CN109233046A - 一种含磷阻燃聚乙烯电缆料的制备方法 - Google Patents
一种含磷阻燃聚乙烯电缆料的制备方法 Download PDFInfo
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- HXBZCHYDLURWIZ-UHFFFAOYSA-N diphenyl hydrogen phosphate;hydrochloride Chemical compound Cl.C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 HXBZCHYDLURWIZ-UHFFFAOYSA-N 0.000 claims abstract description 8
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
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- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
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Abstract
一种含磷阻燃聚乙烯电缆料的制备方法，通过分子设计，首先采用4,4'‑二羟基二苯甲酮(DHBP)和氯磷酸二苯酯(DPCP)反应得到4,4'‑二磷酸二苯酯基二苯甲酮(DHPP)，并以此为原料用硼氢化钠还原得到4,4'‑二磷酸二苯酯基二苯甲醇(DHPP‑OH)。再用DHPP‑OH和对苯二异氰酸酯(NCO)来合成1,4‑二[(4,4'‑二磷酸二苯酯基二苯甲氧基)甲酰基]苯胺(DHPP‑OH‑NCO)，将其用于制备阻燃聚乙烯电缆料，由于其为有机阻燃剂，在聚乙烯中相容性好，添加量比无机阻燃剂少，对聚乙烯力学性能影响小，同时可保证其长效阻燃。
Description
技术领域
本发明涉及含磷阻燃聚乙烯电缆料的制备技术，属于高分子材料技术领域。
背景技术
电线电缆广泛应用于国民经济各个行业，与人们日常生活息息相关，在电力传输、信号控制等领域发挥着至关重要的作用。绝大多数电线电缆用绝缘、护套材料为有机高分子材料。聚乙烯以其优异的绝缘、耐磨、易加工、耐腐蚀性能及使用寿命长在电线电缆绝缘、护套材料中应用广泛。但其在高温条件下易降解，火灾条件下易燃等缺陷会造成火灾损失的进一步增大，因此必须对其进行阻燃才能安全用于电线电缆绝缘、护套材料。
专利CN 102161794 B公开了一种低烟无卤阻燃聚乙烯电缆料，其特征在于包括按重量份计的聚乙烯80～85重量份、乙烯- 醋酸乙烯酯共聚物5～10重量份、阻燃剂5～15重量份、偶联剂0.5～1.5重量份。阻燃剂主要为红磷/蒙脱土插层复合物、氢氧化物、碳酸氢钠、钛酸四异丙酯的混合物。
专利CN 103709486 B公开了一种聚乙烯电缆护套管，由阻燃聚乙烯材料制成。阻燃聚乙烯材料的组成为：高密度聚乙烯45~74份，超高分子量聚乙烯5~15份，微胶囊红磷母粒14~22份，氢氧化铝4~8份，硼酸锌2~5份，炭黑1~5份，乙撑双硬脂酰胺0.1~1份，抗氧剂0.2~1份，颜料0.01~0.1份。
专利CN 104861271 A公开了一种阻燃聚乙烯绝缘电缆料，原料为聚乙烯80份、氧化铝5份、氢氧化镁20~35份、抗老化剂1~5份。
上述几个专利公开的是低烟无卤阻燃聚乙烯电缆料制备方法，为聚乙烯电缆的使用提供了安全保障。但其所用阻燃剂均为无机阻燃剂，在电缆服役期限内受环境中水汽、光、热等作用易从聚乙烯基体中析出，致使在长期使用过程中很难保证同期限的阻燃效果。
发明内容
本发明的目的是提供一种含磷阻燃聚乙烯电缆料的制备方法。
本发明是一种含磷阻燃聚乙烯电缆料的制备方法，其步骤为：
（1）合成DHPP的步骤为：
在装有搅拌装置、控温装置的反应容器中加入4,4'-二羟基二苯甲酮、溶剂、缚酸剂；在惰性气体保护条件下，20~-30℃搅拌30min后加入氯磷酸二苯酯，加料完毕后20~30℃搅拌1h，体系由浑浊变澄清，加水淬灭反应，用二氯甲烷萃取3次，有机相用去离子水洗3次，减压蒸干二氯甲烷，得到无色液体，利用柱层析分离提纯产品，柱层析按V/V为石油醚:乙酸乙酯=5:1，得到白色固体4,4'-二磷酸二苯酯基二苯甲酮，即DHPP；
（2）合成DHPP-OH的步骤为：
在装有搅拌装置、控温装置的反应容器中加入DHPP、溶剂、硼氢化钠；加料完毕后20-30℃搅拌6h，体系由浑浊变澄清，加入浓度为5%wt NaOH溶液，体系变浑浊，搅拌10min，体系由浑浊变澄清；减压蒸干溶剂，用二氯甲烷萃取3次，有机相用去离子水洗3次，减压蒸干二氯甲烷得到无色液体，利用柱层析分离提纯产品，柱层析按V/V为石油醚:乙酸乙酯=5:1，得到无色透明液体4,4'-二磷酸二苯酯基二苯甲醇，即DHPP-OH；
（3）合成DHPP-OH-NCO的步骤为：
在装有回流装置、控温装置、机械搅拌装置的反应容器中加入DHPP-OH、溶剂、催化剂、对苯二异氰酸酯，80-110℃反应6h，体系由无色变为淡黄色；减压蒸出溶剂得到黄色液体，体系用二氯甲烷萃取3次，有机相用去离子水洗3次；减压蒸干二氯甲烷得到淡黄色液体，利用柱层析分离提纯产品，柱层析按V/V为石油醚:乙酸乙酯=5:1，得到黄色透明液体1,4-二[(4,4'-二磷酸二苯酯基二苯甲氧基)甲酰基]苯胺，即DHPP-OH-NCO；
（4）制备含磷阻燃聚乙烯电缆料的步骤为：
将配方量的聚乙烯、阻燃剂、抗氧剂、补强填充剂加到高速混料机中，搅拌混匀后用双螺杆挤出机挤出造粒即可得到含磷阻燃聚乙烯电缆料。
本发明的有益之处是，通过分子设计首先采用4,4'-二羟基二苯甲酮(DHBP)和氯磷酸二苯酯(DPCP)反应得到4,4'-二磷酸二苯酯基二苯甲酮(DHPP)，并以此为原料用硼氢化钠还原得到4,4’-二磷酸二苯酯基二苯甲醇(DHPP-OH)。再用DHPP-OH和对苯二异氰酸酯(NCO)合成1，4-二[(4,4’-二磷酸二苯酯基二苯甲氧基)甲酰基]苯胺(DHPP-OH-NCO)，再将DHPP-OH-NCO 用于聚乙烯阻燃，制备得到阻燃聚乙烯电缆料，在电缆料中引入具有阻燃性能的元素磷、氮，有效提高聚乙烯电缆料的阻燃性能，减少火灾对生命财产造成的损失。
具体实施方式
本发明通过分子设计，首先采用4,4'-二羟基二苯甲酮(DHBP)和氯磷酸二苯酯(DPCP)反应得到4,4'-二磷酸二苯酯基二苯甲酮(DHPP)，并以此为原料用硼氢化钠还原得到4,4'-二磷酸二苯酯基二苯甲醇(DHPP-OH)。再用DHPP-OH和对苯二异氰酸酯(NCO)来合成1,4-二[(4,4'-二磷酸二苯酯基二苯甲氧基)甲酰基]苯胺(DHPP-OH-NCO)，将其用于制备阻燃聚乙烯电缆料，由于其为有机阻燃剂，在聚乙烯中相容性好，添加量比无机阻燃剂少，对聚乙烯力学性能影响小，同时可保证其长效阻燃。
DHPP-OH合成工艺路线如下：
合成DHPP-OH-NCO工艺路线如下：
。
本发明是一种含磷阻燃聚乙烯电缆料的制备方法，其步骤为：
（1）合成DHPP的步骤为：
在装有搅拌装置、控温装置的反应容器中加入4,4'-二羟基二苯甲酮、溶剂、缚酸剂；在惰性气体保护条件下，20~-30℃搅拌30min后加入氯磷酸二苯酯，加料完毕后20~30℃搅拌1h，体系由浑浊变澄清，加水淬灭反应，用二氯甲烷萃取3次，有机相用去离子水洗3次，减压蒸干二氯甲烷，得到无色液体，利用柱层析分离提纯产品，柱层析按V/V为石油醚:乙酸乙酯=5:1，得到白色固体4,4'-二磷酸二苯酯基二苯甲酮，即DHPP；
（2）合成DHPP-OH的步骤为：
在装有搅拌装置、控温装置的反应容器中加入DHPP、溶剂、硼氢化钠；加料完毕后20-30℃搅拌6h，体系由浑浊变澄清，加入浓度为5%wt NaOH溶液，体系变浑浊，搅拌10min，体系由浑浊变澄清；减压蒸干溶剂，用二氯甲烷萃取3次，有机相用去离子水洗3次，减压蒸干二氯甲烷得到无色液体，利用柱层析分离提纯产品，柱层析按V/V为石油醚:乙酸乙酯=5:1，得到无色透明液体4,4'-二磷酸二苯酯基二苯甲醇，即DHPP-OH；
（3）合成DHPP-OH-NCO的步骤为：
在装有回流装置、控温装置、机械搅拌装置的反应容器中加入DHPP-OH、溶剂、催化剂、对苯二异氰酸酯，80-110℃反应6h，体系由无色变为淡黄色；减压蒸出溶剂得到黄色液体，体系用二氯甲烷萃取3次，有机相用去离子水洗3次；减压蒸干二氯甲烷得到淡黄色液体，利用柱层析分离提纯产品，柱层析按V/V为石油醚:乙酸乙酯=5:1，得到黄色透明液体1,4-二[(4,4'-二磷酸二苯酯基二苯甲氧基)甲酰基]苯胺，即DHPP-OH-NCO；
（4）制备含磷阻燃聚乙烯电缆料的步骤为：
将配方量的聚乙烯、阻燃剂、抗氧剂、补强填充剂加到高速混料机中，搅拌混匀后用双螺杆挤出机挤出造粒即可得到含磷阻燃聚乙烯电缆料。
以上所述步骤（1）中，按质量百分数计，合成DHPP的配方为：
4,4'-二羟基二苯甲酮 6.0%~8.5%，氯磷酸二苯酯 16.5%~23.0%，缚酸剂 2.5%~3.5 %，溶剂 70.0%~85.0%。
以上所述步骤（2）中，按质量百分数计，合成DHPP-OH的配方为：
DHPP 37.0%~60.0%，硼氢化钠 2.9%~4.7%，NaOH(5%wt)溶液 5.0%~8.0%，溶剂 45.0%~55.0%。
以上所述步骤（3）中，按质量百分数计，合成DHPP-OH-NCO的配方为：
DHPP-OH 36.0%~58.0%，对苯二异氰酸酯 3.8%~6.3%，催化剂1.0%~1.6%，溶剂 45.0%~55.0%。
以上所述步骤（4）中，按质量百分数计，制备含磷阻燃聚乙烯电缆料的配方为：
聚乙烯 75.0~85.0%，DHPP-OH-NCO 15.0~20.0%，抗氧剂 0.5~1.0%，补强填充剂5.0~10.0%。
以上所述步骤（1）、（3）所述溶剂是苯、甲苯、丁酮中的一种；步骤（1）所述缚酸剂为三乙胺、吡啶中的一种；步骤（1）所述惰性气体为氩气、氦气、氮气中的一种。
以上所述步骤（2）所述溶剂是甲醇和乙醇中的一种。
以上所述步骤（3）所述催化剂为三乙胺。
以上所述的抗氧剂为巴斯夫Irganox 1010或Irganox 245的一种，补强填充剂是炭黑或白炭黑的一种或任意比例混合物。
以下是本发明的实施例，但本发明不局限于下列实施例中。
实施例1.
在装有机械搅拌、控温装置的反应容器中加入4,4'-二羟基二苯甲酮12份，溶剂120份，三乙胺5份。通氮气，20-30℃搅拌30min后加入氯磷酸二苯酯30份，加料完毕后20-30℃搅拌1h，体系由浑浊变澄清，加水淬灭反应，减压蒸干溶剂，用二氯甲烷萃取3次，有机相用去离子水洗3次，减压蒸干二氯甲烷，得到无色液体，利用柱层析(石油醚:乙酸乙酯=5:1，V/V)分离提纯产品，得到白色固体DHPP。
实施例2.
在装有机械搅拌、控温装置的反应容器中加入DHPP 80份，乙醇100份，硼氢化钠8份。加料完毕后20-30℃搅拌6h，体系由浑浊变澄清，加入氢氧化钠(5%wt)溶液15份，体系变浑浊，搅拌5min，体系由浑浊变澄清。减压蒸干溶剂，得到乳白色液体，再用二氯甲烷萃取3次，有机相用去离子水洗3次，减压蒸干二氯甲烷得到无色液体，利用柱层析(PE:EA=4:1，V/V)分离提纯产品，得到无色透明液体DHPP-OH。
实施例3.
在装有回流装置、控温装置、机械搅拌装置的反应容器中加入DHPP-OH 50份，甲苯70份，三乙胺2份，对苯二异氰酸酯6份，110℃回流6h，体系由无色变为淡黄色。减压蒸干溶剂得到黄色液体，体系用二氯甲烷萃取3次，有机相用去离子水洗3次。减压蒸干二氯甲烷得到淡黄色液体，利用柱层析(石油醚:乙酸乙酯=3:1，V/V)分离提纯产品，得到黄色透明液体DHPP-OH-NCO。
实施例4.
将聚乙烯70份、DHPP-OH-NCO 18份、Irganox 1010 0.8份、白炭黑 6份加到高速混料机中，搅拌混匀后用双螺杆挤出机挤出造粒即可得到含磷阻燃聚乙烯电缆料。
Claims (9)
1.一种含磷阻燃聚乙烯电缆料的制备方法，其特征在于，其步骤为：
（1）合成DHPP的步骤为：
在装有搅拌装置、控温装置的反应容器中加入4,4'-二羟基二苯甲酮、溶剂、缚酸剂；在惰性气体保护条件下，20~-30℃搅拌30min后加入氯磷酸二苯酯，加料完毕后20~30℃搅拌1h，体系由浑浊变澄清，加水淬灭反应，用二氯甲烷萃取3次，有机相用去离子水洗3次，减压蒸干二氯甲烷，得到无色液体，利用柱层析分离提纯产品，柱层析按V/V为石油醚:乙酸乙酯=5:1，得到白色固体4,4'-二磷酸二苯酯基二苯甲酮，即DHPP；
（2）合成DHPP-OH的步骤为：
在装有搅拌装置、控温装置的反应容器中加入DHPP、溶剂、硼氢化钠；加料完毕后20-30℃搅拌6h，体系由浑浊变澄清，加入浓度为5%wt NaOH溶液，体系变浑浊，搅拌10min，体系由浑浊变澄清；减压蒸干溶剂，用二氯甲烷萃取3次，有机相用去离子水洗3次，减压蒸干二氯甲烷得到无色液体，利用柱层析分离提纯产品，柱层析按V/V为石油醚:乙酸乙酯=5:1，得到无色透明液体4,4'-二磷酸二苯酯基二苯甲醇，即DHPP-OH；
（3）合成DHPP-OH-NCO的步骤为：
在装有回流装置、控温装置、机械搅拌装置的反应容器中加入DHPP-OH、溶剂、催化剂、对苯二异氰酸酯，80-110℃反应6h，体系由无色变为淡黄色；减压蒸出溶剂得到黄色液体，体系用二氯甲烷萃取3次，有机相用去离子水洗3次；减压蒸干二氯甲烷得到淡黄色液体，利用柱层析分离提纯产品，柱层析按V/V为石油醚:乙酸乙酯=5:1，得到黄色透明液体1,4-二[(4,4'-二磷酸二苯酯基二苯甲氧基)甲酰基]苯胺，即DHPP-OH-NCO；
（4）制备含磷阻燃聚乙烯电缆料的步骤为：
将配方量的聚乙烯、阻燃剂、抗氧剂、补强填充剂加到高速混料机中，搅拌混匀后用双螺杆挤出机挤出造粒即可得到含磷阻燃聚乙烯电缆料。
2.根据权利要求书1所述的含磷阻燃聚乙烯电缆料的制备方法，其特征在于：步骤（1）中，按质量百分数计，合成DHPP的配方为：
4,4'-二羟基二苯甲酮 6.0%~8.5%，氯磷酸二苯酯 16.5%~23.0%，缚酸剂 2.5%~3.5 %，溶剂 70.0%~85.0%。
3.根据权利要求书1所述的含磷阻燃聚乙烯电缆料的制备方法，其特征在于：步骤（2）中，按质量百分数计，合成DHPP-OH的配方为：
DHPP 37.0%~60.0%，硼氢化钠 2.9%~4.7%，NaOH(5%wt)溶液 5.0%~8.0%，溶剂 45.0%~55.0%。
4.根据权利要求书1所述的含磷阻燃聚乙烯电缆料的制备方法，其特征在于：步骤（3）中，按质量百分数计，合成DHPP-OH-NCO的配方为：
DHPP-OH 36.0%~58.0%，对苯二异氰酸酯 3.8%~6.3%，催化剂1.0%~1.6%，溶剂 45.0%~55.0%。
5.根据权利要求书1所述的含磷阻燃聚乙烯电缆料的制备方法，其特征在于：步骤（4）中，按质量百分数计，制备含磷阻燃聚乙烯电缆料的配方为：
聚乙烯 75.0~85.0%，DHPP-OH-NCO 15.0~20.0%，抗氧剂 0.5~1.0%，补强填充剂5.0~10.0%。
6.根据权利要求书1所述的含磷阻燃聚乙烯电缆料的制备方法，其特征在于：步骤（1）、（3）所述溶剂是苯、甲苯、丁酮中的一种；步骤（1）所述缚酸剂为三乙胺、吡啶中的一种；步骤（1）所述惰性气体为氩气、氦气、氮气中的一种。
7.根据权利要求书1所述的含磷阻燃聚乙烯电缆料的制备方法，其特征在于：步骤（2）所述溶剂是甲醇和乙醇中的一种。
8.根据权利要求书1所述的含磷阻燃聚乙烯电缆料的制备方法，其特征在于：步骤（3）所述催化剂为三乙胺。
9.根据权利要求书1所述的含磷阻燃聚乙烯电缆料的制备方法，其特征在于：所述的抗氧剂为巴斯夫Irganox 1010或Irganox 245的一种，补强填充剂是炭黑或白炭黑的一种或任意比例混合物。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4022757A (en) * | 1974-01-17 | 1977-05-10 | Bayer Aktiengesellschaft | Dicarbamic acid diesters containing phosphorus |
| US4904426A (en) * | 1988-03-31 | 1990-02-27 | The Dow Chemical Company | Process for the production of fibers from poly(etheretherketone)-type polymers |
| JP2005273072A (ja) * | 2004-03-24 | 2005-10-06 | Kaneka Corp | 難燃性ポリエステル系人工毛髪 |
| EP1659148A1 (en) * | 2003-08-01 | 2006-05-24 | Fuji Electric Holdings Co., Ltd. | Reactive flame retardant and flame-retardant processed resin obtained with the same |
| CN101415487A (zh) * | 2003-12-08 | 2009-04-22 | 纽约州立大学研究基金会 | 传感器应用中的位点选择性标记和模板分子印记聚合物 |
-
2018
- 2018-08-06 CN CN201810882544.3A patent/CN109233046B/zh not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4022757A (en) * | 1974-01-17 | 1977-05-10 | Bayer Aktiengesellschaft | Dicarbamic acid diesters containing phosphorus |
| US4904426A (en) * | 1988-03-31 | 1990-02-27 | The Dow Chemical Company | Process for the production of fibers from poly(etheretherketone)-type polymers |
| EP1659148A1 (en) * | 2003-08-01 | 2006-05-24 | Fuji Electric Holdings Co., Ltd. | Reactive flame retardant and flame-retardant processed resin obtained with the same |
| CN101415487A (zh) * | 2003-12-08 | 2009-04-22 | 纽约州立大学研究基金会 | 传感器应用中的位点选择性标记和模板分子印记聚合物 |
| JP2005273072A (ja) * | 2004-03-24 | 2005-10-06 | Kaneka Corp | 難燃性ポリエステル系人工毛髪 |
Non-Patent Citations (3)
| Title |
|---|
| B.XIAO: "Studies on curing effect of phosphite monomer by EB radiation in the air", 《RADIATION PHYSICS AND CHEMISTRY》 * |
| BAOPING YANG: "An efficient flame retardant for epoxy resin: Preparation and pyrolytic behaviour", 《HIGH PERFORMANCE POLYMERS》 * |
| YU FU: "Click-based transparent durable films derived from tetrabrachius PDMS-bridged epoxy acrylates and surface modified nanosilica particles", 《PROGRESS IN ORGANIC COATINGS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110407880A (zh) * | 2019-08-26 | 2019-11-05 | 兰州理工大学 | 一种含磷阻燃剂及制备方法 |
| CN110483577A (zh) * | 2019-08-26 | 2019-11-22 | 兰州理工大学 | 一种P、N、Si三元杂化阻燃剂及制备方法 |
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| CN109233046B (zh) | 2020-12-08 |
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