CN113929991A - Anti-scorching CR unvulcanized rubber stored at room temperature for long time, preparation method thereof and preparation method of anti-scorching agent - Google Patents
Anti-scorching CR unvulcanized rubber stored at room temperature for long time, preparation method thereof and preparation method of anti-scorching agent Download PDFInfo
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- C07D277/62—Benzothiazoles
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Abstract
A scorch-resistant CR unvulcanized rubber which is stored for a long time at room temperature and is scorch-resistant, a preparation method thereof and a preparation method of a scorch-resistant agent, the materials comprise: raw rubber, a reinforcing filler, a plasticizer, a vulcanization accelerator, a coupling agent, an anti-aging agent, an anti-scorching agent, an active agent and a processing aid, wherein during the preparation of unvulcanized rubber, the raw rubber is prepared into a prefabricated rubber sheet; then adding the prefabricated rubber sheets into an internal mixer or an open mill, adding an active agent, a reinforcing filler, a plasticizer, a coupling agent, an anti-scorching agent and other processing aids, mixing at low temperature and then discharging rubber to prepare a section of rubber compound; and finally, standing and cooling the first-stage rubber compound, adding the vulcanization accelerator and the anti-aging agent into an open mill for mixing, fully opening cooling water during open milling, thinly passing at a low temperature, uniformly mixing, and then discharging to obtain the final rubber compound. According to the invention, through various improvements, the generated rubber material has excellent scorching safety and can be stored for a long time.
Description
Technical Field
The invention relates to a CR (CR) unvulcanized rubber and a preparation method thereof, in particular to a scorch-proof CR unvulcanized rubber capable of being stored at room temperature for a long time and a preparation method thereof.
Background
Chloroprene rubber is a high-molecular elastomer polymerized from 2-chloro-1, 3-butadiene, one of the main varieties of synthetic rubber, and is also a synthetic rubber developed earlier. As a general special rubber, the special rubber has good physical properties of general rubber, has excellent heat resistance, weather resistance, oil resistance, flame retardance, flex fatigue resistance, chemical corrosion resistance and the like, and is widely applied to manufacturing rubber tubes, adhesive tapes, wires and cables, adhesives, printing rubber rollers, bridge supports, coatings, flame-retardant conveying belts, air ducts, corrosion-resistant linings and the like.
Although the chloroprene rubber has excellent comprehensive performance and is widely applied to a plurality of products, allyl chloride atoms connected with chloroprene rubber 1 and chloroprene rubber 2 structures are very active and are easy to react with other atoms and the like to form an irreversible cross-linked network structure, and CR has more heat generation in the processing process, is sensitive to temperature and easy to scorch, so that the rubber material has poor fluidity, the scorch time is shortened, the extruded rubber blank is rough, the self-adhesiveness is reduced, the quality problems of product starvation, fillet, sulfur mark, bubble, bulging and the like are caused, and the processability is lost in serious cases. Although reasonable storage conditions and processing procedures can avoid CR scorching during storage and processing, neoprene rubber compounds (uncured rubber) are difficult to store at room temperature for long periods of time, typically with a shelf life of no more than 30 days. In addition, certain special industries, rubber compound selling and alternative processing businesses have higher and higher requirements on the storage period of the CR unvulcanized rubber, and how to improve the storage period of the CR unvulcanized rubber becomes an important subject.
The invention patent application with the name of 'a process method for improving the scorching performance of chloroprene rubber' of application No. CN201510799936.X discloses a process method for improving the scorching performance of CR rubber compound, which comprises the steps of firstly adding CR into formula components which do not influence the scorching time to mix and mix into master batch, and then adding the rest small material components when the rubber compound is produced, thereby achieving the purpose of improving the scorching performance of the chloroprene rubber compound. However, this method is not suitable for final mixing, has significant limitations, and is not suitable for manufacturers without mixing equipment to uniformly add the remaining small materials, and is not suitable for products that need to be made into semi-finished products (such as rubberized fabric, film, etc.) and then stored for a long time.
Application No. CN201310661911.4, entitled "a stable neoprene", discloses a neoprene compound having a certain stability, which avoids the problem of decomposition due to unstable CR in a short time, thereby avoiding waste, but does not relate to scorch resistance of the neoprene, and CR compound can be stored at room temperature for a long period of time.
The invention patent application No. CN201510630352.X named "a combined modified chloroprene rubber" discloses that NR is used to improve the problems of poor cold resistance, roller sticking during rubber mixing, easy scorching, high cost and the like of CR, but NR is nonpolar rubber, has poor ozone resistance, oil resistance and fatigue resistance compared with CR, is not suitable for products with higher performance requirements, and does not relate to CR mixed rubber which can be stored at room temperature for a long time.
The articles "storage stability and processing scorch performance of chloroprene rubber" and "measures to avoid scorch during storage and use of chloroprene rubber" relate only to measures to avoid scorch during storage and processing of raw chloroprene rubber, do not relate to specific formulations and specific technological methods, and do not mention measures to long-term storage of CR rubber compounds at room temperature.
Disclosure of Invention
The invention provides a scorch-proof CR unvulcanized rubber stored at room temperature for a long time and a preparation method thereof aiming at the problem that the current unvulcanized chloroprene rubber is easy to crosslink and scorch, and also provides a preparation method of a scorch-proof agent.
The technical means adopted by the invention to solve the problems are as follows: a scorch resistant CR unvulcanized rubber for long-term storage at room temperature, comprising: the rubber comprises raw rubber, a reinforcing filler, a plasticizer, a vulcanization accelerator, a coupling agent, an anti-aging agent, an anti-scorching agent, an active agent and a processing aid, wherein the mass ratio of each component is as follows: raw rubber: 100 parts of reinforcing filler: 10-180 parts of plasticizer: 0-30 parts of a vulcanization accelerator: 0.2-15 parts of coupling agent: 0-5 parts of an anti-aging agent: 0-16 parts of a scorch retarder: 0.1-5 parts of active agent: 1-10 parts of a processing aid: 1-20 parts of raw rubber, wherein the raw rubber is chloroprene rubber or a mixture of chloroprene rubber and more than one of chlorinated polyethylene, chlorohydrin rubber, polyvinyl chloride and ethylene propylene rubber, and the mass ratio of the chloroprene rubber to other high polymers is 60:40-95: 5.
Further, the chloroprene rubber is non-sulfur regulation type chloroprene rubber with medium and low Mooney viscosity, the chlorinated polyethylene is rubber type CM with chlorine content of about 35%, the CM type is low Mooney type, and the polyvinyl chloride is a paste resin high-elasticity product with medium and low polymerization degree.
The reinforcing filler is one or more of carbon black, white carbon black, calcium carbonate, pottery clay, silicate filler and talcum powder.
Furthermore, the silicate filler is a nano-material strong micro powder, and the calcium carbonate is light calcium carbonate.
Further, when the white carbon black and the coupling agent are used together, the mass ratio of the white carbon black to the coupling agent is 10:0-10: 2.
Further, the plasticizer is more than one of alkane oil, paraffin oil, naphthenic oil, aromatic oil, petroleum resin, rosin and dioctyl sebacate.
Further, the vulcanization accelerator is two or more of zinc oxide, ethylene thiourea, 1, 3-trimethylene-2-thiourea, 3-methyl-2-thiazolethione, N' -m-phenylene bismaleimide, insoluble sulfur, N-cyclohexyl-2-benzothiazolesulfenamide, dicumyl peroxide, dimorpholine disulfide, N-oxydiethylene-2-benzothiazolesulfenamide, tetraethylthiuram disulfide and tetraethylthiuram monosulfide.
Further, the dosage of ethylene thiourea and 1, 3-trimethylene-2-thiourea is controlled below 0.8 part; the dosage of the tetraethyl thiuram disulfide and the tetraethyl thiuram monosulfide is not more than 1 part; the zinc oxide is indirect zinc oxide, and the dosage of the zinc oxide is not more than 4 parts.
The antioxidant is more than one of antioxidant 2246, antioxidant ODA, antioxidant 1010, antioxidant 702, antioxidant 4020, antioxidant 3100, and microcrystalline wax.
Further, the scorch retarder is 3, 5-dibenzothiazyl salicylic acid.
Further, the active agent is more than one of magnesium oxide, stearic acid or stearate.
The processing aid is one or more of tackifying resin, compatilizer, dispersant, curing agent, adhesive, exhaust flowing agent and anti-roll agent.
A method for preparing CR unvulcanized rubber with scorch prevention and long-term storage at room temperature comprises the steps of thinly passing or uniformly blending chloroprene rubber raw rubber or chloroprene rubber raw rubber and other high polymers on an internal mixer or an open mill to prepare a prefabricated rubber sheet, wherein the other high polymers are uniformly mixed with a plasticizer firstly and thinly passed and uniformly distributed on the open mill or the internal mixer and then discharged; adding the cooled prefabricated rubber sheet into an internal mixer or an open mill, adding an active agent, a reinforcing filler, a plasticizer, a coupling agent, an anti-scorching agent and other processing aids, mixing at low temperature, and discharging rubber to obtain a rubber compound; and finally, standing and cooling the first-stage rubber compound, adding the vulcanization accelerator and the anti-aging agent into an open mill for mixing, fully opening cooling water during open milling, thinly passing at a low temperature, uniformly mixing, and then discharging to obtain the final rubber compound.
Further, when a section of rubber compound is prepared, the low-temperature mixing time is 6-15 minutes, and the rubber discharging temperature is not more than 115 ℃.
Further, the standing and cooling time of the rubber compound for one section is more than 4 hours, and the low-temperature thin-passing times are more than 5 times.
Further, the temperature of the compound does not exceed 90 ℃ throughout the preparation of the final compound.
The preparation method of the anti-coking agent is characterized in that the anti-coking agent is 3, 5-dibenzothiazole salicylic acid, and is synthesized by adopting one-step reaction of 2-mercaptobenzothiazole and 3, 5-dibrominated salicylic acid.
Further, the synthesis steps are as follows: adding 2-mercaptobenzothiazole (2.0-2.2 eq), 3, 5-dibrominated salicylic acid (1.0 eq), sodium carbonate (3.0-5.0 eq), sodium iodide (0.1-1.0 eq) and an ethanol solvent (50-80 eq) into a reaction container, and reacting at 50-80 ℃ for 24-48 h in a nitrogen atmosphere; and (3) after the reaction is finished, spin-drying the solvent, and performing vacuum drying to obtain the 3, 5-dibenzothiazyl salicylic acid.
The invention has the beneficial effects that:
1. according to the invention, a rubber material with slow reaction is used in a formula, a novel functional scorch inhibitor is combined for use, the effective reactivity of CR is reduced, low-temperature rubber mixing is adopted in a rubber mixing process, the consumption of scorch time in the rubber mixing process is reduced, three modes are combined for use, and the scorch resistance and the storage resistance of CR are obviously improved, so that the CR unvulcanized rubber capable of being stored at room temperature for a long time is provided, the rubber material has excellent scorch safety and storage stability, the CR unvulcanized rubber and a semi-finished product thereof can be kept at room temperature for 6 months and still have good processing manufacturability, and the adhesive strength, flexibility, oil resistance, high tensile property and the like of the product are not obviously reduced when the CR unvulcanized rubber is used for producing the finished product.
2. When the final rubber compound is prepared, an open mill is adopted for vulcanizing and mixing, and cooling water is completely opened so as to control the temperature below 90 ℃ and reduce scorching in the rubber mixing process.
3. The functional group of the salicylic acid of the 3, 5-dibenzothiazole salicylic acid scorch retarder can consume CR sizing material vulcanizing agents zinc oxide and magnesium oxide, and the group of the benzothiazole can react with accelerators such as sulfenamides and the like, so that the double scorch prevention effect is achieved, and the scorch resistance of CR is effectively improved.
Drawings
FIG. 1 is a structural diagram of a 3, 5-dibenzothiazyl salicylic acid molecule of the present invention;
FIG. 2 shows the reaction scheme of 3, 5-dibenzothiazyl salicylic acid of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings. Wherein the showings are for the purpose of illustration only and are shown by way of illustration only and not in actual form, and are not to be construed as limiting the present patent; to better illustrate the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
Example one
This example is a method for producing an anti-scorch agent, in which 2-mercaptobenzothiazole (0.21mol, 35.0 g), 3, 5-dibromo-salicylic acid (0.10 mol, 29.6 g), sodium carbonate (0.3 mol, 31.8 g), sodium iodide (0.02 mol, 3.0 g) and an ethanol solvent (5.0 mol, 288 mol) are added to a reaction vessel, and reacted at 50 to 80 ℃ for 24 to 48 hours in a nitrogen atmosphere. After the reaction is finished, the solvent is dried in a spinning mode, and vacuum drying is carried out, so that the 3, 5-dibenzothiazyl salicylic acid shown in the figure 1 can be obtained, and is abbreviated as DPNTS, and the reaction formula is shown in the figure 2.
The following second to fourth examples are all CR unvulcanized rubber which is scorch resistant and stored at room temperature for a long period of time, and a method for preparing the same.
Example two
The rubber material comprises the following components in parts by weight: 100 parts of chloroprene rubber, 4 parts of high-activity magnesium oxide, 0.5 part of stearic acid, 20 parts of carbon black, 30 parts of white carbon black, 1 part of coupling agent, 15 parts of alkane oil, 2 parts of indirect zinc oxide, 3 parts of dimorpholine disulfide, 0.5 part of insoluble sulfur, 0.5 part of N-oxydiethylene-2-benzothiazole sulfonamide, 0.6 part of ethylene thiourea, 0.2 part of functional anti-scorching agent 3, 5-dibenzothiazole salicylic acid and 2 parts of anti-sticking agent.
The preparation process of the sizing material comprises the following steps: the chloroprene rubber is thinly passed through an open mill and then is sliced, and is put into an internal mixer or an open mill, then carbon black, white carbon black, a coupling agent, a functional anti-scorching agent and an anti-sticking roller agent are added, and rubber is discharged after mixing for 12 minutes, wherein the rubber discharging temperature is 108 ℃, so that a first-stage rubber compound is prepared; placing the cooled rubber compound for 8 hours into an open mill, fully opening cooling water of the open mill, uniformly coating rollers, then adding zinc oxide, dimorpholine disulfide, insoluble sulfur, N-oxydiethylene-2-benzothiazole sulfenamide and ethylene thiourea in batches, thinly passing for 5 times at a low temperature, uniformly mixing, then discharging, wherein the temperature of the rubber compound in the whole process is not more than 80 ℃, and thus obtaining the CR rubber compound.
EXAMPLE III
The rubber material comprises the following components in parts by weight: 75 parts of chloroprene rubber, 25 parts of chlorinated polyethylene CM, 5 parts of magnesium oxide, 0.7 part of stearic acid, 20 parts of calcium carbonate, 30 parts of white carbon black, 0-692.0 part of coupling agent Si-692.0 part, 15 parts of naphthenic oil, 4 parts of indirect zinc oxide, 0.5 part of functional anti-scorching agent 3, 5-dibenzothiazole salicylic acid, 0.3 part of 1, 3-trimethylene-2-thiourea, 2.0 parts of N, N' -m-phenylene bismaleimide, 0.3 part of N-cyclohexyl-2-benzothiazole sulfenamide and 10102 part of antioxidant.
The preparation process of the sizing material comprises the following steps: adding 5-10 parts of naphthenic oil into 100 parts of chlorinated polyethylene, uniformly stirring, thinly passing the mixture on a cold roll open mill for more than 10 times until the film is uniformly translucent, and taking the film down for later use; thinly passing the chloroprene rubber raw rubber and the thin-passing rubber sheet on a low-temperature open mill according to the proportion of 75/25 for 5 times, uniformly blending to prepare CR/CM blended raw rubber, and cooling for later use after sheet feeding; putting the CR/CM blended crude rubber into an internal mixer, adding a functional anti-scorching agent, calcium carbonate, white carbon black, a coupling agent and naphthenic oil, mixing for 12 minutes at a low temperature, and then discharging rubber at a rubber discharging temperature of 110 ℃ to prepare a first-stage rubber compound; placing the rubber compound for 4 hours for cooling, putting the rubber compound into an open mill, fully opening cooling water of the open mill, uniformly wrapping rollers, putting zinc oxide, 1, 3-trimethylene-2-thiourea, N' -m-phenylene bismaleimide, N-cyclohexyl-2-benzothiazole sulfenamide and an antioxidant in batches, thinly passing the mixture at a low temperature for 5 times, uniformly mixing the mixture, then discharging the mixture, and obtaining the rubber compound at the rubber discharge temperature of 85 ℃.
Example four
The rubber material comprises the following components in parts by weight: 85 parts of chloroprene rubber, 15 parts of polyvinyl chloride, 4 parts of magnesium oxide, 0.5 part of stearic acid, 4 parts of indirect zinc oxide, 30 parts of calcium carbonate, 20 parts of white carbon black, Si-691.0 parts of a coupling agent, 10 parts of paraffin oil, 0.3 part of a functional anti-coking agent 3, 5-dibenzothiazole salicylic acid, 0.5 part of sulfur, 1 part of 3-methyl-2-thiazole thioketone, 2 parts of dimorpholine disulfide, 0.2 part of N-cyclohexyl-2-benzothiazole sulfonamide, 0.5 part of tetraethylthiuram monosulfide, 40202 parts of an anti-aging agent and C92 parts of petroleum resin.
The preparation process of the sizing material comprises the following steps: adding 5-15 parts of paraffin oil into 100 parts of polyvinyl chloride, uniformly stirring, uniformly thinly passing on a cold roll open mill, and taking down the sheets for later use; uniformly mixing chloroprene rubber raw rubber and the thin polyvinyl chloride film on a low-temperature open mill according to the proportion of 85/15 to obtain CR/PVC blended raw rubber, and cooling the rubber for later use after the rubber is discharged; putting the CR/PVC blended raw rubber into an internal mixer, adding calcium carbonate, white carbon black, a coupling agent, a functional anti-scorching agent and petroleum resin, mixing for 15 minutes, and then discharging rubber at the temperature of 115 ℃ to prepare a first-stage rubber compound; standing for 8 hours, performing two-stage mixing, putting the first-stage mixed rubber, sulfur, 3-methyl-2-thiazole thione, dimorpholine disulfide, N-cyclohexyl-2-benzothiazole sulfonamide, tetraethylthiuram monosulfide and an anti-aging agent into an open mill, mixing for 10 minutes, discharging rubber, and discharging at the rubber discharging temperature of 90 ℃ to obtain the CR mixed rubber.
After the CR rubber compound generated in the second to fourth embodiments is qualified according to the technical index requirements, the CR rubber compound may be used as a semi-finished rubber material to be vulcanized, and put into a room temperature warehouse for use, or a semi-finished rubber material may be prepared according to the product requirements, and the semi-finished rubber material may be an extruded rubber tube, rubber strip, or the like, and may be rolled on a three-roll calender to prepare a rubber sheet with a certain specification and size, or may be rolled with a framework material (such as glass fiber cloth, carbon fiber cloth, nylon cord cloth, or steel cord cloth, or the like) to prepare a rubber sheet, or the like.
To verify the properties of the respective compounds produced in the above examples two to four, the inventors prepared CR compounds by the following three comparative examples for comparison.
Comparative example 1
The material comprises the following components in parts by weight: 100 parts of chloroprene rubber, 4 parts of high-activity magnesium oxide, 0.5 part of stearic acid, 20 parts of carbon black, 30 parts of white carbon black, 1 part of coupling agent, 15 parts of alkane oil, 2 parts of indirect zinc oxide, 3 parts of dimorpholine disulfide, 0.5 part of insoluble sulfur, 0.3 part of dibenzothiazyl disulfide, 0.6 part of ethylene thiourea and 2 parts of anti-sticking agent.
The preparation process of the sizing material comprises the following steps: the chloroprene rubber is thinly passed through an open mill and then is discharged, the chloroprene rubber is put into an internal mixer or an open mill, then carbon black, white carbon black, a coupling agent and an anti-sticking roller agent are added, the mixture is mixed for 25 minutes and then is discharged, and the discharging temperature is 129 ℃, so that a first-section mixed rubber is prepared; placing the cooled rubber compound for 8 hours into an open mill, fully opening cooling water of the open mill, uniformly coating rollers, then adding zinc oxide, dimorpholine disulfide, insoluble sulfur, dibenzothiazyl disulfide and ethylene thiourea in batches, performing low-temperature thin passing for 5 times, uniformly mixing, then discharging the rubber compound, and obtaining the CR rubber compound at the rubber discharge temperature of 110 ℃.
Comparative example 2
The material comprises the following components in parts by weight: 75 parts of chloroprene rubber, 25 parts of chlorinated polyethylene CM, 4 parts of magnesium oxide, 0.7 part of stearic acid, 20 parts of calcium carbonate, 30 parts of white carbon black, Si-692.0 parts of coupling agent, 15 parts of naphthenic oil, 5 parts of indirect-method zinc oxide, 0.8 part of 1, 3-trimethylene-2-thiourea, 2.0 parts of N, N' -m-phenylene bismaleimide, 0.3 part of N-cyclohexyl-2-benzothiazole sulfenamide and 10102 parts of antioxidant.
The preparation process of the sizing material comprises the following steps: adding 5-10 parts of naphthenic oil into 100 parts of CM, uniformly stirring, thinly passing the mixture on a cold roll open mill for more than 10 times until the film is uniform and semitransparent, and taking the film down for later use; thinly passing the chloroprene rubber raw rubber and the thin-passing CM film on a low-temperature open mill according to the proportion of 75/25 for 5 times, uniformly blending to prepare CR/CM blended raw rubber, and cooling for later use after the rubber is discharged; putting the CR/CM blended crude rubber into an internal mixer, then adding calcium carbonate, white carbon black, a coupling agent and naphthenic oil, mixing for 25 minutes at low temperature, and discharging rubber at the temperature of 130 ℃ to prepare a first-stage rubber compound; placing the rubber compound for 4 hours for cooling, putting the rubber compound into an open mill, fully opening cooling water of the open mill, uniformly wrapping rollers, putting zinc oxide, 1, 3-trimethylene-2-thiourea, N' -m-phenylene bismaleimide, N-cyclohexyl-2-benzothiazole sulfenamide and an antioxidant in batches, performing low-temperature thin passing for about 5 times, uniformly mixing, then discharging, and discharging the rubber at the temperature of 90 ℃ to obtain the rubber compound.
Comparative example 3
The material comprises the following components in parts by weight: 85 parts of chloroprene rubber, 15 parts of polyvinyl chloride, 4 parts of magnesium oxide, 0.5 part of stearic acid, 5 parts of indirect-process zinc oxide, 30 parts of calcium carbonate, 20 parts of white carbon black, Si-691.0 parts of a coupling agent, 10 parts of paraffin oil, 0.5 part of sulfur, 1 part of 3-methyl-2-thiazole thione, 2 parts of dimorpholine disulfide, N-cyclohexyl-2-benzothiazole sulfenamide, 0.5 part of tetraethylthiuram monosulfide, 40202 parts of an anti-aging agent and C92 parts of petroleum resin.
The preparation process of the sizing material comprises the following steps: adding 10-15 parts of paraffin oil into 100 parts of polyvinyl chloride, uniformly stirring, and uniformly thinning and slicing on a cold roll open mill for later use; uniformly blending the chloroprene rubber raw rubber and the thin-passing polyvinyl chloride film on a low-temperature open mill for 5 times according to the proportion of 85/15 to prepare CR/PVC blended raw rubber, and cooling the rubber for later use after the rubber is discharged; putting the CR/PVC blended raw rubber into an internal mixer, adding calcium carbonate, white carbon black, a coupling agent and petroleum resin, mixing for 25 minutes, and then discharging rubber at the temperature of 128 ℃ to prepare a first-section rubber compound; standing for 8 hours, performing second-stage mixing, putting the first-stage mixed rubber, sulfur, 3-methyl-2-thiazole thione, dimorpholine disulfide, N-cyclohexyl-2-benzothiazole sulfonamide, tetraethylthiuram monosulfide and an anti-aging agent 4020 into an internal mixer, mixing for 10 minutes, discharging rubber, and discharging at the rubber discharging temperature of 100 ℃ to obtain the CR mixed rubber.
The sizing properties of examples two to four and comparative examples 1 to 3 were examined, respectively, and the results are shown in the following table:
as can be seen from the above table, the rubber compounds of examples two to four not only have good tensile properties, excellent adhesive properties, flex resistance and ozone aging resistance, but also have very excellent scorching safety and storage resistance, and still have good scorching safety and fluidity after being parked for 6 months at room temperature, and the interlayer adhesion strength of the rubber compounds is still high after being parked for 6 months without significant reduction.
The rubber compound of the second to fourth embodiments is rolled with a framework material (glass fiber cloth, carbon fiber cloth or nylon cloth) on a three-roll or four-roll calender at 70-120 ℃ to prepare a rubber cloth, and the rubber cloth is placed for 6 months and then subjected to performance test, and the results are shown in the following table:
as can be seen from the above table, the rubberized fabrics formed by calendering the rubber materials of the second to fourth embodiments have good spreadability and manufacturability within 6 months of standing at room temperature, and the interlaminar adhesive strength between the rubberized fabrics is high, so that the performance requirements of products such as adhesive tapes, air springs, aprons, blade heating components and the like can be met. The rubber materials of comparative examples 1 to 3 are scorched during the calendering of the rubber fabric, and the qualified rubber fabric can not be calendered, but the rubber materials of the examples are very smooth during the calendering process of the rubber fabric, and the surface of the pressed rubber fabric is flat and smooth.
As can be seen from the above examples, the CR rubber material disclosed by the invention not only has excellent physical properties such as tensile property and adhesive strength, but also has excellent scorch resistance and storage stability, can be parked at room temperature (23 +/-2 ℃) for 6 months without scorching, and has a long storage period; in addition, the rubber material has excellent processing technology performance, can meet the technological requirements of extrusion, calendering and the like, can be processed into semi-finished products such as rubber sheets or rubberized fabric and the like, still has good manufacturability and physical performance after being parked for 6 months at room temperature, and can meet the technological requirements and product performance requirements of products. The problem that the chloroprene rubber compound is easy to scorch is solved, the chloroprene rubber compound or a semi-finished product has enough scorch safety in long-time transportation and storage, and the problem of scrapping caused by early crosslinking is avoided, so that the chloroprene rubber product manufacturing, CR compound selling and other rubber and plastic enterprise substitute processing businesses are smoothly carried out.
The above embodiments are provided for illustrative purposes only and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should fall within the scope of the present invention, and the scope of the present invention should be defined by the claims.
Claims (10)
1. A scorch resistant CR unvulcanized rubber for long-term storage at room temperature, comprising: the method comprises the following steps: the rubber comprises raw rubber, a reinforcing filler, a plasticizer, a vulcanization accelerator, a coupling agent, an anti-aging agent, an anti-scorching agent, an active agent and a processing aid, wherein the mass ratio of each component is as follows: raw rubber: 100 parts of reinforcing filler: 10-180 parts of plasticizer: 0-30 parts of a vulcanization accelerator: 0.2-15 parts of coupling agent: 0-5 parts of an anti-aging agent: 0-16 parts of a scorch retarder: 0.1-5 parts of active agent: 1-10 parts of a processing aid: 1-20 parts of raw rubber, wherein the raw rubber is chloroprene rubber or a mixture of chloroprene rubber and more than one of chlorinated polyethylene, chlorohydrin rubber, polyvinyl chloride and ethylene propylene rubber, and the mass ratio of the chloroprene rubber to other high polymers is 60:40-95: 5.
2. The scorch-resistant, long-term stored CR unvulcanized rubber at room temperature of claim 1, wherein: the reinforcing filler is more than one of carbon black, white carbon black, calcium carbonate, argil, silicate fillers and talcum powder;
the plasticizer is more than one of alkane oil, paraffin oil, naphthenic oil, aromatic oil, petroleum resin, rosin and dioctyl sebacate;
the vulcanization accelerator is more than two of zinc oxide, ethylene thiourea, 1, 3-trimethylene-2-thiourea, 3-methyl-2-thiazole thione, N' -m-phenylene bismaleimide, insoluble sulfur, N-cyclohexyl-2-benzothiazole sulfonamide, dicumyl peroxide, dimorpholine disulfide, N-oxydiethylene-2-benzothiazole sulfonamide, tetraethylthiuram disulfide and tetraethylthiuram monosulfide;
the antioxidant is more than one of antioxidant 2246, antioxidant ODA, antioxidant 1010, antioxidant 702, antioxidant 4020, antioxidant 3100 and microcrystalline wax;
the scorch retarder is 3, 5-dibenzothiazyl salicylic acid;
the active agent is more than one of magnesium oxide, stearic acid or stearate;
the processing aid is more than one of tackifying resin, compatilizer, dispersant, curing agent, adhesive, exhaust flowing agent and anti-sticking agent.
3. A scorch resistant CR uncured rubber for long term storage at room temperature according to claim 2, wherein: the silicate filler is nano-material strong micro powder, and the calcium carbonate is light calcium carbonate.
4. The scorch-resistant, long-term stored CR unvulcanized rubber at room temperature of claim 1, wherein: when the white carbon black and the coupling agent are used together, the mass ratio of the white carbon black to the coupling agent is 10:0-10: 2.
5. The scorch-resistant, long-term stored CR unvulcanized rubber at room temperature of claim 1, wherein: the dosage of ethylene thiourea and 1, 3-trimethylene-2-thiourea is controlled below 0.8; the dosage of the tetraethyl thiuram disulfide and the tetraethyl thiuram monosulfide is not more than 1 part; the zinc oxide is indirect zinc oxide, and the dosage of the zinc oxide is not more than 4 parts.
6. A method for producing a CR unvulcanized rubber for long-term storage at room temperature for realizing scorch prevention according to claim 1, wherein: the chloroprene rubber raw rubber or the chloroprene rubber raw rubber and other high polymers are subjected to thin passing or even blending on an internal mixer or an open mill to prepare a prefabricated rubber sheet, wherein the other high polymers are firstly uniformly mixed with a plasticizer, and then are subjected to thin passing and even discharging on the open mill or the internal mixer; adding the cooled prefabricated rubber sheet into an internal mixer or an open mill, adding an active agent, a reinforcing filler, a plasticizer, a coupling agent, an anti-scorching agent and other processing aids, mixing at low temperature, and discharging rubber to obtain a rubber compound; and finally, standing and cooling the first-stage rubber compound, adding the vulcanization accelerator and the anti-aging agent into an open mill for mixing, fully opening cooling water during open milling, thinly passing at a low temperature, uniformly mixing, and then discharging to obtain the final rubber compound.
7. The method of claim 6 for the preparation of scorch resistant CR uncured rubber for long term storage at room temperature, comprising: when a section of rubber compound is prepared, the low-temperature mixing time is 6-15 minutes, and the rubber discharge temperature is not more than 115 ℃;
the standing and cooling time of the rubber compound for one section is more than 4 hours, and the low-temperature thin-passing times are more than 5 times.
8. The method of claim 6, wherein the CR uncured rubber that is long term stored at room temperature and scorch resistant comprises: the temperature of the rubber mass does not exceed 90 ℃ during the entire process of preparing the final rubber compound.
9. The preparation method of the anti-scorching agent is characterized in that the anti-scorching agent is 3, 5-dibenzothiazole salicylic acid: the compound is synthesized by adopting 2-mercaptobenzothiazole and 3, 5-dibrominated salicylic acid through one-step reaction.
10. The method for preparing a scorch retarder according to claim 9, wherein: the synthesis steps of the 3, 5-dibenzothiazyl salicylic acid are as follows: adding 2-mercaptobenzothiazole (2.0-2.2 eq), 3, 5-dibrominated salicylic acid (1.0 eq), sodium carbonate (3.0-5.0 eq), sodium iodide (0.1-1.0 eq) and an ethanol solvent (50-80 eq) into a reaction container, and reacting at 50-80 ℃ for 24-48 h in a nitrogen atmosphere; and (3) after the reaction is finished, spin-drying the solvent, and performing vacuum drying to obtain the 3, 5-dibenzothiazyl salicylic acid.
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