CN109679159B - Modified composite rubber master batch and preparation method thereof - Google Patents
Modified composite rubber master batch and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2407/00—Characterised by the use of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/06—Sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
Abstract
The invention discloses a modified composite rubber master batch, which comprises raw material composite rubber, an anti-aging agent, stearic acid, microcrystalline wax, an accelerator, sulfur, carbon black, a coupling agent and a stabilizer; the composite rubber comprises natural rubber and acrylate rubber, and the raw materials also comprise a compatibilizer polycaprolactone. The invention also discloses a preparation method of the modified composite rubber master batch, which comprises the steps of preparation of the composite rubber, material extrusion, drying, sealing treatment and the like. The invention improves the technical problems of poor aging resistance, easy dissolution by nonpolar oil medium, poor filling property, low mechanical strength and the like of the existing natural rubber, the improved composite rubber master batch has the characteristics of high strength, good air aging resistance, nonpolar oil resistance and the like, and the preparation method is simple, convenient to operate and convenient to produce and use.
Description
Technical Field
The invention relates to the field of rubber master batches, in particular to a modified composite rubber master batch and a preparation method thereof.
Background
The full-name plastic master batch is a plastic processing aid developed and stood in the 80 th 20 th century and consists of excessive chemical aids, carrier resin, a dispersing agent and the like. The masterbatch is generally composed of a carrier resin, various fillers and various auxiliaries. In the plastic processing and forming process, for the convenience of operation, various required additives and fillers and a small amount of carrier resin are mixed and mixed firstly, and the particles are obtained through the processing processes of metering, mixing, melting, extruding, granulating and the like by using equipment such as an extruder and the like. The limit of the auxiliary agent or the content of the filler in the master batch is several times to dozens of times higher than the required amount in the actual plastic product. The invention relates to a composite rubber master batch, and the natural rubber is known to be a crystalline high molecular compound, is easy to induce crystallization under deformation to be self-reinforced, has excellent mechanical strength and processability, and has better physical properties than synthetic rubber. The natural rubber is widely used in the industrial fields of automobile tires, rubber tubes, sealing elements and the like, and the living fields of rubber shoes, rubber gloves and the like, and is the rubber with the largest use amount at present. However, natural rubber is a nonpolar elastomer with high unsaturation degree, so that it is not resistant to nonpolar oil medium and has poor weather resistance. When the service temperature is higher than 70 ℃ in a hot air environment, the aging can be rapidly carried out, the rebound resilience and the mechanical strength are greatly reduced, and the popularization and the application cannot be realized. The invention discloses a modified composite rubber master batch and a preparation method thereof, aiming at filling a modifier and other fillers through the rubber master batch and then reprocessing the modified rubber master batch and natural rubber for production. So as to improve the characteristics of ageing resistance, nonpolar oil resistance, filling performance, mechanical performance and the like of the natural rubber. Meanwhile, the invention also improves the prior natural rubber production process, the design scheme of the invention has simple process and convenient operation,
disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a modified composite rubber master batch and a preparation method thereof, which are used for solving the technical problems that natural rubber in the prior art is poor in ageing resistance, easy to dissolve by a nonpolar oil medium, poor in filling property, low in mechanical strength and the like;
in order to solve the technical problems, the invention discloses a modified composite rubber master batch which comprises raw material composite rubber, an anti-aging agent, stearic acid, microcrystalline wax, an accelerator, sulfur, carbon black, a coupling agent and a stabilizer, wherein the raw material comprises the following components in parts by weight:
the composite rubber comprises natural rubber and acrylate rubber, and the raw materials further comprise a compatibilizer polycaprolactone, wherein the compatibilizer comprises 1-8 parts by weight. The acrylate rubber (ACM) is an elastomer obtained by copolymerizing acrylate serving as a main monomer, wherein the main chain of the elastomer is a saturated carbon chain, and the side group of the elastomer is a polar ester group. The mechanical property and the processing property are superior to those of fluororubber and silicon rubber, and the high-temperature resistant fluororubber and silicon rubber are widely used for high-temperature resistant oil seals, cylinder gaskets, hydraulic oil pipelines and the like of automobiles. Polycaprolactone (also called poly epsilon-caprolactone, which is a high molecular organic polymer prepared by ring opening polymerization of epsilon-caprolactone monomer under the catalysis of metal anion complex catalyst) can obtain different molecular weights by controlling the polymerization conditions.
Preferably: in order to better improve the aging resistance and the mechanical strength of the rubber, the natural rubber and the acrylate rubber are compounded according to the mass ratio of 4: 1.
Further, in order to improve the ultraviolet resistance of the composite rubber master batch, the anti-aging agent is any one of 2-mercaptobenzimidazole, N-phenyl-beta-naphthylamine, N-cyclohexyl-N' -phenyl-p-phenylenediamine or anti-aging agent RD.
Furthermore, in order to better ensure that the composite rubber and the filler are uniformly filled and have stable performance, the accelerator is an accelerator TMTD, the coupling agent is a phthalate coupling agent, and the stabilizer is triphenyl phosphite, cyanuric chloride or an antioxidant DSTOP.
Further, the application also discloses a preparation method of the modified composite rubber master batch, which comprises the following preparation steps:
step one, preparation of compounded rubber
Drying the weighed natural rubber and acrylate rubber, and adding the dried natural rubber and acrylate rubber and a compatibilizer, an anti-aging agent, stearic acid, sulfur, carbon black and a coupling agent which are weighed in proportion into an internal mixer for mixing to prepare composite rubber;
step two, extruding the materials
Pouring the prepared composite rubber into a co-rotating double-screw extruder, adding the weighed microcrystalline wax, accelerator and stabilizer into the extruder together for extruding, putting strips extruded from a nozzle of the extruder into a water tank for cooling, and then cutting the strips into particles by a granulator;
step three, drying and sealing
Drying the cut granules by a hot air dryer, screening by a material screening machine, and sealing and storing in a sealing bag.
Further, in the first step, the pressure in a mixing chamber of the internal mixer is controlled to be 5-8 bar, and the temperature in the mixing chamber is controlled to be 150-200 ℃.
Further, in order to better facilitate filling and melting, the heating temperature area of the co-rotating twin-screw extruder in the second step is as follows: 110-115 ℃ in zone 1, 115-120 ℃ in zone 2, 115-120 ℃ in zone 3, 120-130 ℃ in zone 4, 120-130 ℃ in zone 5, 130-140 ℃ in zone 6, 140-150 ℃ in zone 7, 150-160 ℃ in zone 8 and 160 ℃ in head.
Further, in order to completely dry the composite master batch and avoid influencing subsequent processing production, the drying temperature of the hot air dryer in the third step is controlled to be 90-110 ℃, and the drying time is 3-5 hours.
The invention discloses a modified composite rubber master batch and a preparation method thereof, wherein natural rubber and acrylate rubber are modified and compounded, the excellent mechanical strength of the natural rubber and the excellent oil resistance of the acrylate rubber are combined, and then the bulking agent polycaprolactone is used for bulking to improve the filling amount of a filler, so that the mechanical strength and the aging resistance of the filler are further improved. The composite rubber master batch prepared by the invention has the characteristics of high mechanical strength, good aging resistance, easy production and processing and the like.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
Embodiment 1 discloses a rubber master batch, which comprises raw materials of natural rubber, an anti-aging agent, stearic acid, microcrystalline wax, an accelerator, sulfur, carbon black, a coupling agent and a stabilizer, wherein the raw materials comprise the following components in parts by weight:
the antioxidant is 2-mercaptobenzimidazole, the accelerator is TMTD, the coupling agent is phthalate ester coupling agent, and the stabilizer is triphenyl phosphite.
A preparation method of rubber master batch comprises the following preparation steps:
step one, preparation of compounded rubber
Drying the weighed natural rubber, adding the dried natural rubber and proportionally weighed polycaprolactone, an anti-aging agent, stearic acid, sulfur, carbon black and a coupling agent into an internal mixer for mixing, controlling the pressure in a mixing chamber of the internal mixer to be 5-8 bar, and controlling the temperature in the mixing chamber to be 150 ℃ to obtain the composite rubber;
step two, extruding the materials
Pouring the prepared composite rubber into a co-rotating double-screw extruder, and adding the weighed microcrystalline wax, the accelerator and the stabilizer into the extruder together for extruding, wherein the heating temperature zone of the double-screw extruder is as follows: 110 ℃ in the 1 region, 115 ℃ in the 2 region, 120 ℃ in the 3 region, 120 ℃ in the 4 region, 120 ℃ in the 5 region, 130 ℃ in the 6 region, 140 ℃ in the 7 region, 150 ℃ in the 8 region and 160 ℃ in the machine head; the temperature deviation of each temperature zone is not more than 5 ℃, the material strips extruded from the nozzle of the extruder are placed in a water tank for cooling, and then a granulator is used for granulating the material strips;
step three, drying and sealing
Drying the cut granules by a hot air dryer, controlling the drying temperature of the hot air dryer at 90 ℃, drying for 3 hours, screening by a screening machine, and sealing and storing in a sealing bag.
Example 2
Embodiment 2 discloses a modified composite rubber master batch, which comprises raw material composite rubber, an anti-aging agent, stearic acid, microcrystalline wax, an accelerator, sulfur, carbon black, a coupling agent and a stabilizer, wherein the raw materials comprise the following components in parts by weight:
in the embodiment, the rubber comprises 90 parts of natural rubber and 10 parts of acrylate rubber, and the raw materials further comprise 1 part of a compatibilizer polycaprolactone; the anti-aging agent is N-phenyl-beta-naphthylamine. The accelerant is an accelerant TMTD, the coupling agent is a phthalate ester coupling agent, and the stabilizing agent is triphenyl phosphite.
A preparation method of modified composite rubber master batch comprises the following preparation steps:
step one, preparation of compounded rubber
Drying the weighed natural rubber and acrylate rubber, adding the dried natural rubber and acrylate rubber and a compatibilizer, an anti-aging agent, stearic acid, sulfur, carbon black and a coupling agent which are weighed in proportion into an internal mixer for mixing, controlling the pressure in a mixing chamber of the internal mixer to be 5-8 bar, and controlling the temperature in the mixing chamber to be 180 ℃ to obtain the composite rubber;
step two, extruding the materials
Pouring the prepared composite rubber into a co-rotating double-screw extruder, and adding the weighed microcrystalline wax, the accelerator and the stabilizer into the extruder together for extruding, wherein the heating temperature zone of the double-screw extruder is as follows: 110 ℃ in the 1 region, 115 ℃ in the 2 region, 120 ℃ in the 3 region, 120 ℃ in the 4 region, 120 ℃ in the 5 region, 130 ℃ in the 6 region, 140 ℃ in the 7 region, 150 ℃ in the 8 region and 160 ℃ in the machine head; the temperature deviation of each temperature zone is not more than 5 ℃, the material strips extruded from the nozzle of the extruder are placed in a water tank for cooling, and then a granulator is used for granulating the material strips;
step three, drying and sealing
Drying the cut granules by a hot air dryer, controlling the drying temperature of the hot air dryer at 110 ℃, drying for 5 hours, screening by a screening machine, and sealing and storing in a sealing bag.
Example 3
Embodiment 3 discloses a modified composite rubber master batch, which comprises raw material composite rubber, an anti-aging agent, stearic acid, microcrystalline wax, an accelerator, sulfur, carbon black, a coupling agent and a stabilizer, wherein the raw materials comprise the following components in parts by weight:
the composite rubber comprises natural rubber and acrylate rubber, and the raw materials also comprise a compatibilizer polycaprolactone, wherein the compatibilizer comprises 5 parts by weight.
80 parts of natural rubber and 20 parts of acrylate rubber are compounded according to the mass ratio of 4:1, and the anti-aging agent is N-phenyl-beta-naphthylamine. The accelerator is an accelerator TMTD, the coupling agent is phthalate ester coupling agent, and the stabilizer is antioxidant DSTOP.
The embodiment also discloses a preparation method of the modified composite rubber master batch, which comprises the following preparation steps:
step one, preparation of compounded rubber
Drying the weighed natural rubber and acrylate rubber, adding the dried natural rubber and acrylate rubber and a compatibilizer, an anti-aging agent, stearic acid, sulfur, carbon black and a coupling agent which are weighed in proportion into an internal mixer for mixing, controlling the pressure in a mixing chamber of the internal mixer to be 5-8 bar, and controlling the temperature in the mixing chamber to be 200 ℃ to obtain the composite rubber;
step two, extruding the materials
Pouring the prepared composite rubber into a co-rotating double-screw extruder, and adding the weighed microcrystalline wax, the accelerator and the stabilizer into the extruder together for extruding, wherein the heating temperature zone of the double-screw extruder is as follows: 115 ℃ in the 1 region, 120 ℃ in the 2 region, 120 ℃ in the 3 region, 120 ℃ in the 4 region, 130 ℃ in the 5 region, 130 ℃ in the 6 region, 140 ℃ in the 7 region, 150 ℃ in the 8 region and 160 ℃ in the head; the temperature deviation of each temperature zone is not more than 5 ℃, the material strips extruded from the nozzle of the extruder are placed in a water tank for cooling, and then a granulator is used for granulating the material strips;
step three, drying and sealing
Drying the cut granules by a hot air dryer, controlling the drying temperature of the hot air dryer at 110 ℃, drying for 5 hours, screening by a screening machine, and sealing and storing in a sealing bag.
Example 4
Embodiment 4 discloses a modified composite rubber master batch, which comprises raw material composite rubber, an anti-aging agent, stearic acid, microcrystalline wax, an accelerator, sulfur, carbon black, a coupling agent and a stabilizer, wherein the raw materials comprise the following components in parts by weight: 100 parts of composite rubber, 1.5 parts of anti-aging agent, 1 part of stearic acid, 7 parts of microcrystalline wax, 0.5 part of accelerator, 4 parts of sulfur, 45 parts of carbon black, 1 part of coupling agent and 0.3 part of stabilizer, wherein the composite rubber comprises 70 parts of natural rubber and 30 parts of acrylate rubber, the raw materials also comprise a compatibilizer polycaprolactone, and the compatibilizer comprises 2 parts by weight. The anti-aging agent is 2-mercaptobenzimidazole, the accelerating agent is accelerating agent TMTD, the coupling agent is phthalate ester coupling agent, and the stabilizing agent is antioxidant DSTOP.
Example 5
Embodiment 5 discloses a modified composite rubber master batch, which comprises raw material composite rubber, an anti-aging agent, stearic acid, microcrystalline wax, an accelerator, sulfur, carbon black, a coupling agent and a stabilizer, wherein the raw materials comprise the following components in parts by weight: 100 parts of composite rubber, 1.5 parts of anti-aging agent, 1.5 parts of stearic acid, 8 parts of microcrystalline wax, 1 part of accelerator, 5 parts of sulfur, 55 parts of carbon black, 2 parts of coupling agent and 0.4 part of stabilizer, wherein the composite rubber comprises 60 parts of natural rubber and 40 parts of acrylate rubber, and the raw material also comprises 8 parts of compatibilizer polycaprolactone. The anti-aging agent is N-cyclohexyl-N' -phenyl-p-phenylenediamine. The accelerant is an accelerant TMTD, the coupling agent is a phthalate ester coupling agent, and the stabilizing agent is triphenyl phosphite.
Example 6
Embodiment 6 discloses a modified composite rubber master batch, which comprises raw material composite rubber, an anti-aging agent, stearic acid, microcrystalline wax, an accelerator, sulfur, carbon black, a coupling agent and a stabilizer, wherein the raw materials comprise the following components in parts by weight: 100 parts of composite rubber, 1 part of anti-aging agent, 2 parts of stearic acid, 7 parts of microcrystalline wax, 1 part of accelerator, 6 parts of sulfur, 50 parts of carbon black, 2 parts of coupling agent and 0.4 part of stabilizer, wherein the composite rubber comprises 50 parts of natural rubber and 50 parts of acrylate rubber, and the raw materials further comprise 3 parts of compatibilizer polycaprolactone. The anti-aging agent is N-cyclohexyl-N' -phenyl-p-phenylenediamine. The accelerant is an accelerant TMTD, the coupling agent is a phthalate ester coupling agent, and the stabilizing agent is triphenyl phosphite.
Example 7
Embodiment 7 discloses a modified composite rubber master batch, which comprises raw material composite rubber, an anti-aging agent, stearic acid, microcrystalline wax, an accelerator, sulfur, carbon black, a coupling agent and a stabilizer, wherein the raw materials comprise the following components in parts by weight: 100 parts of composite rubber, 1.5 parts of anti-aging agent, 1 part of stearic acid, 8 parts of microcrystalline wax, 1 part of accelerator, 5 parts of sulfur, 45 parts of carbon black, 2 parts of coupling agent and 0.4 part of stabilizer, wherein the composite rubber comprises 40 parts of natural rubber and 60 parts of acrylate rubber, and the raw material also comprises 8 parts of compatibilizer polycaprolactone. The anti-aging agent is anti-aging agent RD. The accelerant is an accelerant TMTD, the coupling agent is a phthalate ester coupling agent, and the stabilizing agent is triphenyl phosphite.
Example 8
Embodiment 8 discloses a modified composite rubber master batch, which comprises raw material composite rubber, an anti-aging agent, stearic acid, microcrystalline wax, an accelerator, sulfur, carbon black, a coupling agent and a stabilizer, wherein the raw materials comprise the following components in parts by weight: 100 parts of composite rubber, 1.5 parts of anti-aging agent, 1.5 parts of stearic acid, 7 parts of microcrystalline wax, 1 part of accelerator, 5 parts of sulfur, 55 parts of carbon black, 2 parts of coupling agent and 0.4 part of stabilizer, wherein the composite rubber comprises 30 parts of natural rubber and 70 parts of acrylate rubber, and the raw materials further comprise 5 parts of compatibilizer polycaprolactone. The anti-aging agent is N-cyclohexyl-N' -phenyl-p-phenylenediamine. The accelerator is an accelerator TMTD, the coupling agent is phthalate ester coupling agent, and the stabilizer is antioxidant DSTOP.
Example 9
Embodiment 9 discloses a modified composite rubber master batch, which comprises raw material composite rubber, an anti-aging agent, stearic acid, microcrystalline wax, an accelerator, sulfur, carbon black, a coupling agent and a stabilizer, wherein the raw materials comprise the following components in parts by weight: 100 parts of composite rubber, 1 part of anti-aging agent, 2 parts of stearic acid, 8 parts of microcrystalline wax, 1 part of accelerator, 6 parts of sulfur, 50 parts of carbon black, 2 parts of coupling agent and 0.5 part of stabilizer, wherein the composite rubber comprises 20 parts of natural rubber and 80 parts of acrylate rubber, and the raw material also comprises 8 parts of compatibilizer polycaprolactone. The anti-aging agent is N-cyclohexyl-N' -phenyl-p-phenylenediamine. The accelerator is an accelerator TMTD, the coupling agent is phthalate ester coupling agent, and the stabilizer is cyanuric chloride.
Example 10
Embodiment 10 discloses a modified composite rubber masterbatch, which comprises raw material composite rubber, an anti-aging agent, stearic acid, microcrystalline wax, an accelerator, sulfur, carbon black, a coupling agent and a stabilizer, wherein the raw materials comprise the following components in parts by weight: 100 parts of composite rubber, 1.5 parts of anti-aging agent, 1.5 parts of stearic acid, 8 parts of microcrystalline wax, 1 part of accelerator, 5 parts of sulfur, 55 parts of carbon black, 2 parts of coupling agent and 0.4 part of stabilizer, wherein the composite rubber comprises 10 parts of natural rubber and 90 parts of acrylate rubber, and the raw material also comprises 8 parts of compatibilizer polycaprolactone. The anti-aging agent is N-cyclohexyl-N' -phenyl-p-phenylenediamine. The accelerant is an accelerant TMTD, the coupling agent is a phthalate ester coupling agent, and the stabilizing agent is triphenyl phosphite.
Example 11
Embodiment 11 discloses a rubber masterbatch, which comprises raw materials of acrylate rubber, an anti-aging agent, stearic acid, microcrystalline wax, an accelerator, sulfur, carbon black, a coupling agent and a stabilizer, wherein the raw materials comprise the following components in parts by weight: 100 parts of acrylate rubber, 1.5 parts of anti-aging agent, 1.5 parts of stearic acid, 8 parts of microcrystalline wax, 1 part of accelerator, 5 parts of sulfur, 55 parts of carbon black, 2 parts of coupling agent and 0.4 part of stabilizer, wherein the raw materials also comprise 8 parts of compatibilizer polycaprolactone. The anti-aging agent is N-cyclohexyl-N' -phenyl-p-phenylenediamine. The accelerant is an accelerant TMTD, the coupling agent is a phthalate ester coupling agent, and the stabilizing agent is triphenyl phosphite.
The performance test of the composite rubber master batch in the above embodiment was carried out:
as shown in table 1:
TABLE 1 physical and mechanical Properties of Natural rubber/acrylate rubber at different blending ratios
From the data, it can be clearly seen that when the natural rubber/acrylate rubber composite ratio is in the range of 90/10 and 80/20, the tensile strength of the composite master batch is close to 20MPa, the elongation at break is also close to 450%, and the strength and toughness of the material are obviously improved for single rubber. By adding the filler, the tearing strength of the compounded rubber can reach 51.3KN/m at most, and the hardness of the compounded rubber exceeds 60 degrees. As can be seen from the data in the table, the modified rubber masterbatch has higher improvement in mechanical strength, flexibility and hardness.
In the technology, the natural rubber/acrylate rubber is selected as 80/20, and the influence of different compatibilizer dosage on the aging resistance and oil resistance of the rubber is researched on the basis.
As shown in table 2:
TABLE 2 Effect of different amounts of polycaprolactone on the Properties of the modified rubber masterbatch
The influence of the compatibilizer on the performance of the composite rubber master batch is detected by changing the content of polycaprolactone. From the above data, we can see that the increase of the compatibilizer is a trend of increasing and then decreasing for the tensile strength of the rubber masterbatch; the elongation at break generally tends to increase, which means that the hardness and flexibility of the material are increased by increasing the compatibilizer, but the hardness and flexibility are sharply reduced by increasing the compatibilizer too much. In the aspect of air aging resistance, the composite rubber master batch subjected to artificial air aging treatment is reduced in tensile strength and elongation at break, and the table shows that the sample added with the compatibilizer is slower than the sample without the compatibilizer, which indicates that the use amount of the compatibilizer has a positive influence on the strength performance and the aging resistance of the composite rubber master batch.
Claims (7)
1. A modified composite rubber master batch is characterized in that: the rubber material comprises raw material composite rubber, an anti-aging agent, stearic acid, microcrystalline wax, an accelerator, sulfur, carbon black, a coupling agent and a stabilizer, wherein the raw materials comprise the following components in parts by weight:
the composite rubber comprises natural rubber and acrylate rubber, the raw materials also comprise a compatibilizer polycaprolactone, and the compatibilizer comprises 1-8 parts by weight;
the natural rubber and the acrylate rubber are compounded according to the mass ratio of 4: 1.
2. The modified compounded rubber masterbatch of claim 1, wherein: the anti-aging agent is any one of 2-mercaptobenzimidazole, N-phenyl-beta-naphthylamine, N-cyclohexyl-N' -phenyl p-phenylenediamine or an anti-aging agent RD.
3. The modified compounded rubber masterbatch of claim 1, wherein: the accelerator is an accelerator TMTD, the coupling agent is phthalate ester coupling agent, and the stabilizer is triphenyl phosphite, cyanuric chloride or antioxidant DSTOP.
4. A method for preparing the modified composite rubber masterbatch according to any one of claims 1 to 3, wherein the method comprises the following steps: the preparation method comprises the following preparation steps:
step one, preparation of compounded rubber
Drying the weighed natural rubber and acrylate rubber, and adding the dried natural rubber and acrylate rubber and a compatibilizer, an anti-aging agent, stearic acid, sulfur, carbon black and a coupling agent which are weighed in proportion into an internal mixer for mixing to prepare composite rubber;
step two, extruding the materials
Pouring the prepared composite rubber into a co-rotating double-screw extruder, adding the weighed microcrystalline wax, accelerator and stabilizer into the extruder together for extruding, putting strips extruded from a nozzle of the extruder into a water tank for cooling, and then cutting the strips into particles by a granulator;
step three, drying and sealing
Drying the cut granules by a hot air dryer, screening by a material screening machine, and sealing and storing in a sealing bag.
5. The method for preparing the modified composite rubber masterbatch according to claim 4, wherein: in the first step, the pressure in a mixing chamber of the internal mixer is controlled to be 5-8 bar, and the temperature in the mixing chamber is controlled to be 150-200 ℃.
6. The method for preparing the modified composite rubber masterbatch according to claim 4, wherein: the heating temperature area of the co-rotating double-screw extruder in the step two is as follows: 110-115 ℃ in zone 1, 115-120 ℃ in zone 2, 115-120 ℃ in zone 3, 120-130 ℃ in zone 4, 120-130 ℃ in zone 5, 130-140 ℃ in zone 6, 140-150 ℃ in zone 7, 150-160 ℃ in zone 8 and 160 ℃ in head.
7. The method for preparing the modified composite rubber masterbatch according to claim 4, wherein: and in the third step, the drying temperature of the hot air dryer is controlled to be 90-110 ℃, and the drying time is 3-5 hours.
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| CN109679159B true CN109679159B (en) | 2021-02-09 |
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