CN109366839B - Method for preparing closed-cell structure rubber foam material by mould pressing physical foaming - Google Patents
Method for preparing closed-cell structure rubber foam material by mould pressing physical foaming Download PDFInfo
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- CN109366839B CN109366839B CN201811108784.4A CN201811108784A CN109366839B CN 109366839 B CN109366839 B CN 109366839B CN 201811108784 A CN201811108784 A CN 201811108784A CN 109366839 B CN109366839 B CN 109366839B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/60—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
- B29K2105/041—Microporous
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Abstract
The invention provides a method for preparing a closed-cell structure rubber foam material by mould pressing physical foaming, which comprises the following steps: (1) mixing the raw rubber and a vulcanizing agent uniformly, or mixing the raw rubber, the resin and the vulcanizing agent uniformly; (2) hot-press molding the obtained rubber compound, and pre-vulcanizing the rubber compound in the hot-press molding process to obtain a rubber blank, or radiating the molded rubber compound by using radiation cross-linking equipment to realize pre-vulcanization to obtain a rubber blank; (3) placing the rubber blank in a foaming mould in mould pressing foaming equipment, inputting gas into the foaming mould after mould closing as a foaming agent, controlling the temperature in the foaming mould to be between room temperature and 80 ℃, swelling the rubber blank under the pressure of 0.5-30 MPa, and then releasing pressure to foam the swelled rubber blank; (4) and (4) post-vulcanizing the pre-vulcanized rubber foaming material obtained in the step (3). The method of the invention can improve the quality of the rubber foaming material and promote the industrial production of the high-quality rubber foaming material.
Description
Technical Field
The invention belongs to the field of rubber foam materials, and relates to a method for preparing a closed-cell structure rubber foam material by mould pressing physical foaming.
Background
The rubber foam material is also commonly called sponge rubber, foamed rubber or microcellular rubber, and is a special rubber material with a porous structure prepared by taking rubber as a matrix. Compared with solid rubber, the porous structure gives the foamed rubber a plurality of special properties, such as: the apparent density is small, and the fabric is soft and comfortable; the sealing performance is good, and the dustproof and waterproof effects can be achieved; good damping performance, heat insulation, sound absorption, shock absorption and the like. Therefore, the foamed rubber is widely applied to the fields of sports equipment, automobile interior trims, aerospace, household appliances and the like, and can be processed into various shapes and specifications according to actual needs. The original rubber foaming product mostly adopts natural rubber or reclaimed rubber as a base material, and in recent years, synthetic rubber, elastomer alloy and blends of rubber and plastics are also used as foaming base materials, so that the variety and the performance of rubber foam materials are greatly enriched, and the application range of the rubber foam materials is widened.
Conventional rubber foams are usually prepared by adding chemical blowing agents or pore formers, with blowing agent or pore former residuesThe product is impure, has defects and influences the use performance of the product. Chemical blowing agents are generally organic substances and can also cause environmental pollution and harm to human health. With the increasing requirements of people on product safety, environmental protection and the like, air and CO are used2、N2Physical foaming methods based on blowing agents such as butane and pentane have been widely regarded.
CN 103419371A discloses a method for preparing rubber foam material with open-cell structure by using supercritical carbon dioxide technology, which comprises placing rubber film with low vulcanization degree in a high-pressure reaction kettle, introducing CO2And is converted into supercritical fluid, and the pressure is quickly released after the supercritical fluid is saturated for a period of time to realize foaming. As kettle type foaming is free foaming, the prepared rubber foam material is easy to generate phenomena of warping, uneven products and the like, the quality of the products is difficult to ensure, meanwhile, the rubber completes the whole swelling and foaming processes in a high-pressure reaction kettle, the design of the high-pressure reaction kettle needs to reserve a large space for foaming expansion, more gas is consumed, the efficiency is low, the high-pressure reaction kettle is difficult to amplify, and high requirements are provided for equipment, so that the production of the rubber foam material with large thickness, particularly the rubber foaming thick plate is difficult to realize by using kettle type intermittent foaming. In addition, the method can prepare the rubber foam material with an open-cell structure, and cannot prepare the rubber foam material with a closed-cell structure.
The mould pressing foaming is limited foaming, the warping problem of the rubber foam material in the foaming process can be solved, the shape of the rubber foam obtained by foaming is the shape of a mould, and the feasibility of industrial production is higher. In the prior art, a solid-state die-pressing foaming technology is usually adopted to prepare a rubber foaming plate with a high foaming ratio and a thickness of more than 10mm, but a process report for preparing a rubber foam material, in particular a rubber foaming thick plate by using a die-pressing foaming technology using gas as a foaming agent is not seen yet.
CN 102604171A discloses a production process of a rubber molded foaming material, which adopts azodicarbonamide, 4 '-oxybis-benzenesulfonylhydrazide, N' -dinitrosopentamethylenetetramine and other chemical foaming agents to prepare the rubber foaming material through mold pressing and foaming. Although this approach can solve the problem of warpage, the following disadvantages still exist: (1) the chemical foaming agent can generate toxic gases such as ammonia gas, carbon monoxide and the like in the decomposition process, and generate pungent smell, so that the production environment is severe, the human body health is harmed, the environment is polluted, and the sustainable development is not facilitated; after the chemical foaming agent is decomposed, small molecular chemical substances are remained in a matrix, so that the product is impure, has certain chemical toxicity, and can influence the service performance and the service life of the product. (2) The decomposition of the foaming agent is a process, and the nucleation and growth conditions of each cell are different (have precedence), so that the uniformity of the cells is poor, the size distribution is very wide, and the phenomena of opening and cell combination are easy to occur. (3) According to the method, a pre-vulcanization process is introduced before foaming, the pre-vulcanization temperature is 100-130 ℃, and decomposition of a foaming agent can not be completely avoided at the temperature, so that a secondary foaming phenomenon is easily generated, and the secondary foaming can cause poor uniformity of foam holes, perforation and foam hole combination phenomena and influence the performance of a product. (4) Although the vulcanization starting point is controlled by the prevulcanization process, the foaming process is still carried out simultaneously with the vulcanization, the chemical foaming agent and the decomposition products thereof can affect the vulcanizing agent, and the problem of foaming-vulcanization matching still exists.
Therefore, if the advantages of the mold pressing foaming and the physical foaming can be combined, a method for preparing the rubber foam material, particularly a rubber foaming thick plate by the mold pressing physical foaming is developed, so that the problems that the foam material is easy to warp, the product performance is not uniform, the industrial scale-up production is difficult and the like in the process of adopting the reaction kettle for foaming are solved, the problems that the foam material is poor in uniformity of cells, the foaming agent and the degradation product thereof are remained, the environment is protected, the foaming-vulcanization matching is realized and the like in the process of adopting the chemical mold pressing foaming are solved, and the important significance and the positive promotion effect are generated for improving the quality of the rubber foam material and realizing the industrial.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a method for preparing a rubber foam material with a closed cell structure by mould pressing physical foaming, overcomes the defect that the prior art does not adopt a process for preparing the rubber foam material by the mould pressing physical foaming technology, improves the quality of the rubber foam material, and promotes the industrial production of the high-quality rubber foam material.
The invention provides a method for preparing a closed-cell structure rubber foam material by mould pressing physical foaming, which comprises the following steps:
(1) uniformly mixing the raw rubber and a vulcanizing agent to obtain a rubber compound; the using amount of the raw rubber is 100 parts by mass, and the using amount of the vulcanizing agent is 1-10 parts by mass;
or uniformly mixing the rubber crude rubber, the resin and a vulcanizing agent to obtain a rubber compound, wherein the total using amount of the rubber crude rubber and the resin is 100 parts by mass, and the using amount of the vulcanizing agent is 1-10 parts by mass;
(2) hot-press molding the rubber compound, and pre-vulcanizing the rubber compound in the hot-press molding process to obtain a rubber blank, or radiating the molded rubber compound by using radiation cross-linking equipment to realize pre-vulcanization to obtain a rubber blank; in the step, the pre-vulcanization degree is controlled to ensure that the Shore A hardness of the rubber blank is 30-90;
(3) placing the rubber blank into a foaming mould of mould pressing foaming equipment, inputting gas into the foaming mould after mould closing as a foaming agent, controlling the temperature in the foaming mould to be between room temperature and 80 ℃ and the pressure to be between 0.5 and 30MPa, maintaining the temperature and the pressure to swell the rubber blank, and then releasing pressure to foam the swelled rubber blank to obtain a pre-vulcanized rubber foaming material;
(4) and (3) post-vulcanizing the pre-vulcanized rubber foam material at 90-250 ℃ to obtain the closed-cell structure rubber foam material.
In the step (2) of the method for preparing the closed-cell structure rubber foam material by mould pressing physical foaming, a rubber blank with the thickness of less than 5mm or a rubber blank with the thickness of at least 5mm can be adopted, and the shape of the rubber blank is determined according to the actual application requirements, such as a cuboid, a cube, a cylinder and other three-dimensional shapes; when the thickness of the rubber blank is at least 5mm, the rubber foam material prepared in the step (4) is a rubber foaming thick plate with the thickness of more than 10 mm.
In the step (2) of the method for preparing the closed-cell structure rubber foam material by mould pressing physical foaming, the pre-vulcanization degree is preferably controlled so that the Shore A hardness of the rubber blank is 30-70.
In the step (1) of the method for preparing the closed-cell structure rubber foam material by mould pressing physical foaming, a reinforcing filler is further added, and the adding amount of the reinforcing filler is 10-100 parts by mass, preferably 15-75 parts by mass. The selection principle of the reinforcing filler is the same as that of the conventional rubber processing, the reinforcing filler is selected and added according to the actual application requirements, and the reinforcing filler can be at least one of calcium carbonate, quartz powder, diatomite, montmorillonite, zeolite, wollastonite, kaolin, mica, mullite, clay, ceramic fiber, hollow glass beads, carbon black, white carbon black, titanium dioxide, aluminum oxide, ferric oxide, graphene or carbon nano tubes.
In the step (1) of the method for preparing the closed-cell structure rubber foam material by mould pressing physical foaming, a rubber processing aid is added during mixing, the rubber processing aid is a rubber processing aid used in the conventional rubber processing process and comprises a vulcanization accelerator, a plasticizer, an anti-aging agent, a flame retardant, a structure control agent and the like, the type and the addition amount of the rubber processing aid are selected and determined according to the type of the raw rubber adopted in the step (1) and the actual application requirement, the addition amount of the rubber processing aid is preferably not more than 50 parts by mass, further the addition amount of the vulcanization accelerator is not more than 5 parts by mass, the addition amount of the plasticizer is not more than 10 parts by mass, the addition amount of the flame retardant is not more than 40 parts by mass, and the addition amount of the structure control agent.
The vulcanization accelerator may be at least one member selected from the group consisting of 2,2' -dithiodibenzothiazole, 2-mercaptobenzothiazole, benzothiazole disulfide, N-cyclohexyl-2-thiazolesulfonamide, N-dicyclohexyl-2-thiazolesulfonamide, tetramethylthiuram disulfide, tetramethylthiuram monosulfide, zinc dimethyldithiocarbamate, hexamethylenetetramine, diphenylguanidine and zinc isopropylxanthate.
The plasticizer may be at least one selected from naphthenic oil, aromatic oil, paraffin oil, coal tar, coumarone, coal pitch, pine tar, terpene resin, ointment, stearic acid, vaseline, phthalate ester, and fatty acid ester.
The antioxidant may be at least one selected from paraffin, hydroquinone dibenzyl ether, N-phenyl-alpha naphthylamine, N- (1, 3-dimethylbutyl) -N '-phenylenediamine, 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline, N' -di (beta-naphthyl) p-phenylenediamine, 2-mercaptobenzimidazole and 2, 6-di-tert-butyl-4-methylphenol.
The flame retardant can be at least one selected from aluminum hydroxide, magnesium hydroxide, expanded graphite, magnesium oxide, antimony trioxide, zinc borate, talcum powder, ammonium polyphosphate, decabromodiphenyl ether, triphenyl phosphate or tricresyl phosphate.
The structure control agent is at least one of hydroxyl silicone oil, methyl silicone oil, ethyl silicone oil, methyl phenyl silicone oil, methyl vinyl silicone oil, methyl hydroxyl silicone oil, ethyl hydroxyl silicone oil, hydroxyl hydrogen-containing silicone oil, diphenyl silanediol, octamethylcyclotetrasiloxane, methyltrimethoxysilane, azidosilane, 3-aminopropyltriethoxysilane or hexamethyldisilazane.
In the step (1) of the method for preparing the closed-cell structure rubber foam material by mould pressing physical foaming, mixing can be carried out by adopting mixing equipment such as an open mill, an internal mixer, a kneader, an extruder and the like, the mixing temperature is from room temperature to temperature T, the temperature T is 10-20 ℃ lower than the decomposition temperature of a vulcanizing agent, the mixing temperature can be usually selected from the range of room temperature to 100 ℃, and the mixing time is 15-120 min.
In the step (2) of the method for preparing the rubber foam material with the closed-cell structure by mould pressing physical foaming, the rubber compound can be formed by adopting forming equipment such as a mould press, a calender, an extruder and the like, and the prevulcanization can be realized at the same time of forming or the prevulcanization can be realized by adopting radiation crosslinking equipment for radiation after forming.
In the step (3) of the method for preparing the closed-cell structure rubber foam material by mould pressing physical foaming, the temperature in a foaming mould is controlled to be between room temperature and 80 ℃, the pressure is controlled to be between 0.5 and 30MPa, and the temperature and the pressure are kept for 10 to 240min to swell a rubber blank, preferably for 15 to 120 min.
In the step (3) of the method for preparing the closed-cell structure rubber foam material by mould pressing physical foaming, the gas used as the foaming agent is one or a mixture of carbon dioxide, nitrogen, argon, butane, pentane and air.
In the step (3) of the method for preparing the closed-cell structure rubber foam material by mould pressing physical foaming, the adopted mould pressing foaming equipment is the existing equipment, and the mould pressing foaming equipment comprises a temperature control device, a gas conveying device, a gas pressure control device, a hydraulic mould closing device, a foaming mould, a pressure relief device and a gas recovery device. In order to shorten the diffusion time of the gas as the foaming agent in the foaming mold and the rubber blank and improve the production efficiency, the foaming mold with the surface designed by punching, carving or adding breathable metal and the like can be adopted.
In the step (3) of the method for preparing the closed-cell structure rubber foam material by mould pressing physical foaming, the foaming process of the swelled rubber blank can be completed in a foaming mould, and then the foaming mould is opened, or the foaming mould is opened and popped up for foaming after the rubber blank body swells. The size of a cavity of the foaming mold is larger than that of a rubber blank to be foamed so as to meet the volume expansion generated by swelling of dissolved gas of the rubber blank and the volume expansion generated in the foaming process, when a foaming mode is adopted in the foaming mold, the size of the cavity of the foaming mold meets the volume expansion generated by foaming of the blank, the ratio of the volume of the cavity of the foaming mold to the volume of the rubber blank is usually (2.5-8): 1, when the foaming mold is popped out after swelling, the size of the cavity of the foaming mold meets the volume expansion generated by swelling of the blank, and the ratio of the volume of the cavity of the foaming mold to the volume of the rubber blank is usually (1.3-2.5): 1.
In the step (4) of the method for preparing the rubber foam material with the closed cell structure by mould pressing physical foaming, the pre-vulcanized rubber foam material can be post-vulcanized by adopting an oven, a hot baking channel or radiation crosslinking equipment, the pre-vulcanized rubber foam material can be directly post-vulcanized in a foaming mould without being taken out after foaming is completed in the foaming mould, the post-vulcanization time is usually 5min to 4h, the post-vulcanization time is preferably ensured to be completely crosslinked with the base material, and therefore, the preferred post-vulcanization time is 1 to 4 h.
In the method for preparing the closed-cell structure rubber foam material by mould pressing physical foaming, the raw rubber is at least one of raw natural rubber, raw butyl rubber, raw nitrile rubber, raw ethylene propylene diene monomer rubber, raw styrene butadiene rubber, raw chloroprene rubber, raw silicone rubber, raw fluorine rubber and ethylene-vinyl acetate copolymer. In the method for preparing the closed-cell structure rubber foam material by mould pressing physical foaming, when the raw rubber, the resin and the vulcanizing agent are uniformly mixed in the step (1) of preparing the rubber compound, the mixture of the rubber and the plastic or the elastomer alloy is obtained in the step (4).
In the above method for producing a closed-cell rubber foam by physical foaming under molding, the vulcanizing agent is selected in the same manner as in conventional rubber processing, and the vulcanizing agent includes sulfur, sulfur-containing compounds, organic peroxides, metal oxides, amine compounds, and the like, for example, sulfur, vinyl-containing polysiloxane, magnesium oxide, zinc oxide, calcium oxide, lead oxide, dicumyl peroxide, 2, 4-dichlorobenzoyl peroxide, 2, 5-dimethyl-2, 5-di-t-butylperoxysilane, benzoyl peroxide, phenol resin, benzoquinone, urethane or maleimide vulcanizing agents, and the like.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention provides a complete process for preparing a rubber foam material with a closed cell structure by using a mould pressing physical foaming technology, which combines the advantages of the mould pressing foaming technology and the physical foaming technology, can overcome the problems that a product is easy to warp, the product performance is not uniform, the industrial amplification production is difficult, the rubber foam material with the closed cell structure cannot be prepared and the like in the preparation of the rubber foam material by using the physical foaming of a reaction kettle, can solve the problems of poor uniformity of cells, residual foaming agent and degradation products thereof, environmental protection, foaming-vulcanization matching and the like in the preparation of the rubber foam material by using chemical mould pressing foaming, and has positive effects on improving the quality of the rubber foam material and promoting the industrial production of the high-quality rubber foam material.
2. The method carries out pre-vulcanization on the formed green body before mould pressing physical foaming, carries out post-vulcanization after foaming, completely separates the vulcanization process from the foaming process, reduces the difficulty of matching vulcanization and foaming process parameters, is easier to determine the process parameters, simultaneously leads the matrix strength to be proper by the pre-vulcanization with proper degree, and is key for avoiding the merging and perforation of foam holes in subsequent foaming and preparing the closed-cell rubber foaming material with uniform size and uniform distribution of the foam holes.
3. The method provided by the invention can be used for preparing the rubber foaming plate with the thickness of more than 10mm and high foaming ratio, and the mould pressing foaming mould with the surface being perforated, carved, added with breathable metal and the like can effectively increase the contact area of gas and rubber, further shorten the gas diffusion time and improve the production efficiency, thereby realizing the high-efficiency production of the rubber foaming material.
4. The rubber foam material prepared by the method has uniform foam hole distribution, narrow foam hole size distribution and uniform foam hole structure, can ensure that the stress is uniformly dispersed in a matrix when the rubber foam material is acted by external force, does not generate stress concentration, thereby improving the mechanical property of the rubber foam material, improving the damping property of the rubber foam material and further widening the application of the rubber foam material in the aspects of shock absorption, sound absorption and heat insulation.
5. The equipment adopted by the method is the conventional equipment, one die press can be provided with a plurality of foaming dies, and batch production can be realized; meanwhile, the glass transition temperature of the rubber material is extremely low, the rubber material can be foamed at a lower temperature, even at room temperature, and the pre-vulcanization degree is proper, so that the diffusion rate and the solubility of gas in the rubber matrix are relatively high, the rubber material can be foamed under a lower foaming pressure and a shorter saturation time, the foaming condition is mild, and the process controllability is good; the size and density of the foam holes can be regulated and controlled by controlling the prevulcanization and foaming processes, so that the closed-cell structure rubber foam material suitable for different application requirements is prepared, the applicability is strong, and the application prospect is good.
6. The method adopts gas as the foaming agent to prepare the rubber foam material, is green and environment-friendly, safe and nontoxic, does not have the problem of foaming agent residue, can prepare the food-grade rubber foam material, and simultaneously adopts gas as the foaming agent to recycle the foaming agent, thereby saving resources and protecting the environment.
Drawings
FIG. 1 is a scanning electron microscope image of a cross section of a butyl rubber foamed thick plate prepared in example 1.
FIG. 2 is a scanning electron micrograph of a cross section of the silicone rubber foamed slab prepared in example 2.
FIG. 3 is a scanning electron micrograph of a cross section of the ethylene-vinyl acetate rubber foamed slab prepared in example 3.
FIG. 4 is a scanning electron micrograph of a cross section of a fluororubber foamed thick sheet prepared in example 4.
FIG. 5 is a scanning electron micrograph of a butyl rubber foamed slab prepared in example 7.
FIG. 6 is a scanning electron microscope image of a cross section of a butyl rubber foamed slab prepared in comparative example 1.
FIG. 7 is a scanning electron micrograph of the silicone rubber foam prepared in example 8.
Detailed Description
The following examples further illustrate the method of preparing a closed-cell rubber foam by physical foaming under compression molding provided by the present invention. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make certain insubstantial modifications and adaptations of the present invention based on the above disclosure and still fall within the scope of the present invention.
In the following examples and comparative examples, the rubber crude rubber, vulcanizing agent, reinforcing filler and other rubber processing aids used are commercially available.
The analytical test methods referred to in the following examples and comparative examples are as follows:
the apparent density of the rubber foam is measured according to ASTM D1056 standard, and the expansion ratio (R) of the final rubber foam can be calculatedex)，Rex＝ρp/ρfWhere ρ ispDensity of the unfoamed rubber, rhofIs the apparent density of the rubber foam.
And analyzing the section of the rubber foaming material by adopting a Scanning Electron Microscope (SEM), and observing the cell shape and the pore size of the rubber foaming material. The analytical instrument was a scanning electron microscope model JSM-7500F from Japan Electron corporation (JEOL). The cell density is obtained by analyzing and counting a scanning electron microscope Image of the rubber foaming material by Image Pro 6.0 software, and the cell density (N)f) Is the number of cells per cubic centimeter of rubber foam, Nf＝(nM2/A)3/2Wherein n is the number of cells in a scanning electron micrograph of the rubber foam, and A is the area (cm) in the scanning electron micrograph2) And M is the magnification of the scanning electron micrograph.
Example 1
In this embodiment, a method for preparing a closed-cell-structure butyl rubber foamed thick plate by mold pressing physical foaming is provided, which includes the following steps:
(1) preparation of the rubber mixtures
100 parts by mass of butyl rubber raw rubber, 20 parts by mass of reinforcing filler calcium carbonate, 10 parts by mass of carbon black, 2 parts by mass of vulcanizing agent sulfur, 3 parts by mass of zinc oxide, 1 part by mass of vulcanization accelerator 2,2' -dithiodibenzothiazyl, 0.5 part by mass of tetramethylthiuram monosulfide and 2 parts by mass of plasticizer vaseline are added into a kneader and uniformly mixed at room temperature to obtain a rubber compound.
(2) Preparation of rubber blanks
And placing the rubber compound on a molding press for hot press molding, cutting and cutting, and realizing pre-vulcanization in the hot press molding process to obtain a plate-shaped rubber blank with the Shore A hardness of 32 and the size of 200 multiplied by 8 mm.
(3) Mold pressing foaming
Placing the rubber blank into a foaming mould of mould pressing foaming equipment, wherein the volume ratio of the cavity volume of the foaming mould to the volume of the rubber blank is 5:1, inputting carbon dioxide into the foaming mould after hydraulic mould closing, controlling the temperature in the foaming mould to be 70 ℃ and the pressure to be 15MPa, keeping the temperature and the pressure for 20min to enable the carbon dioxide to enter the rubber blank to swell the rubber blank, then releasing pressure, foaming the swelled rubber blank in the foaming mould, opening the mould after foaming is completed, and taking out the obtained pre-vulcanized rubber foaming material.
(4) Post-vulcanization
And (3) placing the pre-vulcanized rubber foaming material in a hot drying tunnel at 160 ℃ for 3h for post-vulcanization, then taking out and cooling to room temperature to obtain a butyl rubber foaming thick plate with the thickness of 13.5mm, wherein the foaming ratio is 4.35.
The butyl rubber foamed thick plate prepared in the embodiment is even and flat, has no warpage problem, is quenched in liquid nitrogen after being placed at room temperature for more than one day, and is subjected to scanning electron microscope test, the scanning electron microscope image of the section of the butyl rubber foamed thick plate is shown in figure 1, as can be seen from figure 1, the foamed structure of the butyl rubber foamed thick plate prepared in the embodiment is a closed cell structure, the cells are uniformly distributed, the cell size difference is small, the cell size and the cell density are statistically analyzed, and the result shows that the average cell size is 96.1 mu m, and the cell density is 9.73 multiplied by 105Per cm3。
Example 2
In this embodiment, a method for preparing a closed-cell structural silicone rubber foamed thick plate by mold pressing physical foaming is provided, which includes the following steps:
(1) preparation of the rubber mixtures
100 parts by mass of raw silicone rubber, 30 parts by mass of reinforcing filler white carbon black, 25 parts by mass of wollastonite, 20 parts by mass of diatomite, 3 parts by mass of vulcanizing agent dicumyl peroxide and 4 parts by mass of structure control agent methyl vinyl silicone oil are added into an internal mixer and uniformly mixed at 30 ℃ to obtain a rubber compound.
(2) Preparation of rubber blanks
And placing the rubber compound on a molding press for hot press molding, cutting and cutting, and realizing pre-vulcanization in the hot press molding process to obtain a plate-shaped rubber blank with the Shore A hardness of 49 and the size of 800 multiplied by 600 multiplied by 10 mm.
(3) Mold pressing foaming
Placing the rubber blank into a foaming mould of mould pressing foaming equipment, wherein the volume ratio of the cavity volume of the foaming mould to the volume of the rubber blank is 4.5:1, inputting carbon dioxide into the foaming mould after hydraulic mould closing, controlling the temperature in the foaming mould to be 40 ℃ and the pressure to be 8MPa, keeping for 15min under the conditions of the temperature and the pressure to enable the carbon dioxide to enter the rubber blank to swell the rubber blank, then releasing pressure, foaming the swelled rubber blank in the foaming mould, opening the mould after foaming is completed, and taking out the obtained pre-vulcanized rubber foaming material.
(4) Post-vulcanization
And (3) placing the pre-vulcanized rubber foaming material in a hot drying tunnel at 120 ℃ for 0.5h, then taking out and placing in a drying oven at 160 ℃ for 2h, namely, after-vulcanization, taking out and cooling to room temperature after the after-vulcanization is finished to obtain a silicone rubber foaming thick plate with the thickness of 24mm, wherein the foaming ratio is 4.12.
The silicone rubber foamed thick plate prepared in the embodiment is uniform and flat, has no warpage problem, is quenched in liquid nitrogen after being placed at room temperature for more than one day, and is subjected to scanning electron microscope test, the scanning electron microscope image of the cross section of the silicone rubber foamed thick plate is shown in fig. 2, as can be seen from fig. 2, the foam cell structure of the silicone rubber foamed thick plate prepared in the embodiment is a closed cell structure, the foam cells are uniformly distributed, the foam cell size uniformity is good, and the statistical analysis on the foam cell size and the foam cell density shows that the average foam cell size is 282.9 microns, and the foam cell density is 3.89 multiplied by 104Per cm3。
Example 3
In this embodiment, a method for preparing a closed-cell ethylene-vinyl acetate rubber foamed thick plate by mold pressing physical foaming is provided, which includes the following steps:
(1) preparation of the rubber mixtures
100 parts by mass of ethylene-vinyl acetate copolymer, 1.2 parts by mass of vulcanizing agent dicumyl peroxide, 2 parts by mass of flame retardant expanded graphite, 8 parts by mass of ammonium polyphosphate, 20 parts by mass of aluminum hydroxide and 0.8 part by mass of plasticizer stearic acid are added into an extruder and uniformly mixed at 90 ℃ to obtain rubber compound.
(2) Preparation of rubber blanks
And (3) forming the rubber compound through an extruder die, placing the rubber compound into radiation crosslinking equipment for prevulcanization, wherein the radiation dose of the radiation crosslinking equipment is 20kGy, and cutting the rubber compound to obtain a plate-shaped rubber blank with the Shore A hardness of 69 and the size of 1000 multiplied by 500 multiplied by 10 mm.
(3) Mold pressing foaming
Placing the rubber blank into a foaming mould of mould pressing foaming equipment, wherein the volume ratio of the cavity volume of the foaming mould to the volume of the rubber blank is 1.5:1, inputting butane into the foaming mould as a foaming agent after hydraulic mould closing, controlling the temperature in the foaming mould to be 50 ℃ and the pressure to be 4MPa, keeping the temperature and the pressure for 60min to enable the butane to enter the rubber blank to swell the rubber blank, then releasing the pressure and opening the mould, and popping and foaming the swelled rubber blank to obtain the pre-vulcanized rubber foaming material.
(4) Post-vulcanization
And (3) placing the pre-vulcanized rubber foaming material in an oven at 90 ℃ for 1h for post-vulcanization, then taking out and cooling to room temperature to obtain an ethylene-vinyl acetate rubber foaming thick plate with the thickness of 23mm, wherein the foaming ratio is 3.24.
The ethylene-vinyl acetate rubber foamed thick plate prepared in the embodiment is even and flat, has no warpage problem, is quenched in liquid nitrogen after being placed at room temperature for more than one day, and is subjected to scanning electron microscope test, the scanning electron microscope image of the section of the ethylene-vinyl acetate rubber foamed thick plate is shown in fig. 3, as can be seen from fig. 3, the foam structure of the ethylene-vinyl acetate rubber foamed thick plate prepared in the embodiment is a closed-cell structure, the foam distribution is even, the foam size difference is small, the foam size and the foam density are analyzed statistically, and the result shows that the average foam size is 89.5 mu m, and the foam density is 1.71 multiplied by 106Per cm3。
Example 4
In this embodiment, a method for preparing a closed-cell-structure fluororubber foamed thick plate by mold pressing physical foaming is provided, which includes the following steps:
(1) preparation of the rubber mixtures
100 parts by mass of raw fluororubber, 30 parts by mass of reinforcing filler white carbon black, 15 parts by mass of mica, 2.5 parts by mass of vulcanizing agent 2, 5-dimethyl-2, 5-di-tert-butyl peroxy silane, 5 parts by mass of structure control agent hydroxy silicone oil and 10 parts by mass of flame retardant aluminum hydroxide are added into a kneader and mixed uniformly at 25 ℃ to obtain rubber compound.
(2) Preparation of rubber blanks
And placing the rubber compound on a calender for hot press molding, cutting and cutting, and realizing pre-vulcanization in the hot press molding process to obtain a plate-shaped rubber blank with the Shore A hardness of 40 and the size of 800 multiplied by 400 multiplied by 6 mm.
(3) Mold pressing foaming
Placing the rubber blank into a foaming mould of mould pressing foaming equipment, wherein the volume ratio of the cavity volume of the foaming mould to the volume of the rubber blank is 3:1, inputting nitrogen into the foaming mould after hydraulic mould closing, controlling the temperature in the foaming mould to be 60 ℃ and the pressure to be 10MPa, keeping the temperature and the pressure for 60min to ensure that the nitrogen enters the rubber blank to swell the rubber blank, then releasing the pressure, foaming the swelled rubber blank in the foaming mould, opening the mould after foaming is completed, and taking out the obtained pre-vulcanized rubber foaming material.
(4) Post-vulcanization
And (3) heating the foaming mold to 175 ℃ and keeping the temperature for 1h, then taking out and placing the foaming mold in an oven at 250 ℃ for 1h, namely, after vulcanization, taking out and cooling the foaming mold to room temperature after vulcanization, thus obtaining the fluororubber foaming thick plate with the thickness of 11.5mm, wherein the foaming ratio is 2.61.
The fluororubber foamed thick plate prepared in the embodiment is even and flat, has no warpage problem, is quenched in liquid nitrogen after being placed at room temperature for more than one day, and is subjected to scanning electron microscope test, the scanning electron microscope image of the section of the fluororubber foamed thick plate is shown in fig. 4, as can be seen from fig. 4, the cellular structure of the fluororubber foamed thick plate prepared in the embodiment is a closed-cell structure, the cells are uniformly distributed, the cell size uniformity is good, the cell size and the cell density are statistically analyzed, and the result shows that the average cell size is 5.7 mu m, and the cell density is 3.09 multiplied by 109Per cm3。
Example 5
In this embodiment, a method for preparing a closed-cell structural natural rubber foamed thick plate by mold pressing physical foaming is provided, which includes the following steps:
(1) preparation of the rubber mixtures
100 parts by mass of raw rubber of natural rubber, 20 parts by mass of calcium carbonate as a reinforcing filler, 20 parts by mass of montmorillonite, 2.8 parts by mass of sulfur as a vulcanizing agent, 1.2 parts by mass of 2-mercaptobenzothiazole as a vulcanization accelerator, 1.2 parts by mass of tetramethylthiuram disulfide, 3 parts by mass of stearic acid as a plasticizer and 0.8 part by mass of hydroquinone dibenzyl ether are added into an internal mixer and mixed uniformly at 40 ℃ to obtain a rubber compound.
(2) Preparation of rubber blanks
And placing the rubber compound on a calender for hot press molding, cutting and cutting, and realizing pre-vulcanization in the hot press molding process to obtain a plate-shaped rubber blank with the Shore A hardness of 31 and the size of 200 multiplied by 100 multiplied by 5 mm.
(3) Mold pressing foaming
Placing the rubber blank into a foaming mould of mould pressing foaming equipment, wherein the volume ratio of the cavity volume of the foaming mould to the volume of the rubber blank is 1.5:1, inputting nitrogen into the foaming mould after hydraulic mould closing, controlling the temperature in the foaming mould to be 60 ℃ and the pressure to be 10MPa, keeping the temperature and the pressure for 60min to ensure that the nitrogen enters the rubber blank to swell the rubber blank, then releasing the pressure and opening the mould, and ejecting and foaming the swelled rubber blank to obtain the pre-vulcanized rubber foaming material.
(4) Post-vulcanization
Taking out the pre-vulcanized rubber foaming material, placing the pre-vulcanized rubber foaming material in an oven at 170 ℃ for 2.5h for post-vulcanization, then taking out the pre-vulcanized rubber foaming material, and cooling the pre-vulcanized rubber foaming material to room temperature to obtain a natural rubber foaming thick plate with the thickness of 10.5mm, wherein the foaming ratio is 4.68.
Example 6
In this embodiment, a method for preparing a closed-cell structure ethylene propylene diene monomer/styrene butadiene rubber composite rubber (EPDM/SBR composite rubber) foamed thick plate by mold pressing physical foaming is provided, which includes the following steps:
(1) preparation of the rubber mixtures
60 parts by mass of raw Ethylene Propylene Diene Monomer (EPDM) rubber, 40 parts by mass of Styrene Butadiene Rubber (SBR), 15 parts by mass of reinforcing filler white carbon black, 0.5 part by mass of vulcanizing agent dicumyl peroxide, 0.5 part by mass of sulfur and 2 parts by mass of plasticizer paraffin oil are added into an open mill and mixed uniformly at 50 ℃ to obtain a rubber compound.
(2) Preparation of rubber blanks
And placing the rubber compound on a calender for hot press molding, cutting and cutting, and realizing pre-vulcanization in the hot press molding process to obtain a plate-shaped rubber blank with the Shore A hardness of 42 and the size of 500 multiplied by 250 multiplied by 12 mm.
(3) Mold pressing foaming
Placing the rubber blank into a foaming mould of mould pressing foaming equipment, wherein the volume ratio of the cavity volume of the foaming mould to the volume of the rubber blank is 1.8:1, inputting carbon dioxide into the foaming mould after hydraulic mould closing, controlling the temperature in the foaming mould to be 45 ℃ and the pressure to be 8MPa, keeping the temperature and the pressure for 90min to enable the carbon dioxide to enter the rubber blank to swell, then releasing the pressure and opening the mould, and ejecting and foaming the swelled rubber blank to obtain the pre-vulcanized rubber foaming material.
(4) Post-vulcanization
And (3) putting the pre-vulcanized rubber foaming material into an oven at 180 ℃, vulcanizing for 1.5h, taking out, and cooling to room temperature to obtain an EPDM/SBR composite rubber foaming thick plate with the thickness of 28.5mm, wherein the foaming ratio is 6.73.
Example 7
In this embodiment, a method for preparing a closed-cell-structure butyl rubber foamed thick plate by mold pressing physical foaming is provided, which includes the following steps:
(1) preparation of the rubber mixtures
100 parts by mass of butyl rubber raw rubber, 20 parts by mass of reinforcing filler white carbon black, 20 parts by mass of calcium carbonate, 10 parts by mass of carbon black, 1 part by mass of vulcanizing agent sulfur, 3 parts by mass of zinc oxide, 1 part by mass of vulcanization accelerator 2,2' -dithiodibenzothiazyl, 0.5 part by mass of tetramethylthiuram monosulfide, 2 parts by mass of plasticizer vaseline and 4 parts by mass of terpene resin are added into a kneader and mixed uniformly at room temperature to obtain a rubber compound.
(2) Preparation of rubber blanks
And placing the rubber compound on a molding press for hot press molding, cutting and cutting, and realizing pre-vulcanization in the hot press molding process to obtain a plate-shaped rubber blank with the Shore A hardness of 45 and the size of 500 multiplied by 20 mm.
(3) Mold pressing foaming
Placing the rubber blank into a foaming mould of mould pressing foaming equipment, wherein the volume ratio of the cavity volume of the foaming mould to the volume of the rubber blank is 6:1, inputting carbon dioxide into the foaming mould after hydraulic mould closing, controlling the temperature in the foaming mould to be 70 ℃ and the pressure to be 12MPa, keeping the temperature and the pressure for 120min to enable the carbon dioxide to enter the rubber blank to swell the rubber blank, then releasing pressure, foaming the swelled rubber blank in the foaming mould, opening the mould after foaming is completed, and taking out the obtained pre-vulcanized rubber foaming material.
(4) Post-vulcanization
And (3) placing the pre-vulcanized rubber foaming material in a hot drying tunnel at 165 ℃ for 3h for post-vulcanization, then taking out and cooling to room temperature to obtain a butyl rubber foaming thick plate with the thickness of 48mm, wherein the foaming multiplying power is 5.67.
The butyl rubber foamed thick plate prepared in the embodiment is uniform and flat, has no warpage problem, is quenched in liquid nitrogen after being placed at room temperature for more than one day, and is subjected to scanning electron microscope test, a scanning electron microscope image of a cross section of the butyl rubber foamed thick plate is shown in fig. 5, as can be seen from fig. 5, the butyl rubber foamed thick plate prepared in the embodiment has a closed cell structure, uniform cell distribution and small cell size difference, and the cell size and the cell density are statistically analyzed, and the result shows that the average cell size is 70.7 micrometers, and the cell density is 2.46 × 106Per cm3。
Comparative example 1
In the comparative example, the butyl rubber foam material was prepared by a compression molding physical foaming method without post-vulcanization of the rubber base, and the steps were as follows:
(1) same as in step (1) of example 7;
(2) same as in step (2) of example 7;
(3) in the same manner as in the step (3) of example 7, a butyl rubber foam was obtained.
The butyl rubber foam material is cooled to room temperature, then is placed for one day, and is quenched in liquid nitrogen, and is subjected to scanning electron microscope test, and the scanning electron microscope image of the cross section is shown in fig. 6, and as can be seen from fig. 6, the foam material prepared by the comparative example has the foam cells basically completely retracted and disappeared after being placed for one day.
Example 8
In this embodiment, a method for preparing a closed-cell structure silicone rubber foam material by using mold pressing physical foaming is provided, which includes the following steps:
(1) preparation of the rubber mixtures
100 parts by mass of raw silicone rubber, 30 parts by mass of reinforcing filler white carbon black, 20 parts by mass of wollastonite, 15 parts by mass of mica, 2.5 parts by mass of a vulcanizing agent dicumyl peroxide and 6 parts by mass of a structure control agent methyl vinyl silicone oil are added into an internal mixer and mixed uniformly at 30 ℃ to obtain a rubber compound.
(2) Preparation of rubber blanks
And placing the rubber compound on a molding press for hot press molding, cutting and cutting, and realizing pre-vulcanization in the hot press molding process to obtain a rubber blank with the Shore A hardness of 34 and the size of 1000 multiplied by 600 multiplied by 2.5 mm.
(3) Mold pressing foaming
Placing the rubber blank into a foaming mould of mould pressing foaming equipment, wherein the volume ratio of the cavity volume of the foaming mould to the volume of the rubber blank is 5:1, inputting carbon dioxide into the foaming mould after hydraulic mould closing, controlling the temperature in the foaming mould to be 45 ℃ and the pressure to be 5MPa, keeping for 45min under the conditions of the temperature and the pressure to enable the carbon dioxide to enter the rubber blank to swell the rubber blank, then releasing pressure, foaming the swelled rubber blank in the foaming mould, opening the mould after complete foaming, and taking out the obtained pre-vulcanized rubber foaming material.
(4) Post-vulcanization
And (3) placing the pre-vulcanized rubber foam material in a hot drying tunnel at 120 ℃ for 0.5h, taking out the pre-vulcanized rubber foam material, placing the pre-vulcanized rubber foam material in a drying oven at 160 ℃ for 2h, namely, after vulcanization, taking out the pre-vulcanized rubber foam material after the post-vulcanization, and cooling the pre-vulcanized rubber foam material to room temperature to obtain the silicone rubber foam material with the thickness of 5.2mm, wherein the foaming ratio is 4.17.
The silicone rubber foam material prepared in this example is uniform and flat, has no warpage problem, is quenched in liquid nitrogen after being placed at room temperature for more than one day, and is subjected to scanning electron microscope test, and a scanning electron microscope image of a cross section of the silicone rubber foam material is shown in fig. 7, as can be seen from fig. 7, the silicone rubber foam material prepared in this example has a closed cell structure and uniform cell distribution,the uniformity of the cell size was good, and the statistical analysis of the cell size and the cell density of the silicone rubber foam revealed that the average cell size was 211.9 μm and the cell density was 1.04X 105Per cm3。
Claims (7)
1. A method for preparing a closed-cell structure rubber foam material by mould pressing physical foaming is characterized by comprising the following steps:
(1) mixing the raw rubber and a vulcanizing agent at room temperature to temperatureTMixing uniformly to obtain a rubber compound, and heatingTThe temperature is 10-20 ℃ lower than the decomposition temperature of a vulcanizing agentoC; the using amount of the raw rubber is 100 parts by mass, and the using amount of the vulcanizing agent is 1-10 parts by mass;
or the raw rubber, the resin and the vulcanizing agent are mixed at room temperature to temperatureTMixing uniformly to obtain a rubber compound, and heatingTThe temperature is 10-20 ℃ lower than the decomposition temperature of a vulcanizing agentoC, the total amount of the raw rubber and the resin is 100 parts by mass, and the amount of the vulcanizing agent is 1-10 parts by mass;
(2) hot-press molding the rubber compound, and pre-vulcanizing the rubber compound in the hot-press molding process to obtain a rubber blank, or radiating the molded rubber compound by using radiation cross-linking equipment to realize pre-vulcanization to obtain a rubber blank; in the step, the pre-vulcanization degree is controlled to ensure that the Shore A hardness of the rubber blank is 30-70;
(3) placing the rubber blank into a foaming mold of a mold pressing foaming device, inputting gas into the foaming mold after mold closing as a foaming agent, and controlling the temperature in the foaming mold to be room temperature-80 DEG CoC, keeping the pressure of 0.5-30 MPa and the temperature and pressure for 10-240 min to swell the rubber blank, and then releasing the pressure to foam the swelled rubber blank to obtain a pre-vulcanized rubber foam material;
in the step, the swollen rubber blank is foamed by adopting a mode of completing foaming in a foaming mold and then opening the foaming mold, or opening the foaming mold after the rubber blank is swollen and popping up the foaming mold; when the mode of foaming in the foaming mold and then opening the foaming mold is adopted, the volume ratio of the cavity of the foaming mold to the rubber blank is (2.5-8): 1, and when the mode of popping up the foaming mold after swelling is adopted, the volume ratio of the cavity of the foaming mold to the rubber blank is (1.3-2.5): 1;
(4) the pre-vulcanized rubber foaming material is in a range of 90-250%oAnd C, post-vulcanizing to obtain the closed-cell structure rubber foam material.
2. The method for preparing a closed-cell structural rubber foam material by molding physical foaming according to claim 1, wherein when the thickness of the rubber body in the step (2) is at least 5mm, the rubber foam material prepared in the step (4) is a rubber foamed slab with a thickness of more than 10 mm.
3. The method for preparing the closed-cell structural rubber foam material by mould pressing physical foaming according to claim 1, wherein 10-100 parts by mass of reinforcing filler is further added in the step (1).
4. A process for producing a closed-cell rubber foam by compression molding physical foaming according to any one of claims 1 to 3, wherein the step (1) further comprises adding not more than 50 parts by mass of a rubber processing aid during kneading.
5. The process for preparing a closed-cell rubber foam by compression molding physical foaming according to claim 4, wherein the rubber processing aids comprise a vulcanization accelerator, a plasticizer, an anti-aging agent, a flame retardant and a structure-controlling agent.
6. The method for preparing the closed-cell rubber foam material by molding physical foaming according to any one of claims 1 to 3, wherein the time for post-vulcanization in the step (4) is 5min to 4 h.
7. The method for preparing a closed-cell rubber foam material by molding physical foaming according to any one of claims 1 to 3, wherein the raw rubber is at least one of raw natural rubber, raw butyl rubber, raw nitrile rubber, raw ethylene propylene diene monomer rubber, raw styrene butadiene rubber, raw chloroprene rubber, raw silicone rubber, raw fluororubber and ethylene-vinyl acetate copolymer.
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