β晶成核劑鄰苯二甲酸鋅的制備及其對聚丙烯性能的影響研究
發(fā)布時間：2019-03-18 14:56
【摘要】：(β晶型聚丙烯(β-PP)比α晶聚丙烯(α-PP)具有更優(yōu)異的韌性和更高的熱變形溫度,廣泛應(yīng)用于日用品、家居電器、汽車及排水管領(lǐng)域,如何生產(chǎn)穩(wěn)定的β-PP日益成為人們關(guān)注的重點。而添加β晶型成核劑,是目前制備β晶型聚丙烯最有前景且高效可靠的方式,所以開發(fā)穩(wěn)定、高效高選擇性的β晶成核劑已經(jīng)成為β-PP改性領(lǐng)域研究的熱點。首先,本文通過溶液法成功合成出鄰苯二甲酸鋅(PAZn(Solution)),并發(fā)現(xiàn)其在聚丙烯中具有β晶成核效果,但是其在聚丙烯中分散不均,團聚明顯,導(dǎo)致成核效率較低,基于此我們提出在擠出加工過程中原位制備鄰苯二甲酸鋅(PAZn(In situ))的思想和方法,并系統(tǒng)研究兩種方法制備的鄰苯二甲酸鋅對等規(guī)均聚聚丙烯(iPP)成核效果的影響。結(jié)果表明,在添加量為0.2wt%時,PAZn(Insitu)與PAZn(Solution)的抗沖擊強度均達(dá)到最大值,相比于空白iPP分別提升了 215%和151%。在成核效率和β晶型選擇性方面原位制備方法也顯示出了其特有的優(yōu)勢,0.05 wt%的PAZn(In situ)誘導(dǎo)的β晶含量(kβ值)可達(dá)0.95;而對于PAZn(Solution),在其最優(yōu)添加濃度下(0.05wt%),kβ僅為0.64。通過透射電子顯微鏡(TEM)、能譜分析(EDS)得知,原位制備的PAZn(In situ)在聚丙烯體系中具有更好的分散性,顆粒尺徑小且均一,解釋了 PAZn(In situ)具有更高成核效率的原因。其次,研究了 PAZn(Insitu)及PAZn(Solution)對嵌段共聚聚丙烯(PPB)成核效果的影響。當(dāng)成核劑的添加濃度為0.2wt%時,PPB/PAZn(Insitu)常溫沖擊強度和低溫沖擊強度相比空白PPB分別提高了 359%和107%,而PPB/PAZn(Solution)則分別提高了 302%和101%。PAZn(In situ)對PPB韌性改善效果略優(yōu)于PAZn(Solution)。在成核效率和β晶選擇性方面兩種制備方法顯示出了明顯的差異,當(dāng)添加濃度為0.1 wt%時,PAZn(In situ)與PAZn(Solution)誘導(dǎo)的β晶含量都基本上達(dá)到最大值,kβ分別為0.97和0.80。PAZn(In situ)在 0.05-0.8 wt%濃度范圍內(nèi),kβ 均保持在 0.96 以上;而 PAZn(Solution)在 0.05-0.8 wt%濃度范圍內(nèi),kβ逐漸降低直至接近0。表明在PPB體系,PAZn(In situ)是一種高效穩(wěn)定的β晶型成核劑。利用Mo法研究PPB體系非等溫結(jié)晶動力學(xué),PPB/PAZn(In situ)的F(T)值小于PPB/PAZn(Solution),也表明PAZn(In situ)在PPB體系中具有更好的成核效果。最后,探索了結(jié)晶成核劑對高熔體強度聚丙烯(HMSPP)基體性能及發(fā)泡性能的影響。差示掃描量熱儀(DSC)測試表明,成核劑均可以消除實驗室基于長支鏈接枝制備的HMSPP的雙結(jié)晶峰現(xiàn)象,而對商業(yè)化的HMSPP品種WB260體系卻沒有產(chǎn)生明顯的影響。力學(xué)性能方面,成核劑對HMSPP體系的剛性及韌性都沒有明顯的影響。發(fā)泡性能的測試表明,成核劑的加入可以有效調(diào)控HMSPP體系的泡孔直徑,泡孔尺寸可達(dá)到50μm以上,發(fā)泡倍率至少提高2倍以上,均可以得到高發(fā)泡倍率的泡沫產(chǎn)品。
[Abstract]:尾-crystalline polypropylene (尾-PP) has better toughness and higher thermal deformation temperature than 偽-crystalline polypropylene (偽-PP), and is widely used in household appliances, automobiles and drain pipes. How to produce stable 尾-PP has become the focus of attention. The addition of 尾-crystalline nucleating agent is the most promising and reliable way to prepare 尾-crystalline polypropylene at present, so the development of stable, high-efficiency and high-selectivity 尾-crystalline nucleating agent has become a hot spot in the field of 尾-PP modification. Firstly, zinc phthalate (PAZn (Solution), was successfully synthesized by solution method and found to have the effect of 尾 crystal nucleation in polypropylene, but it was unevenly dispersed in polypropylene and agglomerated obviously, which led to lower nucleation efficiency. Based on this, we put forward the idea and method of in-situ preparation of zinc phthalate (PAZn (In situ) during extrusion processing, and systematically study the effect of the two methods on the nucleation effect of zinc phthalate isohomopolymer polypropylene (iPP). The results showed that the impact strength of, PAZn (Insitu) and PAZn (Solution) reached the maximum at 0.2 wt%, which was 215% and 151% higher than that of blank iPP, respectively. In the aspects of nucleation efficiency and 尾 crystal form selectivity, the in situ preparation method also shows its unique advantages. The content of 尾 crystals (k 尾 value) induced by PAZn (In situ) of 0.05 wt% is up to 0.95; The optimal concentration of PAZn (Solution), (0.05wt%), k 尾) was 0.64. The transmission electron microscopy (TEM),) analysis of (EDS) showed that the in-situ prepared PAZn (In situ) had better dispersibility, smaller particle size and uniform size in polypropylene system. The reason why PAZn (In situ) has more Gao Cheng nuclear efficiency is explained. Secondly, the effects of PAZn (Insitu) and PAZn (Solution) on the nucleation of block copolymer polypropylene (PPB) were studied. When the addition concentration as nucleating agent was 0.2 wt%, the impact strength of PPB/PAZn (Insitu) at room temperature and low temperature increased by 35.9% and 107%, respectively, compared with blank PPB. On the other hand, PPB/PAZn (Solution) increased 302% and 101%.PAZn (In situ) slightly improved the toughness of PPB than that of PAZn (Solution). There were obvious differences in nucleation efficiency and 尾-crystal selectivity between the two methods. When the concentration was 0.1 wt%, the content of 尾-crystals induced by, PAZn (In situ) and PAZn (Solution) reached the maximum. K 尾 was 0.97 and 0.80.PAZn (In situ) was within 0. 05 渭 0. 8 wt%, and k 尾 was above 0. 96 in the range of 0. 05 and 0. 8 wt%, respectively. In the range of 0. 05 and 0. 8 wt% of PAZn (Solution), k 尾 gradually decreased to close to 0. 0. The results show that, PAZn (In situ) in PPB system is an efficient and stable nucleating agent in 尾 crystal form. The non-isothermal crystallization kinetics of PPB system was studied by Mo method. The F (T) value of PPB/PAZn (In situ) was less than that of PPB/PAZn (Solution), which indicated that PAZn (In situ) had better nucleation effect in PPB system. Finally, the effects of nucleating agent on the matrix properties and foaming properties of high melt strength polypropylene (HMSPP) were investigated. Differential scanning calorimetry (DSC) showed that nucleating agents could eliminate the biphasic peaks of HMSPP based on long branch links in the laboratory, but had no obvious effect on the WB260 system of commercial HMSPP varieties. In terms of mechanical properties, nucleating agent has no obvious effect on the rigidity and toughness of HMSPP system. The test of foaming property shows that the addition of nucleating agent can effectively control the cell diameter of HMSPP system, the cell size can be more than 50 渭 m, and the foaming rate can be increased by at least 2 times. The foam products with high foaming rate can be obtained by the addition of nucleating agent.
【學(xué)位授予單位】：華東理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ325.14
本文編號：2442965
[Abstract]:尾-crystalline polypropylene (尾-PP) has better toughness and higher thermal deformation temperature than 偽-crystalline polypropylene (偽-PP), and is widely used in household appliances, automobiles and drain pipes. How to produce stable 尾-PP has become the focus of attention. The addition of 尾-crystalline nucleating agent is the most promising and reliable way to prepare 尾-crystalline polypropylene at present, so the development of stable, high-efficiency and high-selectivity 尾-crystalline nucleating agent has become a hot spot in the field of 尾-PP modification. Firstly, zinc phthalate (PAZn (Solution), was successfully synthesized by solution method and found to have the effect of 尾 crystal nucleation in polypropylene, but it was unevenly dispersed in polypropylene and agglomerated obviously, which led to lower nucleation efficiency. Based on this, we put forward the idea and method of in-situ preparation of zinc phthalate (PAZn (In situ) during extrusion processing, and systematically study the effect of the two methods on the nucleation effect of zinc phthalate isohomopolymer polypropylene (iPP). The results showed that the impact strength of, PAZn (Insitu) and PAZn (Solution) reached the maximum at 0.2 wt%, which was 215% and 151% higher than that of blank iPP, respectively. In the aspects of nucleation efficiency and 尾 crystal form selectivity, the in situ preparation method also shows its unique advantages. The content of 尾 crystals (k 尾 value) induced by PAZn (In situ) of 0.05 wt% is up to 0.95; The optimal concentration of PAZn (Solution), (0.05wt%), k 尾) was 0.64. The transmission electron microscopy (TEM),) analysis of (EDS) showed that the in-situ prepared PAZn (In situ) had better dispersibility, smaller particle size and uniform size in polypropylene system. The reason why PAZn (In situ) has more Gao Cheng nuclear efficiency is explained. Secondly, the effects of PAZn (Insitu) and PAZn (Solution) on the nucleation of block copolymer polypropylene (PPB) were studied. When the addition concentration as nucleating agent was 0.2 wt%, the impact strength of PPB/PAZn (Insitu) at room temperature and low temperature increased by 35.9% and 107%, respectively, compared with blank PPB. On the other hand, PPB/PAZn (Solution) increased 302% and 101%.PAZn (In situ) slightly improved the toughness of PPB than that of PAZn (Solution). There were obvious differences in nucleation efficiency and 尾-crystal selectivity between the two methods. When the concentration was 0.1 wt%, the content of 尾-crystals induced by, PAZn (In situ) and PAZn (Solution) reached the maximum. K 尾 was 0.97 and 0.80.PAZn (In situ) was within 0. 05 渭 0. 8 wt%, and k 尾 was above 0. 96 in the range of 0. 05 and 0. 8 wt%, respectively. In the range of 0. 05 and 0. 8 wt% of PAZn (Solution), k 尾 gradually decreased to close to 0. 0. The results show that, PAZn (In situ) in PPB system is an efficient and stable nucleating agent in 尾 crystal form. The non-isothermal crystallization kinetics of PPB system was studied by Mo method. The F (T) value of PPB/PAZn (In situ) was less than that of PPB/PAZn (Solution), which indicated that PAZn (In situ) had better nucleation effect in PPB system. Finally, the effects of nucleating agent on the matrix properties and foaming properties of high melt strength polypropylene (HMSPP) were investigated. Differential scanning calorimetry (DSC) showed that nucleating agents could eliminate the biphasic peaks of HMSPP based on long branch links in the laboratory, but had no obvious effect on the WB260 system of commercial HMSPP varieties. In terms of mechanical properties, nucleating agent has no obvious effect on the rigidity and toughness of HMSPP system. The test of foaming property shows that the addition of nucleating agent can effectively control the cell diameter of HMSPP system, the cell size can be more than 50 渭 m, and the foaming rate can be increased by at least 2 times. The foam products with high foaming rate can be obtained by the addition of nucleating agent.
【學(xué)位授予單位】：華東理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ325.14
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