CN111548593A - 一种环保型发泡丁苯橡胶的制备方法 - Google Patents
一种环保型发泡丁苯橡胶的制备方法 Download PDFInfo
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- CN111548593A CN111548593A CN202010519582.XA CN202010519582A CN111548593A CN 111548593 A CN111548593 A CN 111548593A CN 202010519582 A CN202010519582 A CN 202010519582A CN 111548593 A CN111548593 A CN 111548593A
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- butadiene rubber
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- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920001971 elastomer Polymers 0.000 claims abstract description 75
- 239000005060 rubber Substances 0.000 claims abstract description 75
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003063 flame retardant Substances 0.000 claims abstract description 66
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000006229 carbon black Substances 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 25
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004088 foaming agent Substances 0.000 claims abstract description 15
- 239000011787 zinc oxide Substances 0.000 claims abstract description 14
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 13
- 229920001194 natural rubber Polymers 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
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- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000004073 vulcanization Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
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- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
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- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
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- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 claims description 6
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical group C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 3
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- 230000002776 aggregation Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
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- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
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- 238000000354 decomposition reaction Methods 0.000 description 2
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- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
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- 231100000053 low toxicity Toxicity 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 231100000719 pollutant Toxicity 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
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- -1 diethyl chloride Chemical compound 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 238000009413 insulation Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
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- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
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- 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
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
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Abstract
本发明公开了一种环保型发泡丁苯橡胶的制备方法,该发泡丁苯橡胶由如下重量份原料制成:改性丁苯橡胶90‑100份、天然橡胶16‑20份、白炭黑45‑50份、炭黑8‑10份、氧化锌1.6‑2份、促进剂3‑4份、硫磺1.8‑2份、发泡剂2.7‑3份;制备方法为:第一步、密炼;第二步、开炼机混炼;第三步、硫化。本发明采用自合成的阻燃剂,为P‑N协效阻燃剂,不仅具有优异的阻燃性能,而且与橡胶基体具有较强的相互作用,符合环保要求,提高材料阻燃性能的环保性、高效性和持久性;通过对丁苯橡胶进行改性,在丁苯橡胶分子链上引入环氧基团和柔性分子链,环氧基团促进白炭黑的分散,提高与阻燃剂的结合作用力,柔性分子链能够改善橡胶材料的力学损耗性能。
Description
技术领域
本发明属于橡胶材料制备领域,具体地,涉及一种环保型发泡丁苯橡胶的制备方法。
背景技术
橡胶制品的蜂窝结构使其拥有了一些有价值的特性,如非常低的密度,高绝缘能力和良好的压缩性。其应用范围包括建筑材料(隔音、密封),汽车组件(抗振动、密封),家庭物品(海绵、垫类),以及运动和休闲商品。在制作发泡橡胶制品的过程中,橡胶化合物和一种气体发生了复杂的相互作用。在发泡过程的开始,气体溶解在聚合物中。然后在过饱和度和压力下降或温度上升时导致分离,并形成一个稳定的泡沫结构。丁苯橡胶作为其中重要的种类,其主链上均含有大量的碳、氢等元素,受热熔化时易产生可燃气体,在高温时易与氧作用发生燃烧,造成其氧指数低,阻燃性能较差,限制了SBR的应用范围。
专利号为CN201110346009.4公开了一种环保型丁苯橡胶闭孔二次发泡材料及其制备方法,该发泡材料,由以下重量份配比的原料制得:丁苯橡胶60-100份、硫化剂1.3-2.2份、硫化促进剂0.4-1份、硬脂酸0.5-1份、氧化锌2.5-5.5份、发泡剂3-6.5份、发泡助剂3-6.6份、棕油膏7.5-15.2份、补强填充剂75-85份、镁强粉25-32份、轻质碳酸钙36-73份、奈族软化油25-54份、分散剂1.5-3份、抗臭氧化剂0.6-1.5份、防老化剂0.6-1.5份。该申请虽然通过降低卤素的含量能够提升丁苯橡胶的阻燃性能和环保性能,但是该申请包含的原料种类多,在形成发泡材料时,很难使各成分在产品中分布均匀,继而影响到发泡材料的性能。
发明内容
本发明的目的在于提供一种环保型发泡丁苯橡胶的制备方法,采用自合成的阻燃剂进行提高丁苯橡胶基体的阻燃性能,该阻燃剂为P-N协效阻燃剂,不仅具有优异的阻燃性能,而且与橡胶基体具有较强的相互作用,使得阻燃剂不易迁移和析出,该阻燃剂不包含卤素,燃烧分解不会产生污染物,因此,符合环保要求,提高发泡丁苯橡胶阻燃性能的环保性、高效性和持久性;通过对丁苯橡胶进行改性,能够在丁苯橡胶分子链上引入环氧基团和柔性分子链,环氧基团的引入能够促进白炭黑的分散,提高与阻燃剂的结合作用力,柔性分子链的引入能够改善橡胶材料的力学损耗性能;本发明制得的发泡丁苯橡胶具有环保、低毒、低烟、无污染、改性成本低等优点。
本发明的目的可以通过以下技术方案实现:
一种环保型发泡丁苯橡胶的制备方法,该发泡丁苯橡胶由如下重量份原料制成:改性丁苯橡胶90-100份、天然橡胶16-20份、白炭黑45-50份、氧化锌1.6-2份、促进剂3-4份、硫磺1.8-2份、发泡剂2.7-3份;
该发泡丁苯橡胶的制备方法,包括如下步骤:
第一步、将密炼机打开设定温度为100℃,当仪器的温度达到时,将改性丁苯橡胶和天然橡胶加入到密炼机中密炼13-15min,然后加入白炭黑和氧化锌密炼5-6min,接着添加发泡剂、硫磺和促进剂继续密炼5-6min,得到共混胶;
第二步、共混胶于室温下停放24h后,将开炼机设定温度为80℃,将共混胶在开炼机上进行开炼,打三角包7-10次,然后处理成10-12mm片材,得到混炼胶;
第三步、将混炼胶在平板硫化机上进行预硫化,预硫化温度为125℃,预硫化时间为14-15min,然后进行二次硫化,二次硫化参数150℃×t90,制得所述发泡丁苯橡胶。
进一步地,所述阻燃剂由如下方法制成:
(1)将二乙基氯代磷酸酯溶解于乙腈中,形成浓度为0.8mol/L的含磷溶液;
(2)将2.0g的2,4-二氨基甲苯和3.3g的三乙胺溶于180-200mL的乙腈中,搅拌混合均匀后,通入氮气15min并控制溶液温度在3-4℃,在氮气条件下将38-40mL含磷溶液缓慢滴入混合液中,滴加完成后保持冰浴反应55-65min后,再将整个装置移入52-55℃油浴锅中,氮气下回流反应22-24h,反应结束后,将产物抽滤、洗涤、干燥,得到阻燃剂。
进一步地,所述改性丁苯橡胶由如下方法制备:
S1、按照体积比3.5:1将二氯甲烷和甲醇混合均匀,得到混合溶剂,备用;将烯丙基缩水甘油醚溶解到混合溶剂中,得到质量分数为5%的改性液;
S2、在反应釜中将丁苯橡胶溶解到混合溶剂中,形成质量分数为20%的丁苯橡胶溶液,将反应釜的的温度控制在8-10℃,将上述改性液逐滴滴加到反应釜中,使其缓慢的和丁苯橡胶发生反应,滴加结束保温反应3h;
S3、再加入四氯化锡作为催化剂,体系慢慢升温到40-42℃,继续保温反应9-10h,反应结束后,在蒸馏釜中加入去离子水和乳化剂使其完全溶解,将反应釜的温度提升到90℃,搅拌下将反应结束的溶液慢慢滴加到提取釜中,将析出的产物离心、干燥,得到改性丁苯橡胶;
进一步地,步骤S3中四氯化锡的加入量为丁苯橡胶质量的2%。
进一步地,步骤S3中去离子水的加入量为反应结束时体系质量的1.5-2倍,乳化剂为壬基酚醚磷酸酯,乳化剂的加入量为去离子水质量的3%。
本发明的有益效果:
本发明采用改性丁苯橡胶作为橡胶基体,将烯丙基缩水甘油醚与丁苯橡胶进行改性共聚反应,可在丁苯橡胶分子链中引入烯丙基缩水甘油醚,也即,在丁苯橡胶的分子链中引入了环氧基团和柔性链;引入的环氧基团可以与白炭黑表面的硅羟基相互作用,从而抑制白炭黑粒子间的相互作用,减少团聚,提高白炭黑在橡胶基体中的分散,并且增强白炭黑与橡胶基体的相互作用,进而促进更多的包容橡胶被释放而参与交联,形成三维网络,使发泡丁苯橡胶表现出高弹性;引入的环氧基团还能与阻燃剂分子上含有的-NH2官能团相互作用,提高阻燃剂与橡胶基体的作用力,增强阻燃剂的牢固性,使阻燃剂不易迁移和析出,使阻燃剂更充分发挥其阻燃性能,并且在受热过程中促进丁苯橡胶分子链成炭,提高阻燃效果;此外,在丁苯橡胶的分子链中引入了柔性链,能够改善橡胶材料的力学损耗性能;
本发明在发泡丁苯橡胶中加入了合成的阻燃剂,二乙基氯代磷酸酯分子上的-Cl原子与2,4-二氨基甲苯分子上的氨基-NH2发生取代反应,使二氨基二苯甲烷分子接枝于磷酸酯分子上,形成含P、N两种元素的阻燃剂;由于2,4-二氨基甲苯分子上存在的两个氨基的活性不同,通过控制二乙基氯代磷酸酯和2,4-二氨基甲苯的用量,可使活性较强的氨基(甲基对位上的氨基)与-Cl发生取代反应,而另一个氨基不参与反应,形成含P、N两种元素的阻燃剂,并且该阻燃剂分子中含有裸露的-NH2官能团;该阻燃剂由P-N协同产生多种作用,受热释放出的NH3和H2O,可起到气源的作用,同时起到稀释可燃性气体和氧气浓度的作用,缓减燃烧速度,受热分解产生的磷酸和偏磷酸等可做酸源,苯环和丁苯橡胶部分分子链可做碳源,三源相互作用产生膨胀的致密、厚实的残炭层,隔绝氧气和热量的传递,起到良好的阻燃效果;
本发明采用自合成的阻燃剂进行提高丁苯橡胶基体的阻燃性能,该阻燃剂为P-N协效阻燃剂,不仅具有优异的阻燃性能,而且与橡胶基体具有较强的相互作用,使得阻燃剂不易迁移和析出,该阻燃剂不包含卤素,燃烧分解不会产生污染物,因此,符合环保要求,提高发泡丁苯橡胶阻燃性能的环保性、高效性和持久性;通过对丁苯橡胶进行改性,能够在丁苯橡胶分子链上引入环氧基团和柔性分子链,环氧基团的引入能够促进白炭黑的分散,提高与阻燃剂的结合作用力,柔性分子链的引入能够改善橡胶材料的力学损耗性能;本发明制得的发泡丁苯橡胶具有环保、低毒、低烟、无污染、改性成本低等优点。
具体实施方式
下面将结合实施例对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
一种环保型发泡丁苯橡胶的制备方法,该发泡丁苯橡胶由如下重量份原料制成:改性丁苯橡胶90-100份、天然橡胶16-20份、白炭黑45-50份、氧化锌1.6-2份、促进剂3-4份、硫磺1.8-2份、发泡剂2.7-3份;
其中,促进剂为促进剂TMTD;发泡剂为OBSH-75;
阻燃剂的制备如下:
(1)将二乙基氯代磷酸酯溶解于乙腈中,形成浓度为0.8mol/L的含磷溶液;
(2)将2.0g的2,4-二氨基甲苯和3.3g的三乙胺溶于180-200mL的乙腈中,搅拌混合均匀后,通入氮气15min并控制溶液温度在3-4℃,在氮气条件下将38-40mL含磷溶液缓慢滴入混合液中,滴加完成后保持冰浴反应55-65min后,再将整个装置移入52-55℃油浴锅中,氮气下回流反应22-24h,反应结束后,将产物抽滤、洗涤、干燥,得到阻燃剂;
二乙基氯代磷酸酯分子上的-Cl原子与2,4-二氨基甲苯分子上的氨基-NH2发生取代反应,使二氨基二苯甲烷分子接枝于磷酸酯分子上,形成含P、N两种元素的阻燃剂;由于2,4-二氨基甲苯分子上存在的两个氨基的活性不同,通过控制二乙基氯代磷酸酯和2,4-二氨基甲苯的用量,可使活性较强的氨基(甲基对位上的氨基)与-Cl发生取代反应,而另一个氨基不参与反应,形成含P、N两种元素的阻燃剂,并且该阻燃剂分子中含有裸露的-NH2官能团;该阻燃剂由P-N协同产生多种作用,受热释放出的NH3和H2O,可起到气源的作用,同时起到稀释可燃性气体和氧气浓度的作用,缓减燃烧速度,受热分解产生的磷酸和偏磷酸等可做酸源,苯环和丁苯橡胶部分分子链可做碳源,三源相互作用产生膨胀的致密、厚实的残炭层,隔绝氧气和热量的传递,起到良好的阻燃效果;
改性丁苯橡胶由如下方法制备:
S1、按照体积比3.5:1将二氯甲烷和甲醇混合均匀,得到混合溶剂,备用;将烯丙基缩水甘油醚溶解到混合溶剂中,得到质量分数为5%的改性液;
S2、在反应釜中将丁苯橡胶溶解到混合溶剂中,形成质量分数为20%的丁苯橡胶溶液,将反应釜的的温度控制在8-10℃,将上述改性液逐滴滴加到反应釜中,使其缓慢的和丁苯橡胶发生反应,滴加结束保温反应3h;
S3、再加入四氯化锡作为催化剂(四氯化锡的加入量为丁苯橡胶质量的2%),体系慢慢升温到40-42℃,继续保温反应9-10h,反应结束后,在蒸馏釜中加入足量的去离子水和乳化剂(去离子水的加入量为反应结束时体系质量的1.5-2倍,乳化剂为壬基酚醚磷酸酯,乳化剂的加入量为去离子水质量的3%)使其完全溶解,将反应釜的温度提升到90℃,搅拌下将反应结束的溶液慢慢滴加到提取釜中,将析出的产物离心、干燥,得到改性丁苯橡胶;
将烯丙基缩水甘油醚与丁苯橡胶进行改性共聚反应,可在丁苯橡胶分子链中引入烯丙基缩水甘油醚,也即,在丁苯橡胶的分子链中引入了环氧基团和柔性链;引入的环氧基团可以与白炭黑表面的硅羟基相互作用,从而抑制白炭黑粒子间的相互作用,减少团聚,提高白炭黑在橡胶基体中的分散,并且增强白炭黑与橡胶基体的相互作用,进而促进更多的包容橡胶被释放而参与交联,形成三维网络,使发泡丁苯橡胶表现出高弹性;引入的环氧基团还能与阻燃剂分子上含有的-NH2官能团相互作用,提高阻燃剂与橡胶基体的作用力,增强阻燃剂的牢固性,使阻燃剂更充分发挥其阻燃性能,并且在受热过程中促进丁苯橡胶分子链成炭,提高阻燃效果;此外,在丁苯橡胶的分子链中引入了柔性链,能够改善橡胶材料的力学损耗性能;
该橡胶的制备方法如下:
第一步、将密炼机打开设定温度为100℃,当仪器的温度达到时,将改性丁苯橡胶和天然橡胶加入到密炼机中密炼13-15min,然后加入白炭黑和氧化锌密炼5-6min,接着添加发泡剂、硫磺和促进剂继续密炼5-6min,得到共混胶;
第二步、共混胶于室温下停放24h后,将开炼机设定温度为80℃,将共混胶在开炼机上进行开炼,逐渐调小开炼机辊筒的距离,使共混胶变薄,多次打三角包(7-10次),然后处理成10-12mm片材,得到混炼胶;
第三步、将混炼胶在平板硫化机上进行预硫化(预硫化温度为125℃,预硫化时间为14-15min),然后进行二次硫化(150℃×t90),制得所述发泡丁苯橡胶。
实施例1
一种环保型发泡丁苯橡胶由如下重量份原料制成:改性丁苯橡胶90份、天然橡胶16份、白炭黑45份、氧化锌1.6份、促进剂3份、硫磺1.8份、发泡剂2.7份;
该橡胶由如下步骤制成:
第一步、将密炼机打开设定温度为100℃,当仪器的温度达到时,将改性丁苯橡胶和天然橡胶加入到密炼机中密炼13min,然后加入白炭黑和氧化锌密炼5min,接着添加发泡剂、硫磺和促进剂继续密炼5min,得到共混胶;
第二步、共混胶于室温下停放24h后,将开炼机设定温度为80℃,将共混胶在开炼机上进行开炼,逐渐调小开炼机辊筒的距离,使共混胶变薄,多次打三角包(7次),然后处理成10mm片材,得到混炼胶;
第三步、将混炼胶在平板硫化机上进行预硫化(预硫化温度为125℃,预硫化时间为14min),然后进行二次硫化(150℃×t90),制得所述发泡丁苯橡胶。
实施例2
一种环保型发泡丁苯橡胶由如下重量份原料制成:改性丁苯橡胶95份、天然橡胶18份、白炭黑48份、氧化锌1.82份、促进剂3.5份、硫磺1.9份、发泡剂2.8份;
该橡胶由如下步骤制成:
第一步、将密炼机打开设定温度为100℃,当仪器的温度达到时,将改性丁苯橡胶和天然橡胶加入到密炼机中密炼14min,然后加入白炭黑和氧化锌密炼5.5min,接着添加发泡剂、硫磺和促进剂继续密炼5.5min,得到共混胶;
第二步、共混胶于室温下停放24h后,将开炼机设定温度为80℃,将共混胶在开炼机上进行开炼,逐渐调小开炼机辊筒的距离,使共混胶变薄,多次打三角包(8次),然后处理成11mm片材,得到混炼胶;
第三步、将混炼胶在平板硫化机上进行预硫化(预硫化温度为125℃,预硫化时间为14.5min),然后进行二次硫化(150℃×t90),制得所述发泡丁苯橡胶。
实施例3
一种环保型发泡丁苯橡胶由如下重量份原料制成:改性丁苯橡胶100份、天然橡胶20份、白炭黑50份、氧化锌2份、促进剂4份、硫磺2份、发泡剂3份;
该橡胶由如下步骤制成:
第一步、将密炼机打开设定温度为100℃,当仪器的温度达到时,将改性丁苯橡胶和天然橡胶加入到密炼机中密炼15min,然后加入白炭黑和氧化锌密炼6min,接着添加发泡剂、硫磺和促进剂继续密炼6min,得到共混胶;
第二步、共混胶于室温下停放24h后,将开炼机设定温度为80℃,将共混胶在开炼机上进行开炼,逐渐调小开炼机辊筒的距离,使共混胶变薄,多次打三角包(10次),然后处理成12mm片材,得到混炼胶;
第三步、将混炼胶在平板硫化机上进行预硫化(预硫化温度为125℃,预硫化时间为15min),然后进行二次硫化(150℃×t90),制得所述发泡丁苯橡胶。
对比例1
将实施例1原料中的改性丁苯橡胶换为丁苯橡胶,其余原料及制备过程不变。
对比例2
将实施例1中的阻燃剂换成APP(聚磷酸铵)阻燃剂,其余原料及制备过程不变。
对比例3
普通发泡丁苯橡胶。
对实施例1-3和对比例1-3制得的发泡丁苯橡胶做如下性能测试:邵尔C型硬度按照GB/T 531.1-2008进行测试;拉伸强度和拉断伸长率按照GB/T 528-2009进行测试;测试燃烧性能,包括极限氧指数LOI的测定和自息时间的测定;测试结果如下表:
由上表可知,实施例1-3制得的发泡丁苯橡胶的绍尔C型硬度为74-76,拉伸强度为2.3-2.4MPa,断裂伸长率为220-230%,说明本发明制得的发泡橡胶具有较高的力学性能;实施例1-3制得的发泡丁苯橡胶的极限氧指数为34.2-35.6%,自熄时间为9.2-9.8s,均为难燃材料,说明本发明制得的发泡丁苯橡胶具有较高的阻燃性能;相较于对比例1,说明丁苯橡胶经过改性后,能在丁苯橡胶分子链上引入环氧基团和柔性分子链,环氧基团能够与白炭黑和阻燃剂作用,促进白炭黑的分散,提高阻燃剂与橡胶基体的结合力,进而提高发泡橡胶的力学性能和阻燃性能;相较于对比例2,说明本发明合成的阻燃剂含有氨基官能团,能够与改性丁苯橡胶分子链上的环氧基团作用,进而提高阻燃剂与橡胶基体的结合作用,提高阻燃效果。
以上公开的本发明优选实施例只是用于帮助阐述本发明。优选实施例并没有详尽叙述所有的细节,也不限制该发明仅为所述的具体实施方式。显然,根据本说明书的内容,可作很多的修改和变化。本说明书选取并具体描述这些实施例,是为了更好地解释本发明的原理和实际应用,从而使所属技术领域技术人员能很好地理解和利用本发明。本发明仅受权利要求书及其全部范围和等效物的限制。
Claims (5)
1.一种环保型发泡丁苯橡胶的制备方法,其特征在于,该发泡丁苯橡胶由如下重量份原料制成:改性丁苯橡胶90-100份、天然橡胶16-20份、白炭黑45-50份、氧化锌1.6-2份、促进剂3-4份、硫磺1.8-2份、发泡剂2.7-3份;
该发泡丁苯橡胶的制备方法,包括如下步骤:
第一步、将密炼机打开设定温度为100℃,当仪器的温度达到时,将改性丁苯橡胶和天然橡胶加入到密炼机中密炼13-15min,然后加入白炭黑和氧化锌密炼5-6min,接着添加发泡剂、硫磺和促进剂继续密炼5-6min,得到共混胶;
第二步、共混胶于室温下停放24h后,将开炼机设定温度为80℃,将共混胶在开炼机上进行开炼,打三角包7-10次,然后处理成10-12mm片材,得到混炼胶;
第三步、将混炼胶在平板硫化机上进行预硫化,预硫化温度为125℃,预硫化时间为14-15min,然后进行二次硫化,二次硫化参数150℃×t90,制得所述发泡丁苯橡胶。
2.根据权利要求1所述的一种环保型发泡丁苯橡胶的制备方法,其特征在于,所述阻燃剂由如下方法制成:
(1)将二乙基氯代磷酸酯溶解于乙腈中,形成浓度为0.8mol/L的含磷溶液;
(2)将2.0g的2,4-二氨基甲苯和3.3g的三乙胺溶于180-200mL的乙腈中,搅拌混合均匀后,通入氮气15min并控制溶液温度在3-4℃,在氮气条件下将38-40mL含磷溶液缓慢滴入混合液中,滴加完成后保持冰浴反应55-65min后,再将整个装置移入52-55℃油浴锅中,氮气下回流反应22-24h,反应结束后,将产物抽滤、洗涤、干燥,得到阻燃剂。
3.根据权利要求1所述的一种环保型发泡丁苯橡胶的制备方法,其特征在于,所述改性丁苯橡胶由如下方法制备:
S1、按照体积比3.5:1将二氯甲烷和甲醇混合均匀,得到混合溶剂,备用;将烯丙基缩水甘油醚溶解到混合溶剂中,得到质量分数为5%的改性液;
S2、在反应釜中将丁苯橡胶溶解到混合溶剂中,形成质量分数为20%的丁苯橡胶溶液,将反应釜的的温度控制在8-10℃,将上述改性液逐滴滴加到反应釜中,使其缓慢的和丁苯橡胶发生反应,滴加结束保温反应3h;
S3、再加入四氯化锡作为催化剂,体系慢慢升温到40-42℃,继续保温反应9-10h,反应结束后,在蒸馏釜中加入去离子水和乳化剂使其完全溶解,将反应釜的温度提升到90℃,搅拌下将反应结束的溶液慢慢滴加到提取釜中,将析出的产物离心、干燥,得到改性丁苯橡胶。
4.根据权利要求3所述的一种环保型发泡丁苯橡胶的制备方法,其特征在于,步骤S3中四氯化锡的加入量为丁苯橡胶质量的2%。
5.根据权利要求3所述的一种环保型发泡丁苯橡胶的制备方法,其特征在于,步骤S3中去离子水的加入量为反应结束时体系质量的1.5-2倍,乳化剂为壬基酚醚磷酸酯,乳化剂的加入量为去离子水质量的3%。
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