CN109535695A - 高阻燃低挥发压缩残余变量小的座椅聚氨酯发泡材料及其制备方法和应用 - Google Patents

高阻燃低挥发压缩残余变量小的座椅聚氨酯发泡材料及其制备方法和应用 Download PDF

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CN109535695A
CN109535695A CN201811451133.5A CN201811451133A CN109535695A CN 109535695 A CN109535695 A CN 109535695A CN 201811451133 A CN201811451133 A CN 201811451133A CN 109535695 A CN109535695 A CN 109535695A
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polyurethane foam
mold
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seat
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王淞民
陈芷逍
曹鹏
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Shenyang Jinbei Automobile Parts Co Daotuo
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Abstract

本发明公开一种高阻燃低挥发压缩残余变量小的座椅聚氨酯发泡材料，按重量份比，包括如下组分：聚醚多元醇PPG 40份‑60份，聚合物多元醇POP 40份‑60份，蒸馏水2.5‑3.5份，交联剂0.8‑1.2份，凝胶催化剂0.4‑0.6份，发泡催化剂0.15‑0.19份，表面稳定剂0.65‑0.85份。该座椅聚氨酯发泡材料具有阻燃性能高，更安全；挥发物含量低，更环保；回弹率高，更舒适；压缩残余变量小，更耐用；生产节拍短，更高产等优势。

Description

高阻燃低挥发压缩残余变量小的座椅聚氨酯发泡材料及其制 备方法和应用
技术领域
本发明涉及聚氨酯发泡材料领域，具体涉及一种高阻燃低挥发压缩残余变量小的座椅聚氨酯发泡材料及其制备方法和应用。
背景技术
目前，中国高阻燃座椅发泡原材料是采用普通的阻燃聚醚多元醇，外加普通的卤素阻燃剂，或含磷阻燃剂，或三聚氰胺，又或三氧化二锑来满足。无论是哪种阻燃添加剂都造成其他的物理性能降低，无法达到环保和舒适耐用的效果，且氧指数最多能达到28.5％。目前北方高铁座椅发泡的性能要求为，如表1所示：
表1.聚氨酯泡沫的物理性能要求
2.聚氨酯泡沫的燃烧性能要求和详细的试验方法参照TB/T 3237-2010执行。
2.1氧指数及燃烧性能，氧指数≥28，燃烧性级：A、B级
2.2毒性气体要求符合下表2的规定
表2.聚氨酯泡沫的毒性气体要求
序号 气体种类 浓度mg/m<sup>3</sup>(ppm)
1 CO ＜4000(3500)
2 CO2 ＜90000(50000)
3 HF ＜82(100)
4 HBr ＜330(100)
5 HCl ＜150(100)
6 NOX(以NO2计) ＜190(100)
7 SO2 ＜260(100)
8 HCN ＜110(100)
2.3烟密度要求符合下表3的规定
表3.聚氨酯泡沫的烟密度要求
序号 燃烧方式 DS1.5 DS4
1 无引燃 ≤100 ≤200
2 引燃 ≤100 ≤200
2.4聚氨酯泡沫的环保性能要求
2.4.1甲醛释放量按TB/T3139-2006第3.1.1条要求：甲醛释放量≤1.5mg/L
2.4.2有害物质限量按TB/T3139-2006第3.5.1条要求：可溶性铅≤5mg/Kg；可溶性镉≤5mg/Kg；有机挥发物≤6g/Kg
2.4.3禁限用材料要求为：
4-硝基联苯、芳族胺及其盐类：2-萘胺.对二氨基联苯.4-氨基联苯、八溴二苯醚(Octa-BDE)、五溴二苯醚(Penta-BDE)、短链氯化石蜡(SCCP)、中链氯化石蜡(MCCP)、偶氮著色剂。
高铁对阻燃、VOC和物理性能同时都要求很高，很多制造企业无法制造出满足此标准要求的产品。
发明内容
本发明针对现有技术不足，提供一种高阻燃、低挥发、高回弹、残余变量小的座椅聚氨酯发泡材料配方和选择了一种稳定环保高产能的生产工艺，使该发泡的阻燃性、挥发物及其他物理性能指标满足且远高出高铁座椅发泡材料的要求。
本发明采用的技术方案为：
高阻燃低挥发压缩残余变量小的座椅聚氨酯发泡材料，按重量份比，包括如下组分：
聚醚多元醇PPG 40份-60份，聚合物多元醇POP 40份-60份，蒸馏水2.5-3.5份，交联剂0.8-1.2份，凝胶催化剂0.4-0.6份，发泡催化剂0.15-0.19份，表面稳定剂0.65-0.85份。
所述的座椅聚氨酯发泡材料，所述聚醚多元醇PPG的牌号为F-3531，其具体参数为羟值为33.5～36.5mgKOH/g，黏度为800～1000mPa·s。
所述的座椅聚氨酯发泡材料，所述聚合物多元醇POP的牌号为8033，其具体参数为羟值为27.5～30.5mgKOH/g，黏度为2000～1000mPa·s。
所述的座椅聚氨酯发泡材料，所述交联剂为二乙醇胺。
所述的座椅聚氨酯发泡材料，所述凝胶催化剂三乙烯二胺，具体为迈图33LX。
所述的座椅聚氨酯发泡材料，所述发泡催化剂为叔胺羧酸盐、双(2-二甲基氨乙基)醚；具体为迈图A400。
所述的座椅聚氨酯发泡材料，所述表面稳定剂为硅油。
一种所述的座椅聚氨酯发泡材料的制备方法，包括如下步骤：
1)按配方比例称取各组分投入到搅拌罐内，以500～800转/分钟的搅拌速度，搅拌混合1.5-2.5h，转入存料罐备用；
2)清模：对发泡模具进行清理，确保预留的气道畅通，并且去除模腔内粘留泡沫；
3)喷脱模剂：对模具均匀的喷涂脱模剂；
4)摆埋伏件：将需要埋伏在发泡材料中的零部件摆放在模具中；
5)浇注：将步骤1)混合好并转入存料罐备用的混合物与甲苯二异氰酸酯、多苯基多亚甲基多异氰酸酯混合，再通过发泡机在90-220bar的压力下充分混合，根据预先设计的轨迹浇注在模具内；
6)熟化：模具在转盘线上自动合模后，泡沫在模腔内启发、熟化，时间230s-280s，模具温度控制在55-70℃；
7)脱模：模具在转盘线上自动开模后，用手将模具脱出，模具供下次使用；
8)开孔：脱模后的泡沫，需要尽快经过碾压或抽真空的方式进行开孔；
9)剪边：开孔后对泡沫的工艺飞边进行修剪；
10)修补：如果泡沫有在标准范围内地缺陷，对泡沫进行修补；
11)后熟化：对修补后的发泡进行至少8小时的后熟化时间；
12)储存：达到后熟化时间后，摘下泡沫，按照规定的标准包装装车存储，等待使用。
所述的制备方法，步骤5)中甲苯二异氰酸酯和多苯基多亚甲基多异氰酸酯按体积比4:1的比例混合。
一种所述的座椅聚氨酯发泡材料在制备北方高铁座椅上的应用。
本发明具有以下有益效果：
本发明为一种新型的高阻燃、低挥发、高回弹、压缩残余变量小的座椅聚氨酯发泡材料及其高产能的生产工艺。所述的材料使用特殊高阻燃聚醚多元醇和高阻燃聚合物多元醇，加入少量硅油、交联剂、凝胶催化剂、发泡催化剂和水，按照配方固定比例在混料罐中混合；充分搅拌后，通过自动设备(Krauss Maffei设备)转入发泡机内；通过发泡机将发泡材料与聚异氰酸酯利用高压充分混合。注入放在转盘线上准备好的模具中；模具自动合模后，化料在一定的模温下乳白，凝胶，起升，熟化，成型；出模后对发泡开孔，修剪，后熟化，即可使用。该类座椅发泡的特点是：阻燃性能高，更安全；挥发物含量低，更环保；回弹率高，更舒适；压缩残余变量小，更耐用；生产节拍短，更高产。
本发明适用于高阻燃座椅发泡的新型原材料配方，采用高阻燃、低挥发高分子链的聚醚多元醇和聚合物多元醇，避免加入阻燃剂对制造工艺和产品产生的影响，使座椅发泡具有高阻燃、低挥发、高回弹、压缩残余变量小的性能。配方中部分使用反应型催化剂，使泡沫的TVOC和胺类含量降低，达到低挥发的效果。
本发明发泡工艺采用冷发工艺过程，避免了热发高温造成分子链上的羟基分解成醛类，降低VOC。由于配方中各催化剂比例合适，发泡反应过程平衡稳定，且熟化快，节拍短，产能高。
本发明发泡工艺过程使用Krauss Maffei设备化投料，投放比例精准，环线重复一致性高，生产产品一致稳定。
具体实施方式
实施例1高阻燃低挥发压缩残余变量小的座椅聚氨酯发泡材料
(一)按重量份比包括如下组分：
聚醚多元醇PPG 50份，聚合物多元醇POP 50份，蒸馏水3份，交联剂1份，凝胶催化剂0.5份，发泡催化剂0.17份，表面稳定剂0.75份。
上述材料具体为：
聚醚多元醇PPG的型号为：选购自聚源化工(全称：吉林聚源化工有限公司)，型号为F-3531；其具体参数为羟值为33.5～36.5mgKOH/g，黏度为800～1000mPa·s。
聚合物多元醇POP的型号为：选购自江阴友邦(全称：江阴友邦化工有限公司)，型号为8033；其具体参数为羟值为27.5～30.5mgKOH/g，黏度为2000～1000mPa·s。
交联剂为：二乙醇胺；
凝胶催化剂为：选购自迈图(全称：迈图高新材料有限公司)，型号为33LX；
发泡催化剂为：选购自迈图(全称：迈图高新材料有限公司)，型号为A400；
表面稳定剂为：硅油。
(二)上述高阻燃低挥发压缩残余变量小的座椅聚氨酯发泡材料的制备方法，包括如下步骤：
1)按上述配方比例称取各组分投入到搅拌罐内，以600转/分钟的搅拌速度，搅拌混合2h，转入存料罐备用；
2)清模：先对发泡模具进行清理，确保预留的气道畅通。并且去除模腔内粘留泡沫。
3)喷脱模剂：对模具均匀的喷涂脱模剂，防止发泡粘到模具上，脱模造成发泡损坏。
4)摆埋伏件：将需要埋伏在发泡中的零件摆放在模具中，例如，钢丝、衬布、塑料件。
5)浇注：用步骤1)混合好的组合聚醚与甲苯二异氰酸酯、多苯基多亚甲基多异氰酸酯混合，所得混合物通过发泡机在90-220bar的压力下充分混合。浇注在模具内，设计好机器人浇注的轨迹，确保产品没有缺陷。所述甲苯二异氰酸酯、多苯基多亚甲基多异氰酸酯按体积比4:1的比例混合。
6)熟化：模具在转盘线上自动合模后，泡沫在模腔内启发、熟化。时间约230s-280s，模具温度控制在55-70摄氏度间。
7)脱模：模具在转盘线上自动开模后，用手将模具脱出，模具供下次使用。
8)开孔：脱模后的泡沫，需要尽快经过碾压或抽真空的方式进行开孔。
9)剪边：开孔后对泡沫的工艺飞边进行修剪。
10)修补：如果泡沫有在标准范围内地缺陷，对泡沫进行修补。
11)后熟化：对修补后的发泡进行至少8小时的后熟化时间，如果未达到时间的泡沫受到外力作用，会产生变形。因此，将产品挂在空中的悬链上，确保在空中运转时间在8小时以上，来满足熟化时间。
12)储存：达到熟化时间后，从悬链上摘下泡沫，按照规定的标准包装装车存储，等待使用。并且存储区域需要避光通风。
(三)对上述制备的聚氨酯发泡材料性能进行检测，检测数据如下：
3.1聚氨酯泡沫的物理性能要求如表4
表4
3.2聚氨酯泡沫的燃烧性能要求
燃烧性能要求和详细的试验方法参照TB/T 3237-2010执行。
3.2.1氧指数及燃烧性能，氧指数≥28，燃烧性级：A、B级
测试值：氧指数：32％；燃烧性：A-0。
3.2.2毒性气体要求符合下表的规定
表5聚氨酯泡沫的毒性气体要求
3.2.3烟密度要求符合下表6的规定
表6聚氨酯泡沫的烟密度要求
序号 燃烧方式 DS1.5 测试值 DS4 测试值
1 无引燃 ≤100 70.1 ≤200 178
2 引燃 ≤100 25 ≤200 54.4
3.3聚氨酯泡沫的环保性能要求
3.3.1甲醛释放量按TB/T3139-2006第3.1.1条要求：甲醛释放量≤1.5mg/L
测试值：甲醛释放量：ND
3.3.2有害物质限量按TB/T3139-2006第3.5.1条要求：可溶性铅≤5mg/Kg，可溶性镉≤5mg/Kg，有机挥发物≤6g/Kg
测试值：可溶性铅：ND；可溶性镉：ND；有机挥发物：1g/Kg。
3.3.3禁限用材料要求为：
4-硝基联苯、芳族胺及其盐类：2-萘胺.对二氨基联苯.4-氨基联苯、八溴二苯醚(Octa-BDE)、五溴二苯醚(Penta-BDE)、短链氯化石蜡(SCCP)、中链氯化石蜡(MCCP)、偶氮著色剂。
测试值：
2-萘胺.对二氨基联苯.4-氨基联苯:ND
八溴二苯醚(Octa-BDE):ND
五溴二苯醚(Penta-BDE):ND
短链氯化石蜡(SCCP):ND
中链氯化石蜡(MCCP):ND
偶氮著色剂:ND
由上述测试结果可知：全部符合要求，且阻燃性能高，舒适性高。
对比
使用阻燃剂(具体为：三氧化二锑)增加阻燃性的对标实验数据：
将实施例1配方中的聚醚多元醇PPG 50份，聚合物多元醇POP 50份，替换成天津三石化聚醚PPG 330NG和POP 05/45，其他组分不变，并添加阻燃剂三氧化二锑，制备方法同实施例1，并对添加阻燃剂三氧化二锑制备的聚氨酯发泡材料性能进行检测，检测数据如下：
1、聚氨酯泡沫的物理性能要求如表7
表7
2、聚氨酯泡沫的燃烧性能要求
燃烧性能要求和详细的试验方法参照TB/T 3237-2010执行。
2.1氧指数及燃烧性能，氧指数≥28，燃烧性级：A、B级
测试值：氧指数：28.5％；燃烧性：A-0
由对比例可知：拉伸强度，75％永久压缩变形不合格，舒适性，耐久性较差。

Claims (10)

1.高阻燃低挥发压缩残余变量小的座椅聚氨酯发泡材料，其特征在于，按重量份比，包括如下组分：
聚醚多元醇PPG 40份-60份，聚合物多元醇POP 40份-60份，蒸馏水2.5-3.5份，交联剂0.8-1.2份，凝胶催化剂0.4-0.6份，发泡催化剂0.15-0.19份，表面稳定剂0.65-0.85份。
2.如权利要求1所述的座椅聚氨酯发泡材料，其特征在于，所述聚醚多元醇PPG的牌号为F-3531，其具体参数为羟值为33.5～36.5mgKOH/g，黏度为800～1000mPa·s。
3.如权利要求1所述的座椅聚氨酯发泡材料，其特征在于，所述聚合物多元醇POP的牌号为8033，其具体参数为羟值为27.5～30.5mgKOH/g，黏度为2000～1000mPa·s。
4.如权利要求1所述的座椅聚氨酯发泡材料，其特征在于，所述交联剂为二乙醇胺。
5.如权利要求1所述的座椅聚氨酯发泡材料，其特征在于，所述凝胶催化剂三乙烯二胺，具体为迈图33LX。
6.如权利要求1所述的座椅聚氨酯发泡材料，其特征在于，所述发泡催化剂为叔胺羧酸盐、双(2-二甲基氨乙基)醚；具体为迈图A400。
7.如权利要求1所述的座椅聚氨酯发泡材料，其特征在于，所述表面稳定剂为硅油。
8.一种如权利要求1-7任一项所述的座椅聚氨酯发泡材料的制备方法，其特征在于，包括如下步骤：
1)按配方比例称取各组分投入到搅拌罐内，以500～800转/分钟的搅拌速度，搅拌混合1.5-2.5h，转入存料罐备用；
2)清模：对发泡模具进行清理，确保预留的气道畅通，并且去除模腔内粘留泡沫；
3)喷脱模剂：对模具均匀的喷涂脱模剂；
4)摆埋伏件：将需要埋伏在发泡材料中的零部件摆放在模具中；
5)浇注：将步骤1)混合好并转入存料罐备用的混合物与甲苯二异氰酸酯、多苯基多亚甲基多异氰酸酯混合，再通过发泡机在90-220bar的压力下充分混合，根据预先设计的轨迹浇注在模具内；
6)熟化：模具在转盘线上自动合模后，泡沫在模腔内启发、熟化，时间230s-280s，模具温度控制在55-70℃；
7)脱模：模具在转盘线上自动开模后，用手将模具脱出，模具供下次使用；
8)开孔：脱模后的泡沫，需要尽快经过碾压或抽真空的方式进行开孔；
9)剪边：开孔后对泡沫的工艺飞边进行修剪；
10)修补：如果泡沫有在标准范围内地缺陷，对泡沫进行修补；
11)后熟化：对修补后的发泡进行至少8小时的后熟化时间；
12)储存：达到后熟化时间后，摘下泡沫，按照规定的标准包装装车存储，等待使用。
9.如权利要求8所述的制备方法，其特征在于，步骤5)中甲苯二异氰酸酯和多苯基多亚甲基多异氰酸酯按体积比4:1的比例混合。
10.一种如权利要求1-7任一项所述的座椅聚氨酯发泡材料在制备北方高铁座椅上的应用。
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