CN108530718B - Epoxidized natural rubber composite material and preparation method thereof - Google Patents
Epoxidized natural rubber composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides an epoxidized natural rubber composite material which is prepared from the following raw materials in parts by weight: 100 parts of emulsion epoxidized natural rubber, 0.1-30 parts of zeolite molecular sieve, 0.1-10 parts of rare earth oxide, 0.5-10 parts of ammonia water, 0.05-0.8 part of surfactant, 0.1-4 parts of coagulant and 0.2-12 parts of vulcanization processing aid. The epoxidized natural rubber composite material prepared by the invention has excellent aging resistance, low heat buildup property and good fatigue resistance, and can be applied to epoxidized natural rubber products such as medical latex products, soles, tires, rubber tubes and the like. The method has simple process, stable product quality and easy industrial production.
Description
Technical Field
The invention relates to the technical field of rubber materials, in particular to an epoxidized natural rubber composite material and a preparation method thereof.
Background
The epoxidized natural rubber is a novel polymer obtained by performing epoxidation modification on natural rubber, has excellent air tightness, oil resistance and adhesion, has good wet skid resistance and lower rolling resistance, and has wide application prospect in the application of high-performance green tires.
Although the epoxidized natural rubber overcomes the problem of natural rubber storage hardening, the epoxidized natural rubber has the defect of very poor aging resistance, a molecular chain of the epoxidized natural rubber contains a large number of unsaturated double bonds and epoxy groups, and chemical reaction is very easy to occur, and the epoxidized natural rubber is subjected to chemical change under the action of external factors such as heat, oxygen, light, mechanical force, radiation, chemical media, ozone in air and the like in the using process, so that the original chemical structure of the rubber is damaged, the rubber performance is deteriorated, the epoxidized natural rubber product is easy to age in the processing or using process, and the aging performance of the epoxidized natural rubber product is poorer than that of the natural rubber. Therefore, the epoxidized natural rubber products generally have the problems of short storage time, short service life, aging, stickiness and the like, and the application of the epoxidized natural rubber is limited to a great extent.
Disclosure of Invention
The invention aims to provide an anti-aging epoxidized natural rubber composite material, which improves the anti-aging performance of epoxidized natural rubber, prolongs the storage time of epoxidized natural rubber products and has short service life.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an epoxidized natural rubber composite material which is prepared from the following raw materials in parts by weight: 100 parts of emulsion epoxidized natural rubber, 0.1-30 parts of zeolite molecular sieve, 0.1-10 parts of rare earth oxide, 0.5-10 parts of ammonia water, 0.05-0.8 part of surfactant, 0.1-4 parts of coagulant and 0.2-12 parts of vulcanization processing aid.
Preferably, the epoxidation degree of the milky epoxidized natural rubber is 2-50.
Preferably, the zeolite molecular sieve is one or more of a 3A molecular sieve, a 4A molecular sieve, a 5A molecular sieve, a 10X molecular sieve and a 13X molecular sieve.
Preferably, the rare earth oxide is one or more of lanthanum oxide, neodymium oxide, cerium oxide and praseodymium oxide.
Preferably, the mass concentration of the ammonia water is 0.1-20%.
Preferably, the surfactant is one or more of sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium lignin sulfonate and calcium lignin sulfonate.
Preferably, the coagulant is methanol or ethanol.
Preferably, the vulcanization processing aid is one or more of sulfur, N-tert-butyl-2-benzothiazole hypoxanthamide, zinc oxide and stearic acid.
The invention provides a preparation method of the epoxidized natural rubber composite material, which comprises the following steps:
(1) modifying ammonia water, rare earth oxide and a zeolite molecular sieve in an aqueous phase system to obtain a rare earth modified zeolite molecular sieve dispersion;
(2) mixing the rare earth modified zeolite molecular sieve dispersion in the step (1) with a surfactant and milky epoxidized natural rubber to obtain a latex-state composite material;
(3) mixing the composite material in the latex state in the step (2) with a coagulant, and then sequentially carrying out tabletting, granulation and drying to obtain the composite material in a dry glue state;
(4) and (4) mixing and vulcanizing the composite material in the dry rubber state in the step (3) and a vulcanization processing aid to obtain the epoxidized natural rubber composite material.
Preferably, the modification temperature in the step (1) is 30-80 ℃, and the modification time is 5-120 min; the modification reaction is carried out under the ultrasonic condition, and the power of the ultrasonic is 500-700W.
The invention provides an epoxidized natural rubber composite material which is prepared from the following raw materials in parts by weight: 100 parts of emulsion epoxidized natural rubber, 0.1-30 parts of zeolite molecular sieve, 0.1-10 parts of rare earth oxide, 0.5-10 parts of ammonia water, 0.05-0.8 part of surfactant, 0.1-4 parts of coagulant and 0.2-12 parts of vulcanization processing aid. According to the invention, the special pore structure of the molecular sieve has good barrier effect on heat, oxygen and ultraviolet rays, and meanwhile, rare earth ions in the rare earth modified molecular sieve can capture free radicals, so that the aging resistance of the epoxidized natural rubber is improved. In addition, the rare earth modified molecular sieve dispersoid is alkaline, can neutralize residual acid in the preparation process of the epoxidized natural rubber, and further improves the aging resistance of the epoxidized natural rubber. The data described in the examples show that the tensile strength retention rate and the tensile elongation retention rate of the epoxidized natural rubber composite material of the present invention after hot air aging, ozone aging and ultraviolet aging treatment can be maintained at 85% or more, and the hot air aging resistance, ozone aging resistance and ultraviolet aging resistance of the epoxidized natural rubber composite material of the present invention are significantly improved compared to those of the common epoxidized natural rubber composite material.
The preparation process of the aging-resistant epoxidized natural rubber composite material provided by the invention does not influence the processability and physical and mechanical properties of rubber materials, and the used rare earth oxide has no toxicity and low cost, and is easy for large-scale production.
Detailed Description
The invention provides an epoxidized natural rubber composite material which is prepared from the following raw materials in parts by weight: 100 parts of emulsion epoxidized natural rubber, 0.1-30 parts of zeolite molecular sieve, 0.1-10 parts of rare earth oxide, 0.5-10 parts of ammonia water, 0.05-0.8 part of surfactant, 0.1-4 parts of coagulant and 0.2-12 parts of vulcanization processing aid.
The epoxidized natural rubber composite material provided by the invention takes emulsion epoxidized natural rubber as a matrix, and the weight part (calculated by dry rubber) of the emulsion epoxidized natural rubber is 100 parts. In the invention, the epoxidation degree of the emulsion epoxidized natural rubber is preferably 2-50, and more preferably 25-40. The present invention does not specifically require the source of the milky epoxidized natural rubber, and the milky epoxidized natural rubber derived well known to those skilled in the art may be used, specifically, commercially available milky epoxidized natural rubber.
Based on 100 parts by weight of milky epoxidized natural rubber, the epoxidized natural rubber composite material provided by the invention comprises 0.1-30 parts of zeolite molecular sieve, preferably 1-25 parts, and more preferably 10-20 parts. In the invention, the zeolite molecular sieve is preferably one or more of a 3A molecular sieve, a 4A molecular sieve, a 5A molecular sieve, a 10X molecular sieve and a 13X molecular sieve.
Based on 100 parts by weight of milky epoxidized natural rubber, the epoxidized natural rubber composite material provided by the invention comprises 0.1-10 parts of rare earth oxide, preferably 1-8 parts, and more preferably 2-5 parts. In the invention, the rare earth oxide is preferably one or more of lanthanum oxide, neodymium oxide, cerium oxide and praseodymium oxide.
Based on 100 parts by weight of milky epoxidized natural rubber, the epoxidized natural rubber composite material provided by the invention comprises 0.5-10 parts by weight of ammonia water, preferably 1-8 parts by weight, and more preferably 4-6 parts by weight. In the present invention, the mass concentration of the ammonia water is preferably 0.1 to 20%, more preferably 1 to 15%, and most preferably 5 to 10%. The invention can generate rare earth hydroxide by using ammonia water and rare earth oxide, and the rare earth hydroxide can neutralize residual acid in the preparation process of epoxidized natural rubber.
The epoxidized natural rubber composite material provided by the invention comprises 0.05-0.8 part of surfactant, preferably 0.1-0.5 part of surfactant, and more preferably 0.2-0.4 part of surfactant based on 100 parts by weight of milky epoxidized natural rubber. In the present invention, the surfactant is preferably one or more of sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium lignin sulfonate and calcium lignin sulfonate.
The epoxidized natural rubber composite material provided by the invention comprises 0.1-4 parts of a coagulant, preferably 0.5-3 parts of the coagulant, and more preferably 1-2.5 parts of the coagulant based on 100 parts by weight of milky epoxidized natural rubber. In the present invention, the coagulant is preferably methanol or ethanol.
Based on 100 parts by weight of milky epoxidized natural rubber, the epoxidized natural rubber composite material provided by the invention comprises 0.2-12 parts of vulcanization processing aid, preferably 2-10 parts, and more preferably 5-8 parts. In the invention, the vulcanization processing aid is preferably one or more of sulfur, N-tert-butyl-2-benzothiazole hypoxanthamide (accelerator NS), zinc oxide and stearic acid; more preferably a mixture of sulphur, N-tert-butyl-2-benzothiazolelfenamide, zinc oxide and stearic acid, the weight ratio of sulphur, N-tert-butyl-2-benzothiazolelfenamide, zinc oxide and stearic acid in said mixture preferably being 1.5: 1.3: 5: 2.
the sources of the zeolite molecular sieve, the rare earth oxide, the ammonia water, the surfactant, the coagulant and the vulcanization processing aid are not particularly required in the present invention, and the above substances of which the sources are well known to those skilled in the art, specifically, the above substances are commercially available, can be used.
The invention provides a preparation method of the epoxidized natural rubber composite material, which comprises the following steps:
(1) modifying ammonia water, rare earth oxide and a zeolite molecular sieve in an aqueous phase system to obtain a rare earth modified zeolite molecular sieve dispersion;
(2) mixing the rare earth modified zeolite molecular sieve dispersion in the step (1) with a surfactant and milky epoxidized natural rubber latex to obtain a composite material in a latex state;
(3) mixing the composite material in the latex state in the step (2) with a coagulant, and then sequentially carrying out tabletting, granulation and drying to obtain the composite material in a dry glue state;
(4) and (4) mixing and vulcanizing the composite material in the dry rubber state in the step (3) and a vulcanization processing aid to obtain the epoxidized natural rubber composite material.
According to the invention, ammonia water, rare earth oxide and zeolite molecular sieve are modified in a water phase system to obtain the rare earth modified zeolite molecular sieve dispersion. In the invention, the modification temperature is preferably 30-80 ℃, more preferably 40-60 ℃, and the modification time is preferably 5-120 min, more preferably 10-100 min, and most preferably 30-80 min. In the invention, the modification is preferably carried out under ultrasonic conditions, and the power of the ultrasonic is preferably 500-700W, and more preferably 600-650W. In the invention, the water for providing the water phase system is preferably deionized water, and the mass ratio of the deionized water to the milky epoxidized natural rubber is preferably 1: 0.6-1.
After the rare earth modified zeolite molecular sieve dispersion is obtained, the rare earth modified zeolite molecular sieve dispersion is mixed with a surfactant and milky epoxidized natural rubber to obtain the latex-state composite material. In the invention, the mixing is preferably carried out under ultrasonic conditions, the power of the ultrasonic is preferably 500-700W, more preferably 600-650W, and the time of the ultrasonic is preferably 0.1-2 h, more preferably 1-1.5 h. In the invention, the mixing temperature is preferably 30-80 ℃, and more preferably 40-60 ℃.
After the composite material in the latex state is obtained, the composite material in the latex state is mixed with a coagulant, and then tabletting, granulating and drying are sequentially carried out to obtain the composite material in the dry glue state. The manner of mixing, tabletting, granulating and drying is not particularly limited in the present invention, and mixing, tabletting, granulating and drying may be performed in a manner well known to those skilled in the art.
After the composite material in the dry rubber state is obtained, the composite material in the dry rubber state and a vulcanization processing aid are mixed and vulcanized to obtain the epoxidized natural rubber composite material. The method of mixing and vulcanizing is not particularly limited in the present invention, and mixing and vulcanizing may be performed by a method known to those skilled in the art.
The epoxidized natural rubber composite provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding 0.1 part of lanthanum oxide into 100 parts of deionized water by weight, then adding 0.5 part of ammonia water (the concentration is 0.1%), controlling the ultrasonic power to be 500W, adding 0.1 part of 3A molecular sieve in the ultrasonic dispersion state, placing in a water bath at 30 ℃ for continuous ultrasonic treatment for 5min to prepare a rare earth modified zeolite molecular sieve dispersion body, then adding 0.05 part of sodium dodecyl benzene sulfonate and 100 parts of emulsion epoxidized natural rubber (the epoxidation degree is 2) calculated by dry rubber, and continuing ultrasonic stirring for 1.2h to obtain a composite material in a latex state; and adding 1.5 parts of methanol to solidify the composite material in a latex state, tabletting, granulating and drying after solidification to obtain the composite material in a dry rubber state, and then adding 0.9 part of sulfur, 1.7 parts of accelerator NS, 5 parts of zinc oxide and 1 part of stearic acid into a double-roll open mill to mix and vulcanize, thereby obtaining the epoxidized natural rubber composite material.
Example 2
Adding 10 parts by weight of cerium oxide into 100 parts by weight of deionized water, then adding 10 parts by weight of ammonia water (the concentration is 20%), controlling the ultrasonic power to be 700W, adding 30 parts by weight of 4A molecular sieve in the ultrasonic dispersion state, placing in a water bath at 80 ℃ for continuous ultrasonic treatment for 120min to prepare rare earth modified zeolite molecular sieve dispersion, then adding 0.8 part by weight of sodium dodecyl sulfate and 100 parts by weight of emulsion epoxidized natural rubber (the epoxidation degree is 50) in dry rubber, and continuing to stir ultrasonically for 2h to obtain a composite material in a latex state; and adding 4 parts of ethanol to solidify the composite material in a latex state, tabletting, granulating and drying the solidified composite material to obtain the composite material in a dry rubber state, adding 0.7 part of sulfur, 2 parts of accelerator NS, 6 parts of zinc oxide and 2 parts of stearic acid into a double-roll open mill, mixing, and vulcanizing to obtain the epoxidized natural rubber composite material.
Example 3
Adding 7 parts by weight of neodymium oxide into 100 parts by weight of deionized water, then adding 7 parts by weight of ammonia water (the concentration is 10%), controlling the ultrasonic power to be 600W, adding 20 parts by weight of 5A molecular sieve in the ultrasonic dispersion state, placing the mixture in a water bath at 70 ℃ for continuous ultrasonic treatment for 60min to prepare rare earth modified zeolite molecular sieve dispersion, then adding 0.5 part by weight of sodium lignosulfonate and 100 parts by weight of emulsion epoxidized natural rubber (the epoxidation degree is 40) in dry glue, and continuing ultrasonic stirring for 1.5h to obtain a composite material in a latex state; and 2 parts of ethanol is added to solidify the composite material in a latex state, tabletting, granulating and drying are carried out after solidification to obtain the composite material in a dry rubber state, and then 0.5 part of sulfur, 1.5 parts of accelerator NS, 5 parts of zinc oxide and 1.5 parts of stearic acid are added into a double-roll open mill to be mixed and vulcanized, so as to obtain the epoxidized natural rubber composite material.
Example 4
Adding 10 parts of praseodymium oxide into 100 parts of deionized water by weight, then adding 4 parts of ammonia water (the concentration is 5%), controlling the ultrasonic power to be 650W, adding 7 parts of 10X molecular sieve in an ultrasonic dispersion state, placing in a water bath at 50 ℃ for continuous ultrasonic treatment for 30min to prepare a rare earth modified zeolite molecular sieve dispersion, then adding 0.3 part of sodium dodecyl sulfate and 100 parts of emulsion epoxidized natural rubber (the epoxidation degree is 30) calculated by dry rubber, and continuing to stir for 1h by ultrasonic treatment to obtain a composite material in a latex state; and adding 2 parts of methanol to solidify the composite material in a latex state, tabletting, granulating and drying the solidified composite material to obtain the composite material in a dry rubber state, and then adding 1.5 parts of sulfur, 1.5 parts of accelerator NS, 6 parts of zinc oxide and 2 parts of stearic acid into a double-roll open mill to mix and vulcanize the mixture to obtain the epoxidized natural rubber composite material.
Example 5
Adding 2 parts by weight of cerium oxide into 100 parts by weight of deionized water, then adding 7 parts by weight of ammonia water (the concentration is 5%), controlling the ultrasonic power to be 600W, adding 10 parts by weight of 13X molecular sieve in the ultrasonic dispersion state, placing in a water bath at 40 ℃ for continuous ultrasonic treatment for 100min to prepare rare earth modified zeolite molecular sieve dispersion, then adding 0.4 part by weight of calcium lignosulfonate and 100 parts by weight of emulsion epoxidized natural rubber (the epoxidation degree is 10) in dry rubber, and continuing to stir ultrasonically for 2h to obtain a composite material in a latex state; and adding 4 parts of ethanol to solidify the composite material in a latex state, tabletting, granulating and drying the solidified composite material to obtain the composite material in a dry rubber state, adding 2.5 parts of sulfur, 0.7 part of accelerator NS, 5 parts of zinc oxide and 1 part of stearic acid into a double-roll open mill, mixing, and vulcanizing to obtain the epoxidized natural rubber composite material.
Comparative example
Selecting epoxidized natural rubber (manufacturer: agricultural product processing research institute of tropical agricultural academy of sciences of China) with the epoxidation degree of 40, mixing, and vulcanizing to obtain an epoxidized natural rubber composite material; the formula comprises 100 parts of epoxidized natural rubber with the epoxidation degree of 40, 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of accelerator NS, 2 parts of sulfur and 30 parts of white carbon black.
The air aging resistance, ozone aging resistance and ultraviolet aging resistance of the epoxidized natural rubber composites obtained in examples 1 to 5 and the epoxidized natural rubber composites obtained in the comparative examples were measured according to the methods specified in GB/T3512-2001 (tests for accelerated hot air aging and heat resistance of vulcanized rubber or thermoplastic rubber), GB/T7762-2003 (static tensile test for ozone crack resistance of vulcanized rubber or thermoplastic rubber), and GB/T16585-1996 (test method for artificial weather aging (fluorescent ultraviolet lamp) of vulcanized rubber), and the test results are shown in Table 1.
TABLE 1 Performance test results of epoxidized natural rubber composites obtained in examples 1 to 5 and comparative example
As can be seen from Table 1, the tensile strength retention rate and the tensile elongation retention rate of the epoxidized natural rubber composite material provided by the invention can be kept above 85% after hot air aging, ozone aging and ultraviolet aging treatment, and compared with the epoxidized natural rubber composite material in the comparative example, the epoxidized natural rubber composite material provided by the invention has the advantages that the hot air aging resistance, the ozone aging resistance and the ultraviolet aging resistance are obviously improved, the heat generation performance is obviously reduced, the preparation method is simple, the cost is low, and the large-scale production is easy.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An epoxidized natural rubber composite material is prepared from the following raw materials in parts by weight: 100 parts of emulsion epoxidized natural rubber, 0.1-30 parts of zeolite molecular sieve, 0.1-10 parts of rare earth oxide, 0.5-10 parts of ammonia water, 0.05-0.8 part of surfactant, 0.1-4 parts of coagulant and 0.2-12 parts of vulcanization processing aid;
the preparation method of the epoxidized natural rubber composite material comprises the following steps:
(1) modifying ammonia water, rare earth oxide and a zeolite molecular sieve in an aqueous phase system to obtain a rare earth modified zeolite molecular sieve dispersion;
(2) mixing the rare earth modified zeolite molecular sieve dispersion in the step (1) with a surfactant and milky epoxidized natural rubber to obtain a latex-state composite material;
(3) mixing the composite material in the latex state in the step (2) with a coagulant, and then sequentially carrying out tabletting, granulation and drying to obtain the composite material in a dry glue state;
(4) and (4) mixing and vulcanizing the composite material in the dry rubber state in the step (3) and a vulcanization processing aid to obtain the epoxidized natural rubber composite material.
2. The epoxidized natural rubber composite according to claim 1, wherein the degree of epoxidation of the milky epoxidized natural rubber is 2 to 50.
3. The epoxidized natural rubber composite of claim 1, wherein the zeolite molecular sieve is one or more of a 3A molecular sieve, a 4A molecular sieve, a 5A molecular sieve, a 10X molecular sieve and a 13X molecular sieve.
4. The epoxidized natural rubber composite of claim 1, wherein the rare earth oxide is one or more of lanthanum oxide, neodymium oxide, cerium oxide and praseodymium oxide.
5. The epoxidized natural rubber composite according to claim 1, wherein the mass concentration of the ammonia water is 0.1 to 20%.
6. The epoxidized natural rubber composite of claim 1, wherein the surfactant is one or more of sodium dodecyl sulfate, sodium lignosulfonate, and calcium lignosulfonate.
7. The epoxidized natural rubber composite of claim 1, wherein the coagulant is methanol or ethanol.
8. The epoxidized natural rubber composite of claim 1, wherein the vulcanization processing aid is one or more of sulfur, N-tert-butyl-2-benzothiazolehypoxanthamide, zinc oxide, and stearic acid.
9. A method for producing the epoxidized natural rubber composite according to any one of claims 1 to 8, comprising the steps of:
(1) modifying ammonia water, rare earth oxide and a zeolite molecular sieve in an aqueous phase system to obtain a rare earth modified zeolite molecular sieve dispersion;
(2) mixing the rare earth modified zeolite molecular sieve dispersion in the step (1) with a surfactant and milky epoxidized natural rubber to obtain a latex-state composite material;
(3) mixing the composite material in the latex state in the step (2) with a coagulant, and then sequentially carrying out tabletting, granulation and drying to obtain the composite material in a dry glue state;
(4) and (4) mixing and vulcanizing the composite material in the dry rubber state in the step (3) and a vulcanization processing aid to obtain the epoxidized natural rubber composite material.
10. The preparation method according to claim 9, wherein the temperature of the modification in the step (1) is 30-80 ℃, and the time of the modification is 5-120 min; the modification is carried out under the ultrasonic condition, and the power of the ultrasonic is 500-700W.
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