature of the neutralization reaction is preferably an ordinary temperature. The carboxylic acid groups in the maleic acid monoester undergo a neutralization reaction with a basic compound.
After the neutralization reaction, the present invention preferably sequentially filters, concentrates, crystallizes and dries the obtained neutralization reaction product to obtain the maleic monoester salt. The present invention is not particularly limited as long as the solid residue in the resulting neutralized reaction product is removed by a scheme well known to those skilled in the art.
The structure of unsaturated carboxylic acid ester is introduced while the structure of unsaturated carboxylic acid salt is reserved, so that the compatibility with natural rubber and the ageing resistance and mechanical property of the maleic acid monoester modified natural rubber composite material are improved.
The invention also provides a preparation method of the maleic monoester salt modified natural rubber composite material, which comprises the following steps:
and mixing the preparation raw materials, and performing polymerization reaction to obtain the maleic monoester salt modified natural rubber composite material.
In the present invention, the mixing preferably includes: firstly mixing maleic monoester salt, an initiator and water to obtain a first mixture; the first mixture is mixed with natural latex and smallpox latex for the second time to obtain a second mixture; and thirdly mixing the second mixture with the stabilizer and then mixing with the activator. In the present invention, when the initiator is potassium persulfate, the first mixture is a solution; when the initiator comprises azobisisobutyronitrile, sulfur, benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide or N, N-methylenebisacrylamide, the first mixture is a suspension. In the present invention, the second mixing preferably drops the first mixture into natural latex. In the present invention, the temperature of the third mixing is preferably 60 to 80 ℃, and the third mixing preferably comprises stirring and standing; the stirring time is preferably 2 hours and the parking time is preferably 24 hours. The reaction can be carried out after the components are fully mixed and the activating agent is added for the purpose of uniformly mixing and then reacting, so that the mild reaction is facilitated. In the present invention, the polymerization reaction temperature is preferably 60 to 90 ℃, more preferably 70 to 80 ℃, and the time is preferably 2 to 24 hours, more preferably 10 to 20 hours, still more preferably 12 to 16 hours.
In the course of the polymerization reaction, unsaturated double bonds in the natural rubber and the maleate salt are polymerized under the action of an initiator, so that the maleate monoester salt is grafted onto the natural rubber. In the present invention, the grafting ratio of the maleic acid monoester salt is preferably 20 to 50wt%, more preferably 25 to 45wt%, and still more preferably 30 to 40wt%. In addition, in the course of the polymerization reaction, the polymerization reaction also occurs between the maleic acid monoester salts to produce polymaleic acid monoester salts.
After the polymerization reaction, the polymerization reaction product is preferably subjected to film laying and drying to obtain the maleic acid monoethyl ester gadolinium modified natural rubber composite material.
In order to further illustrate the present invention, the maleic acid monoester salt modified natural rubber composite material and the preparation method thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Maleic anhydride in a molar ratio of 1:1 dissolving in absolute ethanol, heating to 60 ℃, condensing and refluxing for reaction for 3 hours, and distilling under reduced pressure to remove unreacted ethanol to obtain monoethyl maleate;
dissolving 10 parts of maleic acid monoethyl ester in water, adding 20 parts of gadolinium carbonate, filtering to remove solid residues, concentrating filtrate, crystallizing and drying to obtain maleic acid monoethyl ester gadolinium salt;
15 parts of maleic acid monoethyl ester gadolinium salt and 1 part of potassium peroxodisulfate are dissolved in 100 parts of water, the obtained solution is added dropwise into a mixture containing 100 parts of concentrated natural latex with the solid content of 60% and 10 parts of tianjia latex with the solid content of 25%, 1 part of sodium dodecyl sulfate is added at the same time, the mixture is heated to 60 ℃, stirred for 2 hours while being heated, parked for 24 hours, 0.2 part of tetraethyl pentamine is added, and the mixture is reacted for 12 hours at the temperature of 60 ℃, spread with a film and dried to prepare the maleic acid monoethyl ester gadolinium modified natural rubber. Wherein the grafting rate of the maleic acid monoethyl ester gadolinium is 35 weight percent.
Compared with natural rubber material, the mechanical strength of the composite material is greatly improved, the tensile strength is improved from 26Mpa to 30Mpa, and the elongation at break is 581%. The thermal degradation resistance and the thermal oxidative aging resistance are also greatly improved, and the initial thermal degradation temperature is increased by 102 ℃.
Example 2
Maleic anhydride in a molar ratio of 1:1 dissolving in methanol, heating to 65 ℃ for condensation reflux reaction for 3 hours, and distilling under reduced pressure to remove unreacted methanol to obtain monomethyl maleate;
dissolving 10 parts of monomethyl maleate in water, adding into 20 parts of cerium carbonate, filtering to remove solid residues, concentrating filtrate, crystallizing, and drying to obtain monomethyl maleate cerium salt;
10 parts of monomethyl maleate cerium salt, 1 part of benzoyl peroxide and 100 parts of water are taken and mixed, the resulting suspension is added dropwise to a mixture containing 100 parts of concentrated natural latex with a solids content of 60% and 15 parts of tianjia latex with a solids content of 25%, 3.5 parts of peregal "O" are added simultaneously, heated to 80℃and stirred for 2 hours while heating, and then left for 24 hours. Adding 0.1 part of tetraethylenepentamine, reacting for 6 hours at the temperature of 80 ℃, paving a film, and drying to prepare the maleic acid monomethyl cerium modified natural rubber composite material. Wherein, the grafting rate of the monomethyl maleate cerium is 41wt%.
Compared with natural rubber materials, the mechanical strength of the obtained composite material is greatly improved, the tensile strength is improved to 33Mpa, and the elongation at break is 593%. The thermal degradation resistance and the thermal oxidative aging resistance are also greatly improved, and the initial thermal degradation temperature is increased by 80 ℃.
Example 3
Maleic anhydride in a molar ratio of 1:1 dissolving in n-butanol, heating to 85 ℃ for condensation reflux reaction for 3 hours, and distilling under reduced pressure to remove unreacted n-butanol to obtain maleic acid monobutyl ester;
dissolving 10 parts of monobutyl maleate in water, adding 20 parts of zinc carbonate, filtering to remove solid residues, concentrating filtrate, crystallizing and drying to obtain zinc monomethyl maleate salt;
mixing 5 parts of zinc monobutyl maleate, 1 part of tert-butyl hydroperoxide and 100 parts of water, dripping the obtained suspension into a mixture containing 100 parts of concentrated natural latex with the solid content of 60% and 10 parts of toenail latex with the solid content of 25%, simultaneously adding 3 parts of peregal O, heating to 60 ℃, stirring for 2 hours while heating, standing for 24 hours, then adding 0.3 part of tetraethylenepentamine, reacting for 24 hours at 60 ℃, laying a film, and drying to prepare the zinc monobutyl maleate modified natural rubber composite. Wherein the grafting rate of the zinc monobutyl maleate is 38 weight percent.
Compared with the natural rubber material, the mechanical strength of the composite material is greatly improved, the tensile strength is improved to 31Mpa, and the elongation at break is 632%. The thermal degradation resistance and the thermal oxidation aging resistance are also greatly improved, the initial thermal degradation temperature is improved by 105 ℃, and the thermal oxidation aging resistance is also greatly improved, in particular the thermal oxidation aging resistance of the maleic acid monobutyl ester rare earth salt/natural rubber composite material is more obviously improved.
Example 4
10 parts of monoethyl maleate of the example 1 is dissolved in water and added into 20 parts of cadmium carbonate, and after filtering to remove solid residues, filtrate is concentrated, crystallized and dried to obtain monoethyl maleate cadmium salt;
8 parts of maleic acid monoethyl ester cadmium salt and 0.5 part of azodiisobutyronitrile are taken and mixed with 100 parts of water, the obtained suspension is dripped into a mixture containing 100 parts of concentrated natural latex with the solid content of 60% and 10 parts of tianjia latex with the solid content of 25%, 3 parts of peregal O are added simultaneously, the mixture is heated to 60 ℃ and stirred for 2 hours while being heated, and the mixture is parked for 24 hours, 0.1 part of tetraethylenepentamine is added, and the mixture is reacted for 12 hours at the temperature of 80 ℃, paved with a film and dried to prepare the maleic acid monoethyl ester cadmium modified natural rubber composite material. Wherein the grafting rate of the monoethyl maleate cadmium is 40wt%.
Compared with natural rubber materials, the mechanical strength of the composite material is greatly improved, the tensile strength is 32.8Mpa, and the elongation at break is 612%. The thermal degradation resistance and the thermal oxidative aging resistance are also greatly improved, and the initial thermal degradation temperature is increased by 103 ℃.
Example 5
10 parts of monoethyl maleate of the example 1 is dissolved in water and added into 20 parts of magnesium carbonate, after filtering to remove solid residues, filtrate is concentrated, crystallized and dried to obtain monoethyl maleate magnesium salt;
mixing 12 parts of monoethyl maleate magnesium salt, 2 parts of sulfur and 100 parts of water, dripping the obtained suspension into 100 parts of a mixture containing 100 parts of concentrated natural latex with the solid content of 60% and 15 parts of tianjia latex, simultaneously adding 3 parts of peregal O, heating to 60 ℃, stirring for 2 hours while heating, standing for 24 hours, adding 0.3 part of tetraethyl pentamine, reacting for 12 hours at the temperature of 60 ℃, laying a film, and drying to prepare the monoethyl maleate magnesium modified natural rubber composite material. Wherein the grafting rate of the monoethyl magnesium maleate is 45 weight percent.
Compared with natural rubber materials, the mechanical strength of the composite material is greatly improved, the tensile strength is 35Mpa, and the elongation at break is 630%. The thermal degradation resistance and the thermal oxidative aging resistance are also greatly improved, and the initial thermal degradation temperature is increased by 110 ℃.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (5)
1. The maleic monoester salt modified natural rubber composite material is characterized by comprising the following preparation raw materials in parts by mass:
100 parts of natural latex based on dry rubber;
0.5-25 parts of maleic monoester salt;
0-20 parts of toenail latex based on dry gel;
1-6 parts of a stabilizer;
0.1-5 parts of an initiator;
0.01-0.5 parts of an activating agent;
100-200 parts of water;
in the maleic monoester salt modified natural rubber composite material, maleic monoester salt is grafted on natural rubber;
the initiator is sulfur; the maleic monoester salt is maleic monoester magnesium salt;
the activator is tetraethylenepentamine.
2. The method for preparing the maleic monoester salt modified natural rubber composite material as claimed in claim 1, comprising the following steps:
and mixing the preparation raw materials, and performing polymerization reaction to obtain the maleic monoester salt modified natural rubber composite material.
3. The method of preparing according to claim 2, wherein the mixing comprises: firstly mixing maleic monoester salt, an initiator and water to obtain a first mixture; the first mixture is mixed with natural latex and smallpox latex for the second time to obtain a second mixture; and thirdly mixing the second mixture with the stabilizer and then mixing with the activator.
4. The method according to claim 3, wherein the temperature of the third mixing is 60-80 ℃, and the third mixing comprises stirring and standing; the stirring time is 2h, and the parking time is 24h.
5. The method according to claim 2 or 3, wherein the polymerization reaction is carried out at a temperature of 60 to 100 ℃ for a time of 2 to 24 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018138631A (en) * | 2017-02-24 | 2018-09-06 | 日本ゼオン株式会社 | Method for producing modified natural rubber latex |
| JP2018138633A (en) * | 2017-02-24 | 2018-09-06 | 日本ゼオン株式会社 | Method for producing modified natural rubber latex |
| CN111032765A (en) * | 2017-08-25 | 2020-04-17 | 日本瑞翁株式会社 | Latex composition |
| CN113461990A (en) * | 2021-08-10 | 2021-10-01 | 中国热带农业科学院农产品加工研究所 | Natural rubber raw rubber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018138631A (en) * | 2017-02-24 | 2018-09-06 | 日本ゼオン株式会社 | Method for producing modified natural rubber latex |
| JP2018138633A (en) * | 2017-02-24 | 2018-09-06 | 日本ゼオン株式会社 | Method for producing modified natural rubber latex |
| CN111032765A (en) * | 2017-08-25 | 2020-04-17 | 日本瑞翁株式会社 | Latex composition |
| CN113461990A (en) * | 2021-08-10 | 2021-10-01 | 中国热带农业科学院农产品加工研究所 | Natural rubber raw rubber and preparation method thereof |
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