CN109627527B - High-shrinkage-stability and high-hardness rubber-based composite foam material and preparation method thereof - Google Patents
High-shrinkage-stability and high-hardness rubber-based composite foam material and preparation method thereof Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 64
- 239000005060 rubber Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000006261 foam material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 22
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 20
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 229920001084 poly(chloroprene) Polymers 0.000 claims abstract description 18
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 16
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 238000005187 foaming Methods 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004088 foaming agent Substances 0.000 claims abstract description 9
- 239000004156 Azodicarbonamide Substances 0.000 claims abstract description 8
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 8
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims abstract description 8
- 235000019399 azodicarbonamide Nutrition 0.000 claims abstract description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012188 paraffin wax Substances 0.000 claims abstract description 8
- 239000008117 stearic acid Substances 0.000 claims abstract description 8
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- 239000006229 carbon black Substances 0.000 claims abstract description 4
- 238000004073 vulcanization Methods 0.000 claims description 16
- -1 -tert-butyl dicumyl peroxide Chemical compound 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000004132 cross linking Methods 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- ZCZDJNBPZPSQPZ-UHFFFAOYSA-N benzene;prop-1-ene Chemical compound CC=C.C1=CC=CC=C1 ZCZDJNBPZPSQPZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920001821 foam rubber Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
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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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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- 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
- C08J9/0066—Use of inorganic compounding ingredients
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- 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
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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Abstract
本发明涉及一种高收缩稳定性，高硬度橡胶基复合发泡材料及其制备方法。本发明先将热塑性丁苯橡胶、1氯丁橡胶、乙烯‑醋酸乙烯酯与白炭黑、石蜡、氧化锌和硬脂酸充分混炼均匀；再将交联剂双叔丁基过氧化二异丙苯和树脂交联剂SSA‑1252混炼得混合物；接着将发泡剂偶氮二甲酰胺与混合物一起加入到密炼机中充分混炼均匀，将得到的共混胶在开炼机上处理成片材，再放入硫化机，进行模压交联发泡成型出片，冷却，得到高收缩稳定性，高硬度橡胶基复合发泡材料。本发明制备的橡胶基复合发泡材料具有高的硬度、较低的收缩率，低密度及耐拉伸、撕裂的特点。The invention relates to a high shrinkage stability, high hardness rubber-based composite foam material and a preparation method thereof. In the present invention, thermoplastic styrene-butadiene rubber, 1-chloroprene rubber, ethylene-vinyl acetate, white carbon black, paraffin, zinc oxide and stearic acid are fully mixed and uniformly mixed; Propylene benzene and resin cross-linking agent SSA-1252 are mixed to obtain a mixture; then the foaming agent azodicarbonamide is added to the internal mixer together with the mixture, and the mixture is fully mixed and uniformly mixed, and the obtained blended rubber is processed on an open mixer The sheet is formed into a sheet, which is then put into a vulcanizer, molded, cross-linked and foamed to form a sheet, and cooled to obtain a rubber-based composite foam material with high shrinkage stability and high hardness. The rubber-based composite foaming material prepared by the invention has the characteristics of high hardness, low shrinkage rate, low density and resistance to stretching and tearing.
Description
技术领域technical field
本发明涉及橡胶基复合发泡材料的制备领域，具体涉及一种高收缩稳定性，高硬度橡胶基复合发泡材料及其制备方法。The invention relates to the field of preparation of rubber-based composite foamed materials, in particular to a high-shrinkage-stability, high-hardness rubber-based composite foamed material and a preparation method thereof.
背景技术Background technique
橡胶基复合发泡材料是一种由橡胶基高分子基体和发泡气体分子组成的固/气两相复合材料。由于其内部含有大量的气体，赋予了其质轻、耐屈挠、高弹、减震、保温隔热、隔音等优异的性能。橡胶发泡材料又称为橡胶海绵，它以橡胶为主要基体，添加补强剂、发泡助剂、发泡剂、交联剂及其他助剂，制备出具有大量泡孔的发泡橡胶材料。The rubber-based composite foam material is a solid/gas two-phase composite material composed of a rubber-based polymer matrix and foamed gas molecules. Due to the large amount of gas contained in it, it endows it with excellent properties such as light weight, flex resistance, high elasticity, shock absorption, thermal insulation, and sound insulation. Rubber foam material is also known as rubber sponge. It uses rubber as the main matrix and adds reinforcing agent, foaming aid, foaming agent, cross-linking agent and other aids to prepare foamed rubber material with a large number of cells. .
橡胶基发泡材料被广泛应用于包装、密封条、坐垫、隔热板、鞋底、医疗及体育器件行业。近年来，由于共享单车、共享电动车的兴起，实现车胎轻量化成为大家的焦点。目前，市场上主流产品乙烯-醋酸乙烯酯（EVA）和聚氨酯（PU）发泡材料分别存在着压缩永久变形性差和环境压力大的问题。而橡胶基发泡材料具有密度低、比强度高、防震以及良好的耐磨性，将其应用于自行车发泡一体胎、低速电动车发泡一体胎成为研究对象。不同的工作环境要求其应具有不同的使用性能。当其应用于此行业时，要求其硬度在75-90C之间，收缩率小、密度低、耐拉伸、耐撕裂以及良好的稳定性。Rubber-based foam materials are widely used in packaging, sealing strips, cushions, heat insulation boards, shoe soles, medical and sports equipment industries. In recent years, due to the rise of shared bicycles and shared electric vehicles, the realization of lightweight tires has become the focus of everyone. At present, ethylene-vinyl acetate (EVA) and polyurethane (PU) foam materials, the mainstream products on the market, have problems of poor compression set and high environmental pressure, respectively. The rubber-based foam material has low density, high specific strength, shock resistance and good wear resistance, and its application in bicycle foamed one-piece tires and low-speed electric vehicle foamed one-piece tires has become a research object. Different working environments require it to have different performance. When it is used in this industry, it is required to have a hardness between 75-90C, low shrinkage, low density, stretch resistance, tear resistance and good stability.
发明内容SUMMARY OF THE INVENTION
本发明的目的是提供一种高收缩稳定性，高硬度橡胶基复合发泡材料及其制备方法，用本发明所述的制备方法制备得到的橡胶基复合发泡材料具有较低的收缩率，体现了低密度及耐拉伸、撕裂的特点。The purpose of the present invention is to provide a high shrinkage stability, high hardness rubber-based composite foamed material and a preparation method thereof, the rubber-based composite foamed material prepared by the preparation method of the present invention has a lower shrinkage rate, It reflects the characteristics of low density and resistance to stretching and tearing.
本发明所采用的技术方案为：The technical scheme adopted in the present invention is:
一种高收缩稳定性，高硬度橡胶基复合发泡材料的制备方法，包括以下步骤：A preparation method of high shrinkage stability and high hardness rubber-based composite foam material, comprising the following steps:
（1）将40-70重量份的热塑性丁苯橡胶、15-40重量份氯丁橡胶、5-30重量份的乙烯-醋酸乙烯酯与10-30重量份的白炭黑、1.0-6.0重量份石蜡、3.0-12.0重量份的氧化锌和3.0-9.0重量份的硬脂酸在密炼机里充分混炼均匀；(1) 40-70 parts by weight of thermoplastic styrene-butadiene rubber, 15-40 parts by weight of neoprene, 5-30 parts by weight of ethylene-vinyl acetate and 10-30 parts by weight of white carbon black, 1.0-6.0 parts by weight Parts of paraffin, 3.0-12.0 parts by weight of zinc oxide and 3.0-9.0 parts by weight of stearic acid are fully mixed in an internal mixer;
（2）再将0.1-1.0重量份的交联剂双叔丁基过氧化二异丙苯和1.0-10.0重量份树脂交联剂SSA-1252加入到密炼机中，混炼得混合物；(2) 0.1-1.0 parts by weight of cross-linking agent bis-tert-butyl dicumyl peroxide and 1.0-10.0 parts by weight of resin cross-linking agent SSA-1252 are added into the internal mixer, and the mixture is kneaded;
（3）接着将1.0-6.0重量份的发泡剂偶氮二甲酰胺与步骤（2）所得的混合物一起加入到密炼机中充分混炼均匀，将得到的共混胶在开炼机上进行开炼并将其处理成厚度为10-12 mm片材，得到混炼胶；(3) Next, add 1.0-6.0 parts by weight of the foaming agent azodicarbonamide together with the mixture obtained in step (2) into the internal mixer to fully mix evenly, and the obtained blended rubber is carried out on an open mixer. Open and process it into a sheet with a thickness of 10-12 mm to obtain a mixed rubber;
（4）预先将硫化机内嵌模具加热至175-200 ℃，然后均匀地喷涂上聚硅氧烷水性乳液脱模剂，接着将步骤（3）所得的片材放入硫化机，设置一定的预压时间和硫化时间，进行模压交联发泡成型出片，25℃下冷却，得到高收缩稳定性，高硬度橡胶基复合发泡材料。(4) Preheat the embedded mold of the vulcanizer to 175-200 °C, then spray the release agent of the polysiloxane aqueous emulsion evenly, and then put the sheet obtained in step (3) into the vulcanizer, set a certain Pre-pressing time and vulcanization time, molding, cross-linking, foaming and forming into sheets, and cooling at 25 ° C to obtain high shrinkage stability and high hardness rubber-based composite foaming materials.
优选地，步骤（1）中，热塑性丁苯橡胶/氯丁橡胶/乙烯-醋酸乙烯酯中热塑性丁苯橡胶的重量比为1/1-1/2；氯丁橡胶的重量比为1/10-3/10；乙烯-醋酸乙烯酯的重量比为1/10-2/10。Preferably, in step (1), the weight ratio of thermoplastic styrene-butadiene rubber in thermoplastic styrene-butadiene rubber/chloroprene rubber/ethylene-vinyl acetate is 1/1-1/2; the weight ratio of neoprene rubber is 1/10 -3/10; the weight ratio of ethylene-vinyl acetate is 1/10-2/10.
优选地，步骤（1）中，热塑性丁苯橡胶中的苯乙烯单体单元含量为20%-24.5%，熔体流动速率0.10-0.50 g/10min；Preferably, in step (1), the content of styrene monomer units in the thermoplastic styrene-butadiene rubber is 20%-24.5%, and the melt flow rate is 0.10-0.50 g/10min;
氯丁橡胶的玻璃化温度-40-50℃，软化点约80℃；The glass transition temperature of neoprene rubber is -40-50℃, and the softening point is about 80℃;
乙烯-醋酸乙烯酯的醋酸乙烯酯单体单元含量为15%-28%；The vinyl acetate monomer unit content of ethylene-vinyl acetate is 15%-28%;
树脂交联剂SSA-1252中的六亚甲基四胺的含量为8.5-9.5。The content of hexamethylenetetramine in the resin crosslinking agent SSA-1252 is 8.5-9.5.
优选地，步骤（3）中，共混胶开练的具体步骤为：将得到的共混胶在开炼机上进行开炼，先逐渐调小开炼机辊筒的距离，使共混胶变薄，多次打三角包5-10 min，然后逐渐调大开炼机辊筒的距离，并处理成厚10-12 mm的片材，得到混炼胶。Preferably, in step (3), the specific steps of opening and training the rubber blend are as follows: the obtained rubber blend is milled on an open mill, and the distance between the rollers of the open mill is gradually reduced to make the rubber blend become Thin, make the triangular bag for 5-10 minutes several times, then gradually increase the distance of the roller of the open mill, and process it into a sheet with a thickness of 10-12 mm to obtain the mixed rubber.
优选地，步骤（4）中，硫化的预压时间30-45 s，硫化的时间350-500 s。Preferably, in step (4), the pre-pressing time of vulcanization is 30-45 s, and the vulcanization time is 350-500 s.
如上述所述的制备方法制备得到的高收缩稳定性、高硬度橡胶基复合发泡材料。The high shrinkage stability and high hardness rubber-based composite foam material prepared by the above-mentioned preparation method.
本发明具有以下优点：The present invention has the following advantages:
1.本发明采用具有稳定交联键的树脂硫化剂SSA-1252和DCP交联SBR、CR和EVA的三元复配体系制备了SBS/CR/EVA复合发泡材料，相比于传统的发泡材料具有较好的综合性能，即高的硬度：65-90C、收缩率降低至0.25-0.6%、后收缩率为2.0-5.5%、密度为0.35-0.75g/cm3，优异的抗张强度（3.0-4.5 MPa）和撕裂强度（4.0-7.0 N/mm）。1. The present invention adopts the ternary compound system of resin vulcanizing agent SSA-1252 with stable cross-linking bond and DCP cross-linking SBR, CR and EVA to prepare SBS/CR/EVA composite foam material, compared with traditional The foam material has good comprehensive properties, namely high hardness: 65-90C, shrinkage rate reduced to 0.25-0.6%, post-shrinkage rate 2.0-5.5%, density 0.35-0.75g/cm 3 , excellent tensile strength Strength (3.0-4.5 MPa) and tear strength (4.0-7.0 N/mm).
2.由于传统硫化-发泡工艺所采用的硫磺交联结构易发生硫化返原现象；本发明采用的树脂交联剂的交联键为C-O、C-C类型键，具有稳定性的交联结构，高温硫化时不出现硫化返原现象；而且，树脂交联剂具有刚性的分子链，对橡胶分子链起到支撑的作用，进一步缓解了其发泡材料的尺寸稳定性问题。引入氯丁橡胶是为了更好的发挥树脂交联剂SSA-1252交联效果，同时应用其优异的极性（含有-Cl基团），增加材料的力学性能。2. Because the sulfur cross-linking structure adopted by the traditional vulcanization-foaming process is prone to vulcanization reversion; the cross-linking bond of the resin cross-linking agent adopted in the present invention is C-O, C-C type bond, and has a stable cross-linked structure, There is no vulcanization reversion phenomenon during high temperature vulcanization; moreover, the resin crosslinking agent has a rigid molecular chain, which supports the rubber molecular chain and further alleviates the dimensional stability problem of the foamed material. The introduction of neoprene rubber is to better exert the cross-linking effect of the resin cross-linking agent SSA-1252, and at the same time use its excellent polarity (containing -Cl group) to increase the mechanical properties of the material.
具体实施方式Detailed ways
下面结合具体实施方式对本发明进行详细的说明。The present invention will be described in detail below with reference to specific embodiments.
一种高收缩稳定性，高硬度橡胶基复合发泡材料的制备方法，包括以下步骤：A preparation method of high shrinkage stability and high hardness rubber-based composite foam material, comprising the following steps:
（1）将40-70重量份的热塑性丁苯橡胶、15-40重量份氯丁橡胶、5-30重量份的乙烯-醋酸乙烯酯与10-30重量份的白炭黑、1.0-6.0重量份石蜡、3.0-12.0重量份的氧化锌和3.0-9.0重量份的硬脂酸在密炼机里充分混炼均匀；(1) 40-70 parts by weight of thermoplastic styrene-butadiene rubber, 15-40 parts by weight of neoprene, 5-30 parts by weight of ethylene-vinyl acetate and 10-30 parts by weight of white carbon black, 1.0-6.0 parts by weight Parts of paraffin, 3.0-12.0 parts by weight of zinc oxide and 3.0-9.0 parts by weight of stearic acid are fully mixed in an internal mixer;
优选地，步骤（1）中，热塑性丁苯橡胶/氯丁橡胶/乙烯-醋酸乙烯酯中热塑性丁苯橡胶的重量比为1/1-1/2；氯丁橡胶的重量比为1/10-3/10；乙烯-醋酸乙烯酯的重量比为1/10-2/10。Preferably, in step (1), the weight ratio of thermoplastic styrene-butadiene rubber in thermoplastic styrene-butadiene rubber/chloroprene rubber/ethylene-vinyl acetate is 1/1-1/2; the weight ratio of neoprene rubber is 1/10 -3/10; the weight ratio of ethylene-vinyl acetate is 1/10-2/10.
热塑性丁苯橡胶中的苯乙烯单体单元含量为20%-24.5%，熔体流动速率0.10-0.50g/10min；The content of styrene monomer units in thermoplastic styrene-butadiene rubber is 20%-24.5%, and the melt flow rate is 0.10-0.50g/10min;
氯丁橡胶的玻璃化温度-40-50℃，软化点约80℃；The glass transition temperature of neoprene rubber is -40-50℃, and the softening point is about 80℃;
乙烯-醋酸乙烯酯的醋酸乙烯酯单体单元含量为15%-28%；The vinyl acetate monomer unit content of ethylene-vinyl acetate is 15%-28%;
树脂交联剂SSA-1252中的六亚甲基四胺的含量为8.5-9.5。The content of hexamethylenetetramine in the resin crosslinking agent SSA-1252 is 8.5-9.5.
（2）再将0.1-1.0重量份的交联剂双叔丁基过氧化二异丙苯和1.0-10.0重量份树脂交联剂SSA-1252加入到密炼机中，混炼得混合物；(2) 0.1-1.0 parts by weight of cross-linking agent bis-tert-butyl dicumyl peroxide and 1.0-10.0 parts by weight of resin cross-linking agent SSA-1252 are added into the internal mixer, and the mixture is kneaded;
（3）接着将1.0-6.0重量份的发泡剂偶氮二甲酰胺与步骤（2）所得的混合物一起加入到密炼机中充分混炼均匀，将得到的共混胶在开炼机上进行开炼并将其处理成厚度为10-12 mm片材，得到混炼胶；(3) Next, add 1.0-6.0 parts by weight of the foaming agent azodicarbonamide together with the mixture obtained in step (2) into the internal mixer to fully mix evenly, and the obtained blended rubber is carried out on an open mixer. Open and process it into a sheet with a thickness of 10-12 mm to obtain a mixed rubber;
优选地，步骤（3）中，共混胶开练的具体步骤为：将得到的共混胶在开炼机上进行开炼，先逐渐调小开炼机辊筒的距离，使共混胶变薄，多次打三角包5-10 min，然后逐渐调大开炼机辊筒的距离，并处理成厚10-12 mm的片材，得到混炼胶。Preferably, in step (3), the specific steps of opening and training the rubber blend are as follows: the obtained rubber blend is milled on an open mill, and the distance between the rollers of the open mill is gradually reduced to make the rubber blend become Thin, make the triangular bag for 5-10 minutes several times, then gradually increase the distance of the roller of the open mill, and process it into a sheet with a thickness of 10-12 mm to obtain the mixed rubber.
（4）预先将硫化机内嵌模具加热至175-200 ℃，然后均匀地喷涂上聚硅氧烷水性乳液脱模剂，接着将步骤（3）所得的片材放入硫化机，设置一定的预压时间和硫化时间，进行模压交联发泡成型出片，25℃下冷却，得到高收缩稳定性，高硬度橡胶基复合发泡材料。(4) Preheat the embedded mold of the vulcanizer to 175-200 °C, then spray the release agent of the polysiloxane aqueous emulsion evenly, and then put the sheet obtained in step (3) into the vulcanizer, set a certain Pre-pressing time and vulcanization time, molding, cross-linking, foaming and forming into sheets, and cooling at 25 ° C to obtain high shrinkage stability and high hardness rubber-based composite foaming materials.
优选地，步骤（4）中，硫化的预压时间30-45 s，硫化的时间350-500 s。Preferably, in step (4), the pre-pressing time of vulcanization is 30-45 s, and the vulcanization time is 350-500 s.
如上述所述的制备方法制备得到的高收缩稳定性、高硬度橡胶基复合发泡材料。The high shrinkage stability and high hardness rubber-based composite foam material prepared by the above-mentioned preparation method.
实施例一：Example 1:
（1）将50重量份的热塑性丁苯橡胶、20重量份氯丁橡胶、30重量份的乙烯-醋酸乙烯酯与20重量份的白炭黑、5.0重量份的石蜡、9.0重量份的氧化锌和6.0重量份的硬脂酸在120 ℃，转速为30 r/min的密炼机里充分混炼均匀；(1) 50 parts by weight of thermoplastic styrene-butadiene rubber, 20 parts by weight of neoprene, 30 parts by weight of ethylene-vinyl acetate, 20 parts by weight of silica, 5.0 parts by weight of paraffin, and 9.0 parts by weight of zinc oxide Mix well with 6.0 parts by weight of stearic acid at 120 °C in an internal mixer with a rotational speed of 30 r/min;
（2）再将0.6重量份的交联剂双叔丁基过氧化二异丙苯和10重量份树脂交联剂SSA-1252加入到密炼机中，混炼得混合物；(2) 0.6 parts by weight of cross-linking agent di-tert-butyl dicumyl peroxide and 10 parts by weight of resin cross-linking agent SSA-1252 are added to the internal mixer, and the mixture is kneaded;
（3）接着将3.0重量份的发泡剂偶氮二甲酰胺与步骤（2）所得的混合物一起加入到密炼机中充分混炼均匀，将得到的共混胶在开炼机上进行开炼，先逐渐调小开炼机辊筒的距离，使共混胶变薄，多次打三角包约5min，然后逐渐调大开炼机辊筒的距离，并将共混胶处理成厚度为10 mm的片材，得到混炼胶；(3) Next, add 3.0 parts by weight of the foaming agent azodicarbonamide together with the mixture obtained in step (2) into the internal mixer and fully knead it evenly. , first gradually reduce the distance of the mill rollers to make the blended rubber thinner, beat the triangular bag for about 5 minutes several times, then gradually increase the distance of the mill rollers, and process the blended rubber to a thickness of 10 mm sheet to obtain a mixed rubber;
（4）预先将硫化机内嵌模具加热至185 ℃，然后均匀地喷涂上聚硅氧烷水性乳液脱模剂，接着，将步骤（3）所得的片材放入硫化机，设置预压时间25 s，硫化时间450 s，进行模压交联发泡成型出片，25℃下冷却，得到高收缩稳定性，高硬度橡胶基复合发泡材料。(4) Preheat the built-in mold of the vulcanizer to 185 °C, and then spray the polysiloxane aqueous emulsion release agent evenly. Then, put the sheet obtained in step (3) into the vulcanizer and set the pre-pressing time. 25 s, vulcanization time 450 s, molding, cross-linking, foaming and forming into sheets, and cooling at 25 °C to obtain high shrinkage stability and high hardness rubber-based composite foamed materials.
由实施例一制备的发泡材料的硬度为71C、收缩率为0.4%、后收缩率为2.8%、密度为0.39 g/cm3，抗张强度为3.5 MPa，撕裂强度为4.5 N/mm。The hardness of the foamed material prepared by Example 1 is 71C, the shrinkage rate is 0.4%, the post-shrinkage rate is 2.8%, the density is 0.39 g/cm 3 , the tensile strength is 3.5 MPa, and the tear strength is 4.5 N/mm .
实施例二：Embodiment 2:
（1）将60重量份的热塑性丁苯橡胶、20重量份氯丁橡胶20重量份的乙烯-醋酸乙烯酯与20重量份的白炭黑、5.0重量份石蜡、9.0重量份的氧化锌和6.0重量份的硬脂酸在密炼机里充分混炼均匀；(1) 60 parts by weight of thermoplastic styrene-butadiene rubber, 20 parts by weight of chloroprene rubber, 20 parts by weight of ethylene-vinyl acetate, 20 parts by weight of silica, 5.0 parts by weight of paraffin, 9.0 parts by weight of zinc oxide and 6.0 parts by weight of The stearic acid of the weight portion is fully mixed evenly in the internal mixer;
（2）再将0.8重量份的交联剂双叔丁基过氧化二异丙苯和8.0重量份树脂交联剂SSA-1252加入到密炼机中，混炼得混合物；(2) 0.8 parts by weight of the cross-linking agent di-tert-butyl dicumyl peroxide and 8.0 parts by weight of the resin cross-linking agent SSA-1252 are added to the internal mixer, and the mixture is kneaded;
（3）接着将3.0重量份的发泡剂偶氮二甲酰胺与步骤（2）所得的混合物一起加入到密炼机中充分混炼均匀，将得到的共混胶在开炼机上进行开炼，先逐渐调小开炼机辊筒的距离，使共混胶变薄，多次打三角包约6min，然后逐渐调大开炼机辊筒的距离，并将共混胶处理成厚度为10.5mm的片材，得到混炼胶；(3) Next, add 3.0 parts by weight of the foaming agent azodicarbonamide together with the mixture obtained in step (2) into the internal mixer and fully knead it evenly. , first gradually reduce the distance of the mill rollers to make the blended rubber thinner, beat the triangular bag for about 6 minutes for several times, then gradually increase the distance of the mill rollers, and process the blended rubber to a thickness of 10.5 mm sheet to obtain a mixed rubber;
（4）预先将硫化机内嵌模具加热至190 ℃，然后均匀地喷涂上聚硅氧烷水性乳液脱模剂，接着，将步骤（3）所得的片材放入硫化机，设置预压时间30 s，硫化时间400 s，进行模压交联发泡成型出片，25℃下冷却，得到高收缩稳定性，高硬度橡胶基复合发泡材料。(4) Preheat the built-in mold of the vulcanizer to 190 °C, and then spray the release agent of the polysiloxane aqueous emulsion evenly. Then, put the sheet obtained in step (3) into the vulcanizer, and set the pre-pressing time. 30 s, vulcanization time 400 s, molding, cross-linking, foaming and forming into sheets, and cooling at 25 °C to obtain a rubber-based composite foam material with high shrinkage stability and high hardness.
由实施例二制备的发泡材料的硬度为74C、收缩率为0.45%、后收缩率为2.8%、密度为0.57 g/cm3，抗张强度为4.1 MPa，撕裂强度为6.4 N/mm。The hardness of the foamed material prepared by Example 2 is 74C, the shrinkage rate is 0.45%, the post-shrinkage rate is 2.8%, the density is 0.57 g/cm 3 , the tensile strength is 4.1 MPa, and the tear strength is 6.4 N/mm .
实施例三：Embodiment three:
（1）将60重量份的热塑性丁苯橡胶、20重量份氯丁橡胶20重量份的乙烯-醋酸乙烯酯与25重量份的白炭黑、10重量份石蜡、9.0重量份的氧化锌和3.0重量份的硬脂酸在120℃，转速为30 r/min的密炼机里充分混炼均匀；(1) 60 parts by weight of thermoplastic styrene-butadiene rubber, 20 parts by weight of chloroprene rubber, 20 parts by weight of ethylene-vinyl acetate, 25 parts by weight of silica, 10 parts by weight of paraffin, 9.0 parts by weight of zinc oxide and 3.0 parts by weight of The stearic acid in parts by weight is fully kneaded evenly in an internal mixer at 120°C and a rotational speed of 30 r/min;
（2）再将1.0重量份的交联剂双叔丁基过氧化二异丙苯和4.0重量份树脂交联剂SSA-1252加入到密炼机中，混炼得混合物；(2) 1.0 parts by weight of the cross-linking agent di-tert-butyl dicumyl peroxide and 4.0 parts by weight of the resin cross-linking agent SSA-1252 were added to the internal mixer, and the mixture was kneaded;
（3）接着将3.0重量份的发泡剂偶氮二甲酰胺与步骤（2）所得的混合物一起加入到密炼机中充分混炼均匀，将得到的共混胶在开炼机上进行开炼，先逐渐调小开炼机辊筒的距离，使共混胶变薄，多次打三角包约7min，然后逐渐调大开炼机辊筒的距离，并将共混胶处理成厚度为11mm的片材，得到混炼胶；(3) Next, add 3.0 parts by weight of the foaming agent azodicarbonamide together with the mixture obtained in step (2) into the internal mixer and fully knead it evenly. , first gradually reduce the distance of the mill rollers to make the blended rubber thinner, beat the triangular bag for about 7 minutes for several times, then gradually increase the distance of the mill rollers, and process the blended rubber to a thickness of 11mm The sheet is obtained to obtain a mixed rubber;
（4）预先将硫化机内嵌模具加热至190 ℃，然后均匀地喷涂上聚硅氧烷水性乳液脱模剂，接着，将步骤（3）所得的片材放入硫化机，设置预压时间25 s，硫化时间400 s，进行模压交联发泡成型出片，25℃下冷却，得到高收缩稳定性，高硬度橡胶基复合发泡材料。(4) Preheat the built-in mold of the vulcanizer to 190 °C, and then spray the release agent of the polysiloxane aqueous emulsion evenly. Then, put the sheet obtained in step (3) into the vulcanizer, and set the pre-pressing time. 25 s, vulcanization time 400 s, molding, cross-linking, foaming and forming into sheets, and cooling at 25 °C to obtain high shrinkage stability and high hardness rubber-based composite foamed materials.
由实施例三制备的发泡材料的硬度为83C、收缩率为0.21%、后收缩率为2.0%、密度为0.65 g/cm3，抗张强度为4.5 MPa，撕裂强度为6.8 N/mm。The hardness of the foamed material prepared by Example 3 is 83C, the shrinkage rate is 0.21%, the post-shrinkage rate is 2.0%, the density is 0.65 g/cm 3 , the tensile strength is 4.5 MPa, and the tear strength is 6.8 N/mm .
实施例四：Embodiment 4:
（1）将60重量份的热塑性丁苯橡胶、30重量份氯丁橡胶10重量份的乙烯-醋酸乙烯酯与20重量份的白炭黑、5重量份石蜡、9.0重量份的氧化锌和3.0重量份的硬脂酸在120℃，转速为30 r/min的密炼机里充分混炼均匀；(1) 60 parts by weight of thermoplastic styrene-butadiene rubber, 30 parts by weight of chloroprene rubber, 10 parts by weight of ethylene-vinyl acetate, 20 parts by weight of silica, 5 parts by weight of paraffin, 9.0 parts by weight of zinc oxide and 3.0 parts by weight of The stearic acid in parts by weight is fully kneaded evenly in an internal mixer at 120°C and a rotational speed of 30 r/min;
（2）再将1.0重量份的交联剂双叔丁基过氧化二异丙苯和6.0重量份树脂交联剂SSA-1252加入到密炼机中，混炼得混合物；(2) 1.0 parts by weight of the cross-linking agent di-tert-butyl dicumyl peroxide and 6.0 parts by weight of the resin cross-linking agent SSA-1252 were added to the internal mixer, and the mixture was kneaded;
（3）接着将3.0重量份的发泡剂偶氮二甲酰胺与步骤（2）所得的混合物一起加入到密炼机中充分混炼均匀，将得到的共混胶在开炼机上进行开炼，先逐渐调小开炼机辊筒的距离，使共混胶变薄，多次打三角包约9min，然后逐渐调大开炼机辊筒的距离，并将共混胶处理成厚度为12mm的片材，得到混炼胶；(3) Next, add 3.0 parts by weight of the foaming agent azodicarbonamide together with the mixture obtained in step (2) into the internal mixer and fully knead it evenly. , first gradually reduce the distance of the mill rollers to make the blended rubber thinner, beat the triangular bag for about 9 minutes several times, then gradually increase the distance of the mill rollers, and process the blended rubber to a thickness of 12mm The sheet is obtained to obtain a mixed rubber;
（4）预先将硫化机内嵌模具加热至190 ℃，然后均匀地喷涂上聚硅氧烷水性乳液脱模剂，接着，将步骤（3）所得的片材放入硫化机，设置预压时间25 s，硫化时间400 s，进行模压交联发泡成型出片，25℃下冷却，得到高收缩稳定性，高硬度橡胶基复合发泡材料。(4) Preheat the built-in mold of the vulcanizer to 190 °C, and then spray the release agent of the polysiloxane aqueous emulsion evenly. Then, put the sheet obtained in step (3) into the vulcanizer, and set the pre-pressing time. 25 s, vulcanization time 400 s, molding, cross-linking, foaming and forming into sheets, and cooling at 25 °C to obtain high shrinkage stability and high hardness rubber-based composite foamed materials.
由实施例四制备的发泡材料的硬度为82C、收缩率为0.25%、后收缩率为2.5%、密度为0.58 g/cm3，抗张强度为4.7 MPa，撕裂强度为6.6 N/mm。The hardness of the foamed material prepared by Example 4 is 82C, the shrinkage rate is 0.25%, the post-shrinkage rate is 2.5%, the density is 0.58 g/cm 3 , the tensile strength is 4.7 MPa, and the tear strength is 6.6 N/mm .
本发明的内容不限于实施例所列举，本领域普通技术人员通过阅读本发明说明书而对本发明技术方案采取的任何等效的变换，均为本发明的权利要求所涵盖。The content of the present invention is not limited to those listed in the embodiments, and any equivalent transformations taken by those of ordinary skill in the art to the technical solutions of the present invention by reading the description of the present invention are covered by the claims of the present invention.
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| CN110713641B (en) * | 2019-10-25 | 2021-06-15 | 陕西科技大学 | A kind of preparation method of soft shock-absorbing, tear-resistant sports insole material |
| CN111704755A (en) * | 2020-06-28 | 2020-09-25 | 陕西科技大学 | A kind of preparation method of rubber foam material with bubble inner wall shell |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6595321B1 (en) * | 2002-03-28 | 2003-07-22 | Collins & Aikman Products Co. | Floor mats having peripheral apertures with acoustic absorbing material |
| WO2004037872A2 (en) * | 2002-10-24 | 2004-05-06 | Exxonmobil Chemical Patents Inc. | Branched crystalline polypropylene |
| CN102775652A (en) * | 2012-08-16 | 2012-11-14 | 株洲时代新材料科技股份有限公司 | Thermoplastic elastomer micropore foaming material and preparation method thereof |
| CN105566730A (en) * | 2014-09-04 | 2016-05-11 | 张文俊 | Poly vinyl acetate modified foaming body |
| CN107118426A (en) * | 2017-06-12 | 2017-09-01 | 江苏天有贸易有限公司 | EVA/ rubber blends sole material formula and preparation method thereof |
| CN107501806A (en) * | 2017-10-08 | 2017-12-22 | 界首市旭升塑胶制品有限公司 | A kind of hard plastic sole product of wear-resisting height |
-
2018
- 2018-12-29 CN CN201811635936.6A patent/CN109627527B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6595321B1 (en) * | 2002-03-28 | 2003-07-22 | Collins & Aikman Products Co. | Floor mats having peripheral apertures with acoustic absorbing material |
| WO2004037872A2 (en) * | 2002-10-24 | 2004-05-06 | Exxonmobil Chemical Patents Inc. | Branched crystalline polypropylene |
| CN102775652A (en) * | 2012-08-16 | 2012-11-14 | 株洲时代新材料科技股份有限公司 | Thermoplastic elastomer micropore foaming material and preparation method thereof |
| CN105566730A (en) * | 2014-09-04 | 2016-05-11 | 张文俊 | Poly vinyl acetate modified foaming body |
| CN107118426A (en) * | 2017-06-12 | 2017-09-01 | 江苏天有贸易有限公司 | EVA/ rubber blends sole material formula and preparation method thereof |
| CN107501806A (en) * | 2017-10-08 | 2017-12-22 | 界首市旭升塑胶制品有限公司 | A kind of hard plastic sole product of wear-resisting height |
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