CN116001157A - Rubber production and vulcanization method - Google Patents
Rubber production and vulcanization method Download PDFInfo
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- CN116001157A CN116001157A CN202211705153.7A CN202211705153A CN116001157A CN 116001157 A CN116001157 A CN 116001157A CN 202211705153 A CN202211705153 A CN 202211705153A CN 116001157 A CN116001157 A CN 116001157A
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Abstract
The invention discloses a rubber production and vulcanization method, and relates to the technical field of rubber production. The method mainly comprises the steps of placing rubber compound to be vulcanized in a mold cavity, spraying ethanol to the mold cavity and/or the rubber compound until liquid beads are formed on the inner surface of the mold cavity, and after mold closing, raising the temperature in the mold cavity and the temperature of the rubber compound to the vulcanization temperature for vulcanization reaction. The production and vulcanization method of the rubber product can completely exhaust the air in the die cavity in the vulcanization process, avoid air blocking in the die cavity or between the rubber compounds, prevent poor appearance such as lack of materials or unripeness caused by unbalanced heat conduction, and solve the problems of air accumulation defects such as complex structure, deeper die cavity, better rubber compound fluidity and lower hardness in the rubber vulcanization process.
Description
Technical Field
The invention relates to the technical field of rubber production, in particular to a rubber production and vulcanization method.
Background
The rubber is a high-elasticity polymer material with reversible deformation, is elastic at room temperature, can generate larger deformation under the action of small external force, and can recover after the external force is removed. Rubber is classified into natural rubber and synthetic rubber. The natural rubber is prepared by extracting colloid from plants such as rubber tree, rubber grass, etc.; the synthetic rubber is obtained by polymerizing various monomers.
Vulcanized rubber refers to vulcanized rubber, has the characteristics of no tackiness, difficult breakage and the like, and rubber products are mostly made of the rubber. Also known as cooked rubber, known as rubber or rubber skin. The rubber is generally called after being vulcanized. The vulcanized rubber has a space three-dimensional structure, and has high elasticity, heat resistance, tensile strength, insolubility in organic solvents and the like. The rubber products are mostly vulcanized rubber.
When the rubber is formed by compression molding and vulcanization, the rubber compound is preformed into various proper shapes, then the rubber compound is placed in a mold cavity, the mold is closed and pressurized, and vulcanization is completed in the mold cavity, so that the raw rubber molecular chains are crosslinked and bonded to form a net structure, and the tensile strength, rebound performance and the like of the rubber product are achieved.
At present, chinese patent publication No. CN108690207A discloses a three-step vulcanized rubber processing method, natural rubber and artificial rubber raw materials are mixed according to a ratio of 7:3, diluted sulfuric acid with mass fraction of 10-20% is added, three-step vulcanization treatment is carried out, and finally natural cooling to room temperature is waited.
The rubber vulcanization method improves the molecular weight in rubber through three-step vulcanization, is favorable for improving elasticity, but the rubber is frequently in contact with air in a die cavity and is not discharged in the compression molding process, and is blocked in the die cavity or between rubber compounds by rubber compounds, so that poor appearance such as material shortage or unripeness caused by unbalanced heat conduction is caused, and the rubber vulcanization method is particularly used for products with complex structures, deeper die cavities, better rubber compound fluidity and lower hardness, and the appearance defects are short for air accumulation, air pockets or air inclusion in the industry.
Disclosure of Invention
The invention aims at the technical problems and overcomes the defects of the prior art, and provides a rubber production and vulcanization method.
In order to solve the technical problems, the invention provides a rubber production and vulcanization method.
The technical effects are as follows: the air in the die cavity can be completely discharged in the vulcanization process, so that air is prevented from being blocked in the die cavity or between the rubber compounds, and poor appearance such as lack of materials or incoordination caused by unbalanced heat conduction is prevented, namely, the problems of air accumulation defects of complex structure, deeper die cavity, better rubber compound fluidity and lower hardness are solved in the rubber vulcanization process.
The technical scheme of the invention is as follows:
the vulcanizing method of rubber mainly comprises the steps of placing rubber compound to be vulcanized in a mold cavity, spraying ethanol to the mold cavity and/or the rubber compound until liquid beads are formed on the inner surface of the mold cavity, and raising the temperature in the mold cavity and the temperature of the rubber compound to vulcanization temperature after mold closing to carry out vulcanization reaction;
the sulfiding temperature is greater than or equal to the vaporization temperature of ethanol.
Further, the ethanol is 75% ethanol or absolute ethanol, and the rubber compound is one of ethylene propylene rubber, styrene butadiene rubber or chloroprene rubber.
In the method for vulcanizing rubber, the Mooney viscosity (ML1+4 at 100 ℃) of the rubber compound is 5-40 N.m.
The invention also provides a production method of the rubber product, in the vulcanization process of the rubber product, the rubber is vulcanized by any one of the vulcanization methods, and the rubber is composed of the following components by weight
The vulcanization method for the rubber comprises the following steps:
s1, mixing all materials according to a proportion, putting a rubber base material into an internal mixer for plasticating for 1min, and putting white carbon black, filler, filling oil and stearic acid into the internal mixer for mixing for 3min;
s2, discharging glue when the temperature in the internal mixer is 100 ℃, rolling into sheets by an open mill, and standing for 24 hours;
s3, putting the sheet-shaped rubber material after standing into an internal mixer, adding a functional additive, sulfur and an accelerator for internal mixing, discharging the rubber material when the temperature reaches 85 ℃, adjusting the roll gap to be 1.2mm thin and 2 times on the open mixer, adjusting the roll gap to be 5mm for 3 times of rubber turning, and adjusting the roll gap to be 8mm for standby;
s4, forming the thinned sheet-shaped sizing material into a required shape and weight, putting the sheet-shaped sizing material into a mold cavity, spraying absolute ethyl alcohol on the sizing material and/or the surface of the mold cavity until a liquid bead is formed in the mold cavity, closing the mold, and vulcanizing for 200-300S under the pressure condition of 15+/-1 MPa and the temperature condition of 150-165 ℃ to obtain a rubber product finished product.
The vulcanization method of the rubber is used for vulcanization, and the filler is clay, kaolin or light calcium carbonate.
The rubber vulcanizing method is used for vulcanizing, and the filling oil is naphthenic oil, paraffinic oil or polar oil.
The vulcanization method of the rubber is used for vulcanization, and the functional additive is zinc oxide or active zinc oxide.
The vulcanization method of the rubber is characterized in that vulcanization is carried out, and the accelerator is at least one of accelerator TT, accelerator MTT or accelerator BZ.
The beneficial effects of the invention are as follows:
(1) According to the invention, the problem of air accumulation or wind inclusion in the vulcanization process of the rubber product can be effectively solved by adopting the method of spraying absolute ethyl alcohol for vulcanization, and the method is particularly effective for products which have complex structures, deeper cavities, better flowability of the rubber compound and lower hardness and can not be solved by the conventional method. The principle is that after the product is sprayed with absolute ethyl alcohol and is clamped in a die, the lower boiling point evaporates into a gaseous state when the die is clamped, so that the air pressure in a die cavity is increased, positive pressure is externally formed, the die generates gaps through the exhaust action of a machine, and air in the die cavity is taken out of the die cavity together, thereby solving the air accumulation problem;
(2) In the invention, the method of spraying distilled water is used for vulcanization, and the distilled water is found to be easy to cause ethylene propylene diene monomer foam and is not suitable for exhaust of ethylene propylene diene monomer; in addition, the aqueous venting agent can sometimes be wrapped in the sizing material to generate bubbles because of higher boiling point and lower evaporation; in the sizing material containing more water absorbing components (inorganic filler) in the formula, the water can be absorbed after the sizing material contacts water, and bubbles or foaming of the product are caused in the vulcanization process; therefore, the invention supplements the application defect of distilled water in ethylene propylene diene monomer rubber and high light color filling rubber;
(3) According to the invention, absolute ethyl alcohol (99% alcohol) is used for remarkably improving bad air accumulation of ethylene propylene rubber, high-light color filled products with low hardness and lower hardness, so that the quality of corresponding rubber products is optimized;
(4) According to the invention, by comparing the effects of several volatile substances on rubber exhaust, an efficient vulcanization method and a rubber production method are confirmed, the problems of air accumulation defects of complex structure, deeper cavity, over-good flowability of the rubber compound and lower hardness are solved, the application defects of distilled water in ethylene propylene diene monomer rubber and high-light-color filled rubber are supplemented, and the method has great application value.
Drawings
FIG. 1 is a view showing the external appearance of an SBR pedal skin;
fig. 2 is an outline view of a CR low-hardness bellows.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and the detailed description. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The production method of the rubber product provided by the embodiment comprises the following components in parts by weight:
wherein the filler is clay, kaolin or light calcium carbonate; the filling oil is naphthenic oil, paraffinic oil or polar oil; the functional additive is zinc oxide or active zinc oxide; the promoter is at least one of promoter TT, promoter MTT or promoter BZ.
In the preparation of rubber articles, the method comprises the following steps:
s1, mixing all materials according to a proportion, putting a rubber base material into an internal mixer for plasticating for 1min, and putting white carbon black, filler, filling oil and stearic acid into the internal mixer for mixing for 3min;
s2, discharging glue when the temperature in the internal mixer is 100 ℃, rolling into sheets by an open mill, and standing for 24 hours;
s3, putting the sheet-shaped rubber material after standing into an internal mixer, adding a functional additive, sulfur and an accelerator for internal mixing, discharging the rubber material when the temperature reaches 85 ℃, adjusting the roll gap to be 1.2mm thin and 2 times on the open mixer, adjusting the roll gap to be 5mm for 3 times of rubber turning, and adjusting the roll gap to be 8mm for standby;
s4, forming the thinned sheet-shaped sizing material into a required shape and weight, putting the sheet-shaped sizing material into a mold cavity, spraying absolute ethyl alcohol on the sizing material and/or the surface of the mold cavity until a liquid bead is formed in the mold cavity, closing the mold, and vulcanizing for 200-300S under the pressure condition of 15+/-1 MPa and the temperature condition of 150-165 ℃ to obtain a rubber product finished product.
Wherein, the most critical step is vulcanization of rubber, and the specific steps are as follows: and placing the rubber compound to be vulcanized in a mold cavity, spraying ethanol to the mold cavity and/or the rubber compound until the inner surface of the mold cavity forms liquid beads, and after the mold is closed, raising the temperature in the mold cavity and the temperature of the rubber compound to the vulcanization temperature to carry out vulcanization reaction.
In the vulcanization, the vulcanization temperature is equal to or higher than the gasification temperature of ethanol (78 ℃). The ethanol is 75% ethanol or absolute ethanol, and the rubber compound is one of ethylene propylene rubber, styrene butadiene rubber or chloroprene rubber. In the vulcanization step, the Mooney viscosity (ML1+4 at 100 ℃) of the compound is 5 to 40 N.multidot.m.
The invention also verifies the effect of using the vulcanization method through a plurality of examples and comparative examples.
Example 1: preparation of SBR pedal skin. The shape of the SBR pedal skin is shown in fig. 1.
Proportioning: 100 parts of styrene-butadiene rubber, 20 parts of white carbon black, 60 parts of clay, 10 parts of carbon black, 20 parts of naphthenic oil, 5 parts of active zinc oxide, 1 part of stearic acid, 2 parts of sulfur and 1.5 parts of accelerator CZ.
Rubber mixing: firstly, pouring styrene-butadiene rubber into an internal mixer to plasticate for 2 minutes, pouring white carbon black, clay, carbon black, naphthenic oil, active zinc oxide, stearic acid and naphthenic oil, mixing for 4 minutes, discharging rubber when the temperature in the internal mixer is 120 ℃, and calendaring into a sheet shape for standby application by an open mill; placing the mixture into an internal mixer after standing for 24 hours, adding sulfur and an accelerant for banburying, discharging the mixture when the temperature reaches 85 ℃, adjusting the roll spacing to 1mm thin through 2 times on an open mill, adjusting the roll spacing to 5mm thin through 3 times, and adjusting the roll spacing to 8mm thin through for standby.
And (3) forming: the sizing material is preformed into the required shape and weight, the sizing material is put into a mould cavity of a mould pressing product, absolute ethyl alcohol is sprayed on the surface of the sizing material or the mould cavity (based on the condition that liquid beads exist before mould closing), the mould is closed, and the product is vulcanized for 230s at the temperature of 155-160 ℃ under the pressure of 15+/-1 MPa, so as to obtain the vulcanized pedal skin product.
Example 2 preparation of epdm strands.
Proportioning: 100 parts of ethylene propylene diene monomer, 10 parts of white carbon black, 40 parts of carbon black, 30 parts of kaolin, 50 parts of paraffin oil, 5 parts of active zinc oxide, 1 part of stearic acid, 1 part of sulfur, 1.5 parts of accelerator BZ and 0.4 part of accelerator TT.
Rubber mixing: firstly, adding ethylene propylene diene monomer into an internal mixer for plasticating for 1 minute, adding white carbon black, kaolin, paraffin oil, active zinc oxide and stearic acid for mixing for 5 minutes, discharging rubber at 130 ℃ in the internal mixer, calendaring into a sheet shape for standby use by an open mill, standing for 24 hours, adding rubber into the internal mixer, adding sulfur and an accelerant for banburying, discharging rubber when the temperature reaches 85 ℃, regulating the roll gap to be 1mm for 2 times, regulating to be 5mm for 3 times, and regulating to be 8mm for standby use.
And (3) forming: and (3) preforming the sizing material into the required shape and weight, putting the sizing material into a mold cavity of a mold pressing product, spraying absolute ethyl alcohol (based on the condition that liquid beads exist before mold closing) on the surface of the sizing material or the mold cavity, closing the mold, and vulcanizing the product at the temperature of 160-165 ℃ for 250s under the pressure of 15+/-1 MPa to obtain a vulcanized wire harness product.
Example 3 preparation of cr low durometer bellows.
Proportioning: 100 parts of neoprene, 8 parts of white carbon black, 30 parts of carbon black, 50 parts of light calcium carbonate, 50 parts of polar oil, 1 part of stearic acid, 5 parts of zinc oxide, 0.5 part of sulfur and 1 part of accelerator MTT.
Rubber mixing: firstly, adding chloroprene rubber into an internal mixer to plasticate for 1 minute, adding white carbon black, light calcium, polar oil and stearic acid to mix for 3 minutes, discharging rubber at the temperature of 100 ℃ in the internal mixer, calendaring into a sheet shape for standby use by an open mill, standing for 24 hours, adding zinc oxide, sulfur and an accelerator into the internal mixer to banburying, discharging rubber when the temperature reaches 85 ℃, regulating the roll gap to be 1.2mm and thin for 2 times on the open mill, regulating to be 5mm and turning over the rubber for 3 times, and regulating to be 8mm and discharging the sheet for standby use.
And (3) forming: and (3) preforming the sizing material into the required shape and weight, putting the sizing material into a mold cavity of a mold pressing product, spraying absolute ethyl alcohol (based on the condition that liquid beads exist before mold closing) on the surface of the sizing material or the mold cavity, closing the mold, and vulcanizing the product at the temperature of 150-155 ℃ for 300s under the pressure of 15+/-1 MPa to obtain the vulcanized low-hardness corrugated pipe product.
In the three examples, tap water, distilled water, 75% alcohol and absolute ethyl alcohol are sprayed in the vulcanization process respectively, the air accumulation reject ratio of the obtained rubber products is shown in table 1, and the comparative example is a rubber product prepared by directly vulcanizing without spraying a medium.
TABLE 1 air accumulation failure rate for various examples under different spray media
From table 1, it can be seen that, the air accumulation reject ratio of the three rubber products sprayed with the absolute ethyl alcohol is greatly reduced, and is approximately 20 times lower than that of the spray water, so that the air accumulation reject ratio is greatly optimized compared with that of the product sprayed with the absolute ethyl alcohol, and the superiority of the product sprayed with the absolute ethyl alcohol for vulcanization in the scheme is illustrated.
In addition to the embodiments described above, other embodiments of the invention are possible. All technical schemes formed by equivalent substitution or equivalent transformation fall within the protection scope of the invention.
Claims (9)
1. A vulcanization method of rubber is characterized in that: placing the rubber compound to be vulcanized in a mold cavity, spraying ethanol to the mold cavity and/or the rubber compound until the inner surface of the mold cavity forms liquid beads, and after mold closing, raising the temperature in the mold cavity and the temperature of the rubber compound to the vulcanization temperature for vulcanization reaction;
the sulfiding temperature is greater than or equal to the vaporization temperature of ethanol.
2. A method of vulcanizing rubber as claimed in claim 1, wherein: the ethanol is 75% ethanol or absolute ethanol, and the rubber compound is one of ethylene propylene rubber, styrene butadiene rubber or chloroprene rubber.
3. A method of vulcanizing rubber as claimed in claim 1, wherein: the Mooney viscosity (ML1+4 at 100 ℃) of the rubber compound is 5-40 N.m.
4. A process for producing a rubber article, characterized in that vulcanization is carried out by the vulcanization method of a rubber according to any one of claims 1 to 3, and the rubber is composed of the following components by weight
5. The method for producing a rubber product according to claim 4, comprising the steps of:
s1, mixing all materials according to a proportion, putting a rubber base material into an internal mixer for plasticating for 1min, and putting white carbon black, filler, filling oil and stearic acid into the internal mixer for mixing for 3min;
s2, discharging glue when the temperature in the internal mixer is 100 ℃, rolling into sheets by an open mill, and standing for 24 hours;
s3, putting the sheet-shaped rubber material after standing into an internal mixer, adding a functional additive, sulfur and an accelerator for internal mixing, discharging the rubber material when the temperature reaches 85 ℃, adjusting the roll gap to be 1.2mm thin and 2 times on the open mixer, adjusting the roll gap to be 5mm for 3 times of rubber turning, and adjusting the roll gap to be 8mm for standby;
s4, forming the thinned sheet-shaped sizing material into a required shape and weight, putting the sheet-shaped sizing material into a mold cavity, spraying absolute ethyl alcohol on the sizing material and/or the surface of the mold cavity until a liquid bead is formed in the mold cavity, closing the mold, and vulcanizing for 200-300S under the pressure condition of 15+/-1 MPa and the temperature condition of 150-165 ℃ to obtain a rubber product finished product.
6. The method for producing a rubber product according to claim 5, wherein: the filler is clay, kaolin or light calcium carbonate.
7. The method for producing a rubber product according to claim 5, wherein: the filling oil is naphthenic oil, paraffinic oil or polar oil.
8. The method for producing a rubber product according to claim 5, wherein: the functional additive is zinc oxide or active zinc oxide.
9. The method for producing a rubber product according to claim 5, wherein: the accelerator is at least one of accelerator TT, accelerator MTT or accelerator BZ.
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