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    泰州科德橡膠機械-密煉機:橡膠的硫化體系

    發布時間:2019-08-19 12:06:00 點擊:    關鍵詞:密煉機,捏煉機,開煉機,橡膠機械

    1. 交聯密度的表征

    泰州科德橡膠機械-密煉機開煉機捏煉機廠家2019年8月19日訊  交聯點間分子量 -Mc:兩個相鄰的交聯點間鏈段的平均分子量。具有多分散性,Mc 越大,交聯密度越小。

         交聯密度:單位體積硫化膠內的交聯點數目。硫化膠的交聯密度經常用 1/2Mc表示。

        交聯密度的測定方法:平衡溶脹法、機械測試法 、磁共振法

    1. 橡膠的硫化歷程

    ① 焦燒延遲( Scorch delay)階段

       焦燒:混煉膠在儲存和加工過程中產生的早期硫化現象。

       操作焦燒時間 :橡膠在加工過程中由于混煉、壓延、壓出等消耗掉的焦燒間。

        剩余焦燒時間 :指膠料在定型前尚能流動的時間。

    ② 熱硫化( crosslink)階段

    ③ 平坦硫化階段

    ④ 過硫化( post-cure)階段

    第一種曲線繼續上升, 產生結構化作用 所致:非硫黃硫化的丁苯膠、 丁腈膠、氯丁膠和乙丙膠;

    第二種曲線下降, 網構裂解 所致:天然橡膠的普通硫黃硫化。

    第三種曲線長時間保持平坦:平衡硫化體系,通常硫黃硫化的合成橡膠平坦

    期都比較長。

      硫化返原(過硫) - reversion :橡膠達到正硫化狀態后繼續硫化,硫化膠的交聯密度下降,性能下降的現象。

         焦燒時間(T10):膠料從加入到模具中受熱開始到轉矩為 M10 所對應的時間。

       理論正硫化時間( TH ):膠料從加入到模具中受熱開始到轉矩達到最大值所需要的時間。

       工藝正硫化時間 (T90):膠料從加入到模具中受熱開始到轉矩達到 M90 所需

    要的時間。

      2. 硫黃的品種:粉末硫黃(硫八環,易噴霜) 、不溶性硫黃(不易噴霜)

    噴霜:又名噴出 ,指混煉膠或硫化膠中的配合劑在橡膠中的溶解度超過其飽和

    溶解度而遷移到橡膠表面的現象。

       噴霜的原因:超量配合、欠硫(網絡交聯密度相對較小,其他助劑穿梭于網絡的機會增大, 噴霜幾率相應增大)、老化噴霜— (局部老化如光照使網絡吸附的微粒脫離橡膠基質噴出) 、降溫使溶解度急劇下降。

        噴霜的危害:(1)影響外觀質量,尤其是生活用橡膠制品。(2)降低制品表面的粘著性,影響膠料半成品的貼合成型。

       防噴霜措施:避免超量配合;硫黃在低溫下加入;采用不溶性硫黃;以硒替代部分硫黃 ;加強工藝管理,防止混煉不均勻和硫化不完全。

      交聯效率參數 E:形成每摩爾交聯鍵所需要的平均的硫黃摩爾數目。

    3. 促進劑的分類

    按結構和酸堿性分,

    密煉機,開煉機,捏煉機,橡膠機械

        按促進速度分,以促進劑 M對 NR的使用效果作為標準,比 M快的屬于超速或超超速級;比 M慢的屬于慢速或中速級。

       噻唑類:酸性、準速級;無污染;有苦味(只有促進基)

       次磺酰胺類:遲效性(促進基、活化基、防焦基)

        秋蘭姆類:制作耐熱膠種,可作硫化劑(活化基、促進基、硫化基)

        二硫代氨基甲酸鹽類:(促進基、活化基)超超速級促進劑,室溫硫化

       胍類:(只有活化基)中慢速,變色污染性。

        硫脲類:(只有活化基) NA—22 是 CR常用的促進劑

        醛胺類:(只有活化基)堿性慢速

    4. 促進劑的并用

        目的:提高促進劑的作用效果及出于工藝上的需要,如避免焦燒、防止噴霜、改善硫化平坦性。

        活化劑氧化鋅的作用:活化硫化體系 , 使硫環更容易斷裂;提高硫黃的利用率 ,提高硫化膠的交聯密度;吸收硫化過程產生的硫化氫氣體。

    5. 各種硫黃硫化體系

       (1) 普通硫黃硫化體系:常溫、動態情況下使用的制品。以多硫交聯鍵為主。高硫低促。

       (2) 有效硫化體系:90%以上是單硫和雙硫交聯鍵,高溫、靜態制品。高促低硫。

       (3) 半有效硫化體系:耐中等程度的高溫 , 又有一定動態疲勞性能。

       (4) 高溫快速硫化體系:選用耐熱膠種, 使用足量的硬脂酸以增加鋅鹽的溶解度,提高體系的活化功能。

       (5) 平衡硫化體系:解決不飽和橡膠尤其是 NR的硫化返原問題。加入抗硫化返原劑- Si-69 。大型厚制品抗硫化返原的方法:(1)采用硫黃給體或有效硫化體系;( 2)低溫長時間硫化;(3)使用抗硫化返原劑;

    6. 非硫黃硫化體系:

    過氧化物硫化體系、 金屬氧化物硫化體系、 樹脂硫化體系、通過鏈增長進行交聯長而柔性的交聯鍵有利于提高硫化膠的強度性能,即鍵能高而強度低。


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