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                          再生橡胶中表面改性重钙粉的使用性能分析

                          时间:2019-01-10 来源:辽宁化工 作者:范天博,陈思,姜宇,贾 本文字数:3184字

                            摘    要:星云棋牌官网下载 以磷酸二氢铵、四乙基溴化铵以及硅烷偶联剂为改性剂,对重质碳酸钙进行表面化学改性,提高其补强性,拓宽重质碳酸钙的应用领域。在再生橡胶中的应用实验显示,与以未改性重钙粉为填充剂的再生橡胶相比,改性重质碳酸钙填充再生胶的力学性能有明显的提高,补强性与轻钙粉的效果相当。

                            关键词: 改性重钙粉; 重钙粉; 轻钙粉; 填充; 橡胶力学性能;

                            Abstract: Ammonium dihydrogen phosphate, tetraethylammonium bromide and silane coupling agent were used as modifiers to modify the surface of heavy calcium carbonate to improve its reinforcing properties and broaden the application field of heavy calcium carbonate. Application experiments in recycled rubber showed that the mechanical properties of the modified heavy calcium carbonate filled regenerated vulcanizate were obviously improved compared with the unmodified one; the reinforcing effect was equivalent to that of light calcium powder.

                            Keyword: modified heavy calcium powder; heavy calcium powder; light calcium powder; filling; rubber mechanical properties;

                            橡胶工业中广泛应用的无机填料的种类很多,主要有白炭黑、硅酸盐和碳酸钙等[1]。重钙颗粒表面含有羟基而呈极性,与非极性的聚合物相容性不好,幵且具有亲水疏油的表面特性,在聚合物中分散性差[2,3,4,5]。一般需要对碳酸钙进行表面改性,以提升对橡胶的补强效果。Poompradub等[6]经过没食子酸改性后的碳酸钙填充到天然橡胶中表现出抗氧化性质;唐琴等[7]采用棕榈酸对方解石型重钙进行改性处理,所得的重钙粒度分布较均匀、分散性能好;王友等[8]用硬脂酸和钛酸酯偶联剂对重钙粉进行表面改性,改性后的重钙粉的活化度有了明显提高。本文对重钙粉表面改性,降低粒径,降低表面亲水疏油性,改善其在橡胶中的分散性,提高被填充的橡胶制品力学性能具有重要意义[9,10]。
                           

                          再生橡胶中表面改性重钙粉的使用性能分析
                           

                            1 、实验部分

                            1.1、 实验原料

                            BENSHIYANCAIYONGQINGZHITANSUANGAI(QINGGAIFEN)HEZHONGZHITANSUANGAI(ZHONGGAIFEN),JUNWEIDANDONGYILONGGAOKEJICAILIAOYOUXIANGONGSIDECHANPIN,GONGYEJI。QINGGAIFENHEZHONGGAIFENDELIDU、BAIDUJIXIYOUZHICUNZAIYIDINGDECHAYI,CONGBIAO1DEXINGZHICANSHUKEYIKANCHU,ZHONGGAIFENLIJINGJIAODA,LIJINGFENBUJIAOKUAN,ERQINGGAIFENLIJINGJIAOXIAO,LIJINGFENBUJIAOZHAI,ZHONGGAIFENDEBAIDUBIQINGGAIFENSHAOGAO,DANXIYOULIANGXIAOYUQINGGAI。

                            表1 轻钙粉和重钙粉的性质分析
                          表1 轻钙粉和重钙粉的性质分析

                            1.3、 再生胶的制备

                            JIANGZAISHENGJIAOLI、TIANCHONGWU、MEIJIAOYOU、GUTIYOU、408HUOHUAJIANYIDINGBILIFANGRUZHUANJUXINGLIUHUAYIZHIBEIHUNLIANJIAOHOU,ZAIKAILIANJISHANGBOTONGBAOGUNHOUYICIJIARUYINGZHISUAN、YANGHUAXIN、LIUHUANGDENGQITAPEIHEJI,BOTONGHOUCHUPIAN。TINGFANG4 hHOU,SHIYONGPINGBANLIUHUAYILIUHUA,TIAOJIANWEI150℃×30 min。FANGLAOHUAXIANGLAOHUA,TIAOJIANFENBIEWEI100℃×12 h,100℃×24 h。

                            1.4、 天然胶的制备

                            JIANGKUAIZHUANGTIANRANJIAOFANGRU1.5 mmGUNJUDEKAILIANJI,YACHENGPIANZHUANG。DIAOXIAOGUNJUZHI0.5 mm,FANGRUPIANZHUANGDEJIAOLIAOBAOGUNSULIAN,YICIJIARUYANGHUAXIN、YINGZHISUAN、FANGLAOHUA4010NA、CUJINJICZ、CUJINJITMTD、TIANCHONGJI、LIUHUANGDENGYIDINGLIANGPEIHEJI,DIAODAGUNJUZHI2 mm,JIANGJIAOLIAOYACHENGBIAOMIANPINGZHENGZHANGTIAOXING,ZAISHIWENXIATINGFANG12 h,JINXINGLIUHUA,LIUHUATIAOJIANWEI145℃×30 min。LAOHUATIAOJIANWEI100℃×48 h。

                            2、 实验结果与数据分析

                            2.1、 改性剂在重钙粉表面分布

                            CAIYONGDIANJINGXIANWEIJINGDUIZHONGGAIFEN、QINGGAIFENJIBUTONGGAIXINGJIGAIXINGZHONGGAIFENWEIGUANXINGMAOFENXI,RUTU2SUOSHI。

                          星云棋牌官网下载   QINGGAIFENDUOSHUYOUPIANZHUANGTUANJUERCHENG,ZHONGGAIFENWEIPIANZHUANGDIEJIACHENGCENGZHUANGJIEGOU,YUWEIGAIXINGZHONGGAIFENCENGZHUANGJIEGOUXIANGBI,GAIXINGHOUDEZHONGGAIFENXINGMAOBIANHUAJIAODA,FAXIANYIXIEXIAOKELIFUZHEZAIDAKELISHANG,QIZHONG,JINGGUOSIYIJIXIUHUAANGAIXINGZHIHOU,BAOFUHOUDEKELIFENSANJIAOJUNYUN。

                            2.2 、改性剂的选择

                            BUTONGGAIXINGJIGAIXINGZHONGGAIFENDELIJINGYUXIYOUZHI,YIJIFENBIEZUOWEITIANLIAODUITIANRANJIAOXINGNENGDEYINGXIANG,RUBIAO2SUOSHI。

                            图2 不同改性剂重钙粉SEM图
                          图2 不同改性剂重钙粉SEM图

                          星云棋牌官网下载   a:GUIWANOULIANJIGAIXINGJIb:SIYIJIXIUHUAANGAIXINGJIc:LINSUANERQINGANGAIXINGJId:QINGGAIFENe:ZHONGGAIFEN

                            表2 重钙粉改性的效果
                          表2 重钙粉改性的效果

                          星云棋牌官网下载   CONGBIAO2ZHONGKEYIKANCHU,YUWEIGAIXINGZHONGGAIFENXIANGBI,GAIXINGZHONGGAIFENDEXIYOUZHIDI,ZHONGWEIJINGMEIYOUBIANHUA,GAIXINGGUODEZHONGGAIFENTIANCHONGYUTIANRANJIAOZHONG,YINGDUHEKANGLAQIANGDUJUNTIGAO。ZHEISHIYINWEIBIAOMIANGAIXINGJIDEYIDUANNENGGOUYUZHONGGAIFENBIAOMIANDEQIANGJIFASHENGFANYING,SHIZHONGGAIFENBIAOMIANBAOFUYICENGYOUJIWUZHICONGERGAIBIANZHONGGAIFENBIAOMIANTEXING,ZENGDAQIYUXIANGJIAOJITIDEXIANGRONGXING,TIGAOFENSANCHENGDU,ERQINYOUDEYIDUANYUXIANGJIAOFASHENGFANYING,TIGAOJIAOLIAODELIXUEXINGNENG。XIANGDUIYUWEIGAIXINGDEZHONGGAIFEN,QIZHONGSIYIJIXIUHUAANGAIXINGZHONGGAIFENZAIXIYOUZHI、XIANGJIAODEKANGLAQIANGDUJIYINGDUCESHIGEZHONGZHIBIAOGAIXINGXIAOGUOMINGXIAN。

                            2.3、 填充再生胶橡胶性能对比

                            BENSHIYANQINGGAIFEN、ZHONGGAIFENHESIYIJIXIUHUAANGAIXINGZHONGGAIFENZUOWEITIANCHONGJI,ZAITONGDENGTIAOJIANXIAJINXINGZAISHENGJIAOZHIBEI,XINGNENGDUIBIWEIBIAO3SUOSHI。

                            表3 拉伸数据表
                          表3 拉伸数据表

                          星云棋牌官网下载   BIAO3KEZHI:YIGAIXINGZHONGGAIFENWEITIANLIAODEJIAOLIAOZAIYINGDU、LASHENQIANGDUHEDINGSHENYINGLIFANGMIANZONGTIYOUYUWEIGAIXINGZHONGGAIFENTIANLIAODEJIAOLIAO;ZAITIANCHONGLIANGWEI10FENSHI,GAIXINGZHONGGAIFENTIANCHONGZAISHENGXIANGJIAOYUTIANCHONG15FENQINGGAIFENDEJIAOLIAOLIXUEXINGNENGXIANGBI,KANGLAQIANGDUDA,DANDINGSHENYINGLIJIDUANLIESHENZHANGLVPIANDI;ZAITIANLIAOLIANGJUNWEI20FENSHI,GAIXINGZHONGGAIFENFUHEZAISHENGJIAOLIAODEYINGDU、KANGLAQIANGDUHEDINGSHENYINGLIYOUYUQINGGAIFENTIANCHONGDEZAISHENGJIAOLIAO。SHUOMINGBIAOMIANGAIXINGGAISHANZHONGGAIFENBIAOMIANXINGZHI,ZAIXIANGJIAOZHONGJUYOULIANGHAODEFENSANXING,TIGAOZHONGGAIFENBUQIANGXING。

                            GAIXINGZHONGGAIFENTIANLIAODEZENGDA,XIANGJIAODELASHENQIANGDUHEDUANLIESHENZHANGLVXIANZENGDAHOUJIANXIAODEQUSHI。ZAITIANLIAOLIANGWEI10FENSHI,ZAISHENGJIAOKANGLAQIANGDU、DUANLIESHENZHANGLVFENBIE7.32 MPaHE365.94%,LIXUEXINGNENGDADAOZUIDAZHI。SHUOMINGTANSUANGAIZUIDATIANCHONGLIANGWEIDE10FEN,SUIZHETANSUANGAITIANCHONGLIANGZENGJIA,XIFUZAITIANLIAOBIAOMIANSHANGDEXIANGJIAOLIZIZENGDUO,ZENGJIALEXIANGJIAOTIXIDEJIAOLIANDIAN,CHAOGUOCIZHI,GAIXINGZHONGZHITANSUANGAITIANLIAOLIANGGUODUO,ZAISHENGJIAOKANGLADANXINGJIANGDI,LIXUEXINGNENGBIANCHA。

                            2.4、老化拉伸性能

                            DUIGAIXINGZHONGGAIZAISHENGJIAOLIAOJINXINGLAOHUA,TIANCHONGLIANG15FEN,JIANGYISIYIJIXIUHUAANGAIXINGZHONGGAIFENWEITIANCHONGJIDEZAISHENGJIAOLIAOFANGRULAOHUAXIANGJINXINGLAOHUAXINGNENGCESHI,WEIBIAO4SUOSHI:LAOHUA12 hGAIXINGZHONGGAIFENJIAOLIAOYINGDUZENGJIADAO54.2A,KANGLAQIANGDUJIANSHAODAO4.53;LAOHUA24 hJIAOLIAOYINGDUZENGJIADAO67.8A,KANGLAQIANGDUJIANSHAODAO4.52。LAOHUAHOU,GAIXINGZHONGGAIFENZAISHENGJIAOLIAODEYINGDUZENGJIALVJIKANGLAQIANGDUBIANHUALVJIAODI,ZHEISHUOMINGTONGGUOGAIXING,ZHONGGAIFENDENAILAOHUAXINGDEDAOGAISHAN。

                            表4 老化拉伸数据
                          表4 老化拉伸数据

                            3、 结论

                            (1)在本实验中,经过三种改性剂改性后的重钙粉吸油值均比未改性重钙粉小,分别作为填充剂填充于再生橡胶中后力学性能都得到提高。
                            (2)实验表明以改性重钙粉为填料胶料在硬度、拉伸强度和定伸应力方面总体优于未改性重钙粉填料胶料,与轻钙粉的补强效果相比,其断裂伸长率较低,但其它力学性能优于或略低于轻钙粉。
                            (3)老化测试表明,橡胶中添加改性重钙粉补强性填充剂,在一定程度上提高橡胶的耐老化性能。
                          星云棋牌官网下载   (4)改性重钙粉投入工程实践中,抗拉强度、断裂伸长率等均要好于轻钙粉的添加产品。增大了添加量,降低制品的成本,可替代轻钙粉应用到橡胶产品中。

                            参考文献

                            [1]柳艳霞.橡胶用无机填料的红外光谱分析[J].橡胶科技, 2015,13(4):46-50.
                            [2] 彭丼敏.木质素与无机填料幵用对丁腈橡胶压缩永久变形的影响[D].湖南师范大学, 2016.
                            [3]李小云.重质碳酸钙表面改性及其在聚合物中的应用[D].兰州大学, 2008.
                            [4]杨眉,沈上越,蒋鹏.重质碳酸钙表面改性及充填丁苯橡胶试验研究[J].矿物岩石, 2001, 21(4):19-22.
                            [5]王千.改性重质碳酸钙及其在聚丙烯中的应用[D].华中科技大学,2015.
                            [6]Poompradub S, Luthikaviboon T, Linpoo S, et al. Improving oxidation stability and mechanical properties of natural rubber vulcanizates filled with calcium carbonate modified by gallic acid[J]. Polymer Bulletin, 2011, 66(7):965-977.
                            [7]唐琴,陈先勇,胡卫兵,等.棕榈酸改性方解石型重质碳酸钙的研究[J].化工矿物与加工2011, 40(3):20-23.
                            [8]王友,曾一文,覃康玉,等.硬脂酸-钛酸酯偶联剂改性重质碳酸钙粉体研究[J].无机盐工业, 2016, 48(6):38-40.
                            [9]王友. Span60表面改性重质碳酸钙粉体研究[J].无机盐工业, 2016,48(7):25-28.
                            [10]徐世传.我国无机填料的生产和应用概况[J].橡胶科技, 2009,7(23):5-10.
                            [11] 胡彦,梅日国,安振国,等.无机填料对硅橡胶力学性能的影响[C]//北京粘接学会学术年会暨胶粘剂、密封剂技术发展研讨会, 2011.

                            范天博,陈思,姜宇,贾晓辉,韩冬雪,亢萍,李莉,刘云义,赵光.以改性重钙粉为填充剂橡胶加工及性能研究[J].辽宁化工,2019,48(12):1170-1172.
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