CN105330985A - Salt bath vulcanization technology for ethylene propylene diene monomer foamed profile - Google Patents
Salt bath vulcanization technology for ethylene propylene diene monomer foamed profile Download PDFInfo
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- CN105330985A CN105330985A CN201510771799.9A CN201510771799A CN105330985A CN 105330985 A CN105330985 A CN 105330985A CN 201510771799 A CN201510771799 A CN 201510771799A CN 105330985 A CN105330985 A CN 105330985A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a rubber material production technology, in particular to a salt bath vulcanization technology for an ethylene propylene diene monomer foamed profile. The salt bath vulcanization technology for the ethylene propylene diene monomer foamed profile comprises the following steps that foaming materials are taken, mechanically mixed, extruded through an extruder for formation and subjected to salt bath vulcanization foaming, and the ethylene propylene diene monomer foamed profile is obtained, wherein the foaming raw materials include ethylene propylene diene monomers, naphthenic oil, carbon black, calcium carbonate, stearic acid, zinc oxide, sulphur, accelerant dialkyldithiocarbamate salt and azodicarbonamide. The continuous production technology of extruding formation and salt bath vulcanization is adopted, the production cost is reduced, and the production efficiency is improved.
Description
Technical field
The present invention relates to a kind of elastomeric material production technique, particularly a kind of salt bath vulcanization technique of ethylene propylene diene rubber foaming section bar.
Background technology
The relatively common dense rubber material of rubber expanded material, the most general common feature is that density is little, quality is light, specific area is large, energy absorption capability is strong, the series of advantages such as damping, sound insulation and heat-proof quality are good, both artistic and practical, obtain a wide range of applications in the field such as industry, agricultural, building, communications and transportation, military project, aerospace, daily necessities.As for sealing, heat insulating, vibrationproof is crashproof, many occasions such as sound insulation.In scientific and technical research and the development of the national economy, play huge effect, become people and produced and indispensable material in life.
Terpolymer EP rubber (EPDM) is by the rubber of ethene, propylene and a small amount of Third monomer copolymerization, its main chain is made up of chemically stable stable hydrocarbon, only in side chain, contain unsaturated double-bond, nonpolarity substituting group in molecule, molecule inner injection can be low, and molecule segment keeps flexible in wide temperature range.Thus there is excellent chemical stability, ageing resistance, chemical proofing, electrical insulating property, shock elasticity and low-temperature performance, and heat-proof water performance etc.For this reason, EPDM obtains and applies more and more widely in rubber item industry, be mainly used in many aspects such as auto parts, electrical apparatus product, mechanicals, material of construction and household supplies and plastic modifier etc., its foam material is then widely used in the weather strip manufacturing automobile, cushion rubber bumper, construction work gasket seal, the thermal insulation material of light current parts, damping material, the easy goods such as submarine armour and footwear.
Current domestic EPDM foamed profile be all adopt prevulcanized add-technique (two step compression moldings) of secondary sulfuration produces, but the length of product is less and can not continuous prodution, be temperature, the volume requirement meeting prevulcanized and sulfur foam in production process, need repeatedly more mold exchange, production cycle needs half hour, production efficiency is very low, and centre more mold exchange can cause the change of products temperature, affect the quality of final rubber pange sheet material.Only have Italy in the world, Japan and other countries is proposed rubber pange plate foaming sulfuration tinuous production, but price is very expensive, maintenance cost is very high.Although EPDM foamed profile excellent performance, due to production cost and production efficiency etc. reason, limit its suitability for industrialized production.Adopt salt bath vulcanization-foam process, the EPDM foamed profile uniform in foaming of preparation, form unicellular structure, thermal insulation and sound-proofing good, length is larger, production rate is very high, is conducive to its application in industries such as building heat preservation, auto parts machinery, water-proof material, electric wire, air conditioner refrigerating, military project apparatuses.
Summary of the invention
The present invention is directed to the defect of prior art, provide a kind of salt bath vulcanization technique of ethylene propylene diene rubber foaming section bar, this technique achieves the continuous seepage of ethylene propylene diene rubber foaming section bar, shortens the production time.
The technical solution adopted for the present invention to solve the technical problems is:
A salt bath vulcanization technique for ethylene propylene diene rubber foaming section bar, after this technique comprises the steps: to get foaming raw material mechanically mixing, through extruder for shaping, after salt bath sulfur foam, obtained ethylene propylene diene rubber foaming section bar; Described foaming raw material comprises terpolymer EP rubber, naphthenic oil, carbon black, calcium carbonate, stearic acid, zinc oxide, sulphur, promotor dialkyl dithiocarbamate, Cellmic C 121.
As preferably, terpolymer EP rubber is put on double roll mill and plasticate 3 minutes, add naphthenic oil, carbon black, calcium carbonate, stearic acid, mixing 10 minutes of zinc oxide respectively, add sulphur again, promotor dialkyl dithiocarbamate, AC mix, after thin-pass 10 times, blanking obtains terpolymer EP rubber pre-composition; Then terpolymer EP rubber pre-composition is again through single screw extrusion machine extrusion moulding, under the effect of tractor after salt bath sulfur foam, and obtained ethylene propylene diene rubber foaming section bar.
As preferably, described foaming raw material is made up of the component of following weight part: 100 parts of terpolymer EP rubbers, 10 ~ 50 parts of naphthenic oils, 5 ~ 40 parts of carbon blacks, 5 ~ 30 parts of calcium carbonate, 0.5 ~ 3.0 part of stearic acid, 1.0 ~ 5.0 parts of zinc oxide, 2.0 ~ 8.0 parts of sulphur, 1.0 ~ 5.0 parts of promotor dialkyl dithiocarbamates, 1.0 ~ 5.0 parts of Cellmic C 121s (AC).
As preferably, described promotor dialkyl dithiocarbamate is selected from ziram (PZ), zinc diethyldithiocarbamate (ZDEC), zinc dibutyl dithiocarbamate (BZ), zinc-ethylphenyl dithiocarbamate (PX).
As preferably, described single screw extrusion machine each section of temperature controls at 50 ~ 110 DEG C, and wherein feeding section temperature is 50 ~ 60 DEG C, and die temperature is 90 ~ 110 DEG C.
As preferably, in described salt bath, the temperature of fused salt controls at 180 ~ 220 DEG C, and material is 3 ~ 8 minutes in the residence time of salt bath.
Compared with prior art, beneficial effect of the present invention is embodied in following several respects:
1, the ethylene propylene diene rubber foaming section bar that obtains of the present invention, sulfuration-foaming system used is sulphur/dialkyl dithiocarbamate/Cellmic C 121, wherein vulcanizing agent is sulphur, promotor is dialkyl dithiocarbamate, whipping agent is Cellmic C 121, promotor dialkyl dithiocarbamate not only accelerates the sulfuration of terpolymer EP rubber, and cause Cellmic C 121 to activate its decomposition temperature of reduction, improve the rate of decomposition of Cellmic C 121, make terpolymer EP rubber sulfuration and foaming process form good coupling;
2, present invention employs salt bath vulcanization foam process, the section bar uniform in foaming of preparation, form unicellular structure, good stability of the dimension;
3, present invention employs extrusion moulding-salt bath vulcanization continuous production processes, reduce production cost, improve production efficiency.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation make the present invention and/or change all will fall into scope.
In the present invention, if not refer in particular to, all parts, per-cent are weight unit, and the equipment adopted and raw material etc. all can be buied from market or this area is conventional.Method in following embodiment, if no special instructions, is the ordinary method of this area.
Embodiment 1
100 parts of terpolymer EP rubbers are put on double roll mill and plasticate 3 minutes, 50 parts of naphthenic oils, 40 parts of carbon blacks, 5 parts of calcium carbonate, 0.5 part of stearic acid, mixing 10 minutes of 1.0 parts of zinc oxide, add 8.0 parts of sulphur again, 5.0 parts of promotor PZ, 5.0 parts of AC mix, bottom sheet after thin-pass 10 times, obtained terpolymer EP rubber pre-composition, then terpolymer EP rubber pre-composition is again through single screw extrusion machine extrusion moulding, wherein single screw extrusion machine each section of temperature controls at 50 ~ 110 DEG C, wherein feeding section temperature is 50 ~ 60 DEG C, die temperature is 90 ~ 110 DEG C, through 180 DEG C of salt bath sulfur foams 8 minutes under the effect of tractor, obtained ethylene propylene diene rubber foaming section bar.
Embodiment 2
The preparation manipulation of ethylene propylene diene rubber foaming section bar is with embodiment 1.The formula of ethylene propylene diene rubber foaming section bar is 100 parts of terpolymer EP rubbers, 10 parts of naphthenic oils, 5 parts of carbon blacks, 30 parts of calcium carbonate, 3.0 parts of stearic acids, 5.0 parts of zinc oxide, 2.0 parts of sulphur, 1.0 parts of ZDEC, 1.0 parts of AC, in salt bath, the temperature of fused salt is 220 DEG C, and the salt bath vulcanization time is 3 minutes.
Embodiment 3
The preparation manipulation of ethylene propylene diene rubber foaming section bar is with embodiment 1.The formula of ethylene propylene diene rubber foaming section bar is 100 parts of terpolymer EP rubbers, 20 parts of naphthenic oils, 15 parts of carbon blacks, 20 parts of calcium carbonate, 2.0 parts of stearic acids, 2.0 parts of zinc oxide, 6.0 parts of sulphur, 3.0 parts of BZ, 2.0 parts of AC, in salt bath, the temperature of fused salt is 200 DEG C, and the salt bath vulcanization time is 5 minutes.
Embodiment 4
The preparation manipulation of ethylene propylene diene rubber foaming section bar is with embodiment 1.The formula of ethylene propylene diene rubber foaming section bar is 100 parts of terpolymer EP rubbers, 30 parts of naphthenic oils, 30 parts of carbon blacks, 10 parts of calcium carbonate, 3.0 parts of stearic acids, 3.0 parts of zinc oxide, 6.0 parts of sulphur, 4.0 parts of PX, 4.0 parts of AC, in salt bath, the temperature of fused salt is 190 DEG C, and the salt bath vulcanization time is 6 minutes.
As comparing, in the ethylene propylene diene rubber foaming section bar formula of embodiment 1, promotor PZ is replaced by the tetramethyl-thiuram disulfide of equal parts (TMTD), sulfur foam carries out at vulcanization bed, curing temperature is identical with salt bath vulcanization technique with the time, and the performance test of gained ethylene propylene diene rubber foaming section bar and production efficiency results contrast are in table 1.
Table 1
| Ethylene propylene diene rubber foaming section bar I | Ethylene propylene diene rubber foaming section bar II | |
| Density (g/cm 3） | 0.581 | 0.466 |
| Breaking tenacity (MPa) | 7.62 | 7.70 |
| Tension set (%) | 544 | 609 |
| Production time (minute/100 meters) | 115 | 52 |
Ethylene propylene diene rubber foaming section bar I: formula is 100 parts of terpolymer EP rubbers, 50 parts of naphthenic oils, 40 parts of carbon blacks, 5 parts of calcium carbonate, 0.5 part of stearic acid, 1.0 parts of zinc oxide, 8.0 parts of sulphur, 5.0 parts of Vulcanization accelerator TMTDs, 5.0 parts of AC; Ethylene propylene diene rubber foaming section bar II: formula and preparation technology are together by embodiment 6.
As can be seen from product density, compare sulphur/TMTD/AC, invent the expansion ratio that sulphur/dialkyl dithiocarbamate/AC used effectively improves terpolymer EP rubber section bar, reduce rubber profile proportion, this is mainly because the zine ion peripheral electron arrangement in dialkyl dithiocarbamate is 4S
24P
2there is unoccupied orbital, and in blowing agent AC structure, N, O all have lone-pair electron, according to Louis's acid-alkali coordination principle, the two in conjunction with time, the lone-pair electron on N, O atom on AC enter Zn
2+unoccupied orbital, on the Л key simultaneously on-N-C-, electronic cloud flowing, makes-N-C-electronic cloud concentration flow to both sides, and middle degree of overlapping reduces, and thus causes-N-C-key easily to rupture, and causes AC to activate its decomposition temperature and reduces.
From mechanical property, the intensity of ethylene propylene diene rubber foaming section bar prepared by salt bath vulcanization and ductility are all better than material prepared by conventional vulcanized bed, this cell diameter size being attributable to ethylene propylene diene rubber foaming section bar prepared by salt bath vulcanization is less, distributes more even.From the angle of production efficiency, the production rate adopting salt bath vulcanization production technique to prepare ethylene propylene diene rubber foaming section bar is higher than traditional vulcanization bed production technique.
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (6)
1. a salt bath vulcanization technique for ethylene propylene diene rubber foaming section bar, after it is characterized in that this technique comprises the steps: to get foaming raw material mechanically mixing, through extruder for shaping, after salt bath sulfur foam, obtained ethylene propylene diene rubber foaming section bar; Described foaming raw material comprises terpolymer EP rubber, naphthenic oil, carbon black, calcium carbonate, stearic acid, zinc oxide, sulphur, promotor dialkyl dithiocarbamate, Cellmic C 121.
2. salt bath vulcanization technique according to claim 1, it is characterized in that: terpolymer EP rubber is put on double roll mill and plasticate 3 minutes, add naphthenic oil, carbon black, calcium carbonate, stearic acid, mixing 10 minutes of zinc oxide respectively, add sulphur again, promotor dialkyl dithiocarbamate, AC mix, after thin-pass 10 times, blanking obtains terpolymer EP rubber pre-composition; Then terpolymer EP rubber pre-composition is again through single screw extrusion machine extrusion moulding, under the effect of tractor after salt bath sulfur foam, and obtained ethylene propylene diene rubber foaming section bar.
3. salt bath vulcanization technique according to claim 1, is characterized in that described foaming raw material is made up of the component of following weight part: 100 parts of terpolymer EP rubbers, 10 ~ 50 parts of naphthenic oils, 5 ~ 40 parts of carbon blacks, 5 ~ 30 parts of calcium carbonate, 0.5 ~ 3.0 part of stearic acid, 1.0 ~ 5.0 parts of zinc oxide, 2.0 ~ 8.0 parts of sulphur, 1.0 ~ 5.0 parts of promotor dialkyl dithiocarbamates, 1.0 ~ 5.0 parts of Cellmic C 121s (AC).
4. salt bath vulcanization technique according to claim 1, is characterized in that: described promotor dialkyl dithiocarbamate is selected from ziram (PZ), zinc diethyldithiocarbamate (ZDEC), zinc dibutyl dithiocarbamate (BZ), zinc-ethylphenyl dithiocarbamate (PX).
5. salt bath vulcanization technique according to claim 2, is characterized in that: described single screw extrusion machine each section of temperature controls at 50 ~ 110 DEG C, and wherein feeding section temperature is 50 ~ 60 DEG C, and die temperature is 90 ~ 110 DEG C.
6. salt bath vulcanization technique according to claim 1, is characterized in that: in described salt bath, the temperature of fused salt controls at 180 ~ 220 DEG C, and material is 3 ~ 8 minutes in the residence time of salt bath.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875834A (en) * | 2020-06-29 | 2020-11-03 | 桐乡市洲泉振强塑业有限公司 | Foamed rubber anti-collision strip and production process thereof |
| CN113185743A (en) * | 2021-04-30 | 2021-07-30 | 宁波新安东密封保温系统有限公司 | Sealing rubber strip capable of turning directly and preparation method thereof |
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| CN101824189A (en) * | 2010-04-21 | 2010-09-08 | 北京市射线应用研究中心 | Preparation process of ethylene propylene diene rubber foaming materials |
| CN102690519A (en) * | 2012-06-19 | 2012-09-26 | 西华大学 | Continuous silicon rubber foam plate with low compression stress relaxation and preparation method of continuous silicon rubber foam plate |
| CN103131091A (en) * | 2013-02-28 | 2013-06-05 | 长城汽车股份有限公司 | Foamed rubber seal strip |
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2015
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| CN101824189A (en) * | 2010-04-21 | 2010-09-08 | 北京市射线应用研究中心 | Preparation process of ethylene propylene diene rubber foaming materials |
| CN102690519A (en) * | 2012-06-19 | 2012-09-26 | 西华大学 | Continuous silicon rubber foam plate with low compression stress relaxation and preparation method of continuous silicon rubber foam plate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875834A (en) * | 2020-06-29 | 2020-11-03 | 桐乡市洲泉振强塑业有限公司 | Foamed rubber anti-collision strip and production process thereof |
| CN113185743A (en) * | 2021-04-30 | 2021-07-30 | 宁波新安东密封保温系统有限公司 | Sealing rubber strip capable of turning directly and preparation method thereof |
| CN113185743B (en) * | 2021-04-30 | 2022-08-09 | 宁波新安东密封保温系统有限公司 | Sealing rubber strip capable of turning directly and preparation method thereof |
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