CN114133414B - 一种含磷氮植物油多元醇及其制备方法和应用 - Google Patents
一种含磷氮植物油多元醇及其制备方法和应用 Download PDFInfo
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- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 42
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 38
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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Abstract
本发明公开了一种含磷氮植物油多元醇及其制备方法和应用。本发明的含磷氮植物油多元醇的制备方法包括以下步骤:1)将环氧大豆油、9,10‑二氢‑9‑氧杂‑10‑磷杂菲‑10‑氧化物和酸性/碱性催化剂混合,进行反应,得到含磷植物油多元醇;2)将含磷植物油多元醇和胺类化合物混合,进行反应,即得含磷氮植物油多元醇。本发明的含磷氮植物油多元醇同时含有具有协同阻燃效应的P和N两种元素,阻燃效率高,用于聚氨酯产品无阻燃剂析出现象,且不会对聚氨酯产品本身的物理性能造成影响。
Description
技术领域
本发明涉及有机合成技术领域,具体涉及一种含磷氮植物油多元醇及其制备方法和应用。
背景技术
硬质聚氨酯泡沫塑料,简称聚氨酯硬泡,多为闭孔结构,具有绝热效果好、重量轻、比强度大、施工方便等优良特性,同时还具有隔音、防震、电绝缘、耐热、耐寒、耐溶剂等特点,广泛用作冰箱、冷库、冷藏车等的绝热材料以及建筑物、储罐、管道等的保温材料。然而,聚氨酯硬泡易燃,且燃烧过程中会产生大量的有毒有害烟雾和气体,极大地限制了其应用范围。目前,主要是通过在聚氨酯硬泡中添加含氯、含溴、含磷等阻燃元素的化合物作为阻燃剂来提高其阻燃性能,而要想达到较好的阻燃效果,阻燃剂的添加量通常较大。聚氨酯硬泡中大量添加阻燃剂不仅易出现阻燃剂迁移的问题,而且还会对发泡工艺以及聚氨酯硬泡的物理性能带来较大影响,难以满足实际应用需求。
因此,亟需寻求新的途径在不影响聚氨酯硬泡本身优异物理性能的前提下解决聚氨酯硬泡易燃的问题。
以上陈述仅仅是提供与本发明有关的背景信息,而不必然构成现有技术。
发明内容
本发明的目的在于提供一种含磷氮植物油多元醇及其制备方法和应用。
本发明所采取的技术方案是:
一种含磷氮植物油多元醇的制备方法包括以下步骤:
1)将环氧大豆油、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物和酸性/碱性催化剂混合,进行反应,得到含磷植物油多元醇;
2)将含磷植物油多元醇和胺类化合物混合,进行反应,即得含磷氮植物油多元醇。
优选的,所述环氧大豆油、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、胺类化合物的质量比为1:0.2~0.6:0.1~0.7。
优选的,步骤1)所述环氧大豆油的环氧值≥6.2%。
优选的,步骤1)所述酸催化剂为盐酸、硫酸、磷酸、氟硼酸、对甲苯磺酸中的至少一种。
优选的,步骤1)所述碱催化剂为氢氧化钾、氢氧化钠、甲醇钠、乙醇钠、甲醇钾、乙醇钾中的至少一种。
优选的,步骤1)所述反应在120℃~170℃下进行,反应时间为2h~5h。
优选的,步骤2)所述胺类化合物为氨水、乙二胺、苯胺、2,6-甲苯二胺、对甲基苯胺中的一种。
优选的,步骤2)所述反应在40℃~70℃下进行,反应时间为3h~6h。
本发明的含磷氮植物油多元醇的制备过程中发生的反应包括:
式中,R选自-H、-NHCH2CH2NH2、/>中的一种,R1和R2均为饱和碳链、含1个或多个环氧基团的碳链中的一种。
本发明的含磷氮植物油多元醇的阻燃机理:
1)含磷氮植物油多元醇的热稳定性高、耐析出性好、高效低毒,高温燃烧时会生成不容易挥发的磷酸或聚磷酸,可以在燃烧物表面形成高粘度的熔融玻璃质和致密的碳化层,碳化层可以将基质与热和氧隔绝开来;
2)含磷氮植物油多元醇在燃烧过程中会分解生成PO·、HPO·等游离基,在气相状态下可以捕捉活性H·游离基或OH·游离基;
3)含磷氮植物油多元醇在燃烧过程中会释放出不可燃气体,在有酸源(含磷化合物)存在的情况下可以使炭层膨胀,形成一定厚度的膨胀炭层,能够更好地隔绝热量的传递,大大提高阻燃效率。
本发明的有益效果是:本发明的含磷氮植物油多元醇同时含有具有协同阻燃效应的P和N两种元素,阻燃效率高,用于聚氨酯产品无阻燃剂析出现象,且不会对聚氨酯产品本身的物理性能造成影响。
具体而言:
1)本发明先进行环氧大豆油中的环氧基团和DOPO分子中活泼的P-H键的反应,在环氧大豆油的分子链中引入P元素,制得含磷植物油多元醇,再进行含磷植物油多元醇中的环氧基团与胺类化合物的反应,继续在环氧大豆油的分子链中引入N元素,制得含P、N两种阻燃元素的植物油多元醇,P和N具有阻燃协同效应,制得的含磷氮植物油多元醇的阻燃效率高,用于聚氨酯产品阻燃性能优异,且无阻燃剂析出现象,同时还可以确保得到的聚氨酯产品的物理性能不会发生明显下降;
2)本发明的含磷氮植物油多元醇具备含磷阻燃剂的优点,且含有的联苯结构的化学稳定性和热稳定性高,可以赋予分子结构中的P-C键优异的化学稳定性,阻燃性优于通用的有机磷酸酯类阻燃剂,此外,联苯结构被引入植物油多元醇后还可以提高植物多元醇的化学稳定性和热稳定性;
3)本发明的含磷氮植物油多元醇引入了环氧大豆油的长碳链,增加了与发泡剂正戊烷、环戊烷等的相容性,有利于硬质聚氨酯泡沫塑料的配备,制备的硬质聚氨酯泡沫塑料具有韧性高、不粉脆、泡孔细腻等特点,且保温性能显著优于由石油基多元醇制成的硬质聚氨酯泡沫塑料;
4)本发明的含磷氮植物油多元醇不含卤素元素,燃烧时不会产生有毒有害的黑烟,更加安全和环保;
5)本发明的含磷氮植物油多元醇的制备工艺简单,且不存在溶剂处理的问题,安全环保,适合进行大规模工业化生产。
具体实施方式
下面结合具体实施例对本发明作进一步的解释和说明。
实施例1:
一种含磷氮植物油多元醇,其制备方法包括以下步骤:
1)将500g环氧值6.20%的环氧大豆油、100g的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物和0.2g的KOH混合,搅拌升温至120℃后保温反应5h,再自然冷却至40℃,得到含磷植物油多元醇;
2)将60g的乙二胺加入步骤1)的含磷植物油多元醇中,40℃保温反应6h,再升温至100℃抽真空2h,即得含磷氮植物油多元醇(羟值:372mgKOH/g)。
实施例2:
一种含磷氮植物油多元醇,其制备方法包括以下步骤:
1)将500g环氧值6.22%的环氧大豆油、150g的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物和0.4g质量分数98%的浓硫酸混合,搅拌升温至130℃后保温反应4h,再自然冷却至50℃,得到含磷植物油多元醇;
2)将140g的2,6-甲苯二胺加入步骤1)的含磷植物油多元醇中,50℃保温反应5h,再升温至100℃抽真空2h,即得含磷氮植物油多元醇(羟值:368mgKOH/g)。
实施例3:
一种含磷氮植物油多元醇,其制备方法包括以下步骤:
1)将500g环氧值6.25%的环氧大豆油、200g的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物和0.6g的NaOH混合,搅拌升温至140℃后保温反应3h,再自然冷却至50℃,得到含磷植物油多元醇;
2)将150g的2,6-甲苯二胺加入步骤1)的含磷植物油多元醇中,50℃保温反应4h,再升温至100℃抽真空2h,即得含磷氮植物油多元醇(羟值:375mgKOH/g)。
实施例4:
一种含磷氮植物油多元醇,其制备方法包括以下步骤:
1)将500g环氧值6.20%的环氧大豆油、220g的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物和0.8g质量分数85%的浓磷酸混合,搅拌升温至140℃后保温反应4h,再自然冷却至60℃,得到含磷植物油多元醇;
2)将245g的苯胺加入步骤1)的含磷植物油多元醇中,60℃保温反应4h,再升温至100℃抽真空2h,即得含磷氮植物油多元醇(羟值:365mgKOH/g)。
实施例5:
一种含磷氮植物油多元醇,其制备方法包括以下步骤:
1)将500g环氧值6.28%的环氧大豆油、250g的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物和0.8g的对甲苯磺酸混合,搅拌升温至150℃后保温反应3.5h,再自然冷却至70℃,得到含磷植物油多元醇;
2)将335g的对甲基苯胺加入步骤1)的含磷植物油多元醇中,70℃保温反应3h,再升温至100℃抽真空2h,即得含磷氮植物油多元醇(羟值:381mgKOH/g)。
实施例6:
一种含磷氮植物油多元醇,其制备方法包括以下步骤:
1)将500g环氧值6.24%的环氧大豆油、300g的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物和1g的甲醇钾混合,搅拌升温至160℃后保温反应3h,再自然冷却至50℃,得到含磷植物油多元醇;
2)将98g质量分数25%的氨水加入步骤1)的含磷植物油多元醇中,50℃保温反应4h,再升温至100℃抽真空2h,即得含磷氮植物油多元醇(羟值:362mgKOH/g)。
实施例7:
一种含磷氮植物油多元醇,其制备方法包括以下步骤:
1)将500g环氧值6.26%的环氧大豆油、200g的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物和1g的甲醇钠混合,搅拌升温至170℃后保温反应2h,再自然冷却至40℃,得到含磷植物油多元醇;
2)将65g的乙二胺加入步骤1)的含磷植物油多元醇中,40℃保温反应6h,再升温至100℃抽真空2h,即得含磷氮植物油多元醇(羟值:380mgKOH/g)。
应用例1:
一种硬质聚氨酯泡沫塑料,其组成如下:
A组分:
聚醚多元醇4110(羟值:430mgKOH/g±30mgKOH/g):100g;水:2.1g;正戊烷:14g;胺类催化剂:2.5g;硅油:2g;
B组分:
多亚甲基多苯基多异氰酸酯(PM-200):100g。
应用例2:
一种硬质聚氨酯泡沫塑料,其组成如下:
A组分:
聚醚多元醇4110(羟值:430mgKOH/g±30mgKOH/g):90g;实施例3的含磷氮植物油多元醇:10g;水:2.1g;正戊烷:14g;胺类催化剂:2.5g;硅油:2g;
B组分:
多亚甲基多苯基多异氰酸酯(PM-200):100g。
应用例3:
一种硬质聚氨酯泡沫塑料,其组成如下:
A组分:
聚醚多元醇4110(羟值:430mgKOH/g±30mgKOH/g):80g;实施例3的含磷氮植物油多元醇:20g;水:2.1g;正戊烷:14g;胺类催化剂:2.5g;硅油:2g;
B组分:
多亚甲基多苯基多异氰酸酯(PM-200):100g。
应用例4:
一种硬质聚氨酯泡沫塑料,其组成如下:
A组分:
聚醚多元醇4110(羟值:430mgKOH/g±30mgKOH/g):70g;实施例3的含磷氮植物油多元醇:30g;水:2.1g;正戊烷:14g;胺类催化剂:2.5g;硅油:2g;
B组分:
多亚甲基多苯基多异氰酸酯(PM-200):100g。
应用例5:
一种硬质聚氨酯泡沫塑料,其组成如下:
A组分:
聚醚多元醇4110(羟值:430mgKOH/g±30mgKOH/g):60g;实施例3的含磷氮植物油多元醇:40g;水:2.1g;正戊烷:14g;胺类催化剂:2.5g;硅油:2g;
B组分:
多亚甲基多苯基多异氰酸酯(PM-200):100g。
应用例6:
一种硬质聚氨酯泡沫塑料,其组成如下:
A组分:
聚醚多元醇4110(羟值:430mgKOH/g±30mgKOH/g):50g;实施例3的含磷氮植物油多元醇:50g;水:2.1g;正戊烷:14g;胺类催化剂:2.5g;硅油:2g;
B组分:
多亚甲基多苯基多异氰酸酯(PM-200):100g。
性能测试:
将应用例1~6的硬质聚氨酯泡沫塑料制成硬质聚氨酯泡沫塑料样品1~6,具体制备过程为:室温下将A组分中的各原料高速搅拌60s使原料充分混匀,再称取100g混合好的A组分加入塑料杯中,再迅速加入B组分,继续高速搅拌5s~10s至塑料杯内的混合物发白并且冒出气泡,再快速倒入底面密封的模具中进行自然发泡,室温下冷却1h,脱去模具,再裁切成符合相应标准的样条后进行性能测试,测试结果如下表所示:
表1硬质聚氨酯泡沫塑料样品1~6的性能测试结果
注:
密度:参照“GB/T 6343-2009泡沫塑料及橡胶表观密度的测定”进行测试,样品尺寸为10mm×10mm×150mm;
10%压缩强度:参照“GB/T 8813-2020硬质泡沫塑料压缩性能的测定”进行测试,试验速度为5mm/min,样品尺寸为50mm×50mm×50mm;
拉伸强度:参照“GB 9641-1988硬质泡沫塑料拉伸性能试验方法”进行测试;
极限氧指数:参照“GB/T 2406.2-2009塑料用氧指数法测定燃烧行为第2部分:室温试验”进行测试,样品尺寸为100mm×10mm×10mm;
导热系数:参照“GB/T 10295-2008绝热材料稳态热阻及有关特性的测定热流计法”进行测试,样品尺寸为30mm×30mm×20mm;
垂直燃烧级别:参照“GB/T 2408-2008塑料燃烧性能的测定水平法和垂直法”进行测试,样品尺寸为125mm×13mm×10mm。
由表1可知:
1)随着含磷氮植物油多元醇的添加量增加,制得的硬质聚氨酯泡沫塑料样品的泡沫密度略有上升,原因在于:含磷氮植物油多元醇的结构中引入了磷、氮元素,比重相对较大;
2)含磷氮植物油多元醇对硬质聚氨酯泡沫塑料样品的压缩强度提高非常明显,而在较低密度下(36kg/m3左右)硬质聚氨酯泡沫塑料样品表现高的压缩强度(0.2MPa)是非常有使用价值的,原因在于:含磷氮植物油多元醇的结构中引入了DOPO,DOPO含有刚性较大的联苯环结构和菲环结构,而且多元醇能够参与聚氨酯的交联反应,对泡沫交联具有一定的贡献;
3)纯聚氨酯(硬质聚氨酯泡沫塑料样品1)的极限氧指数仅为18.2%,而随着含磷氮植物油多元醇的添加量增加,硬质聚氨酯泡沫塑料样品的极限氧指数逐步提高,当添加30g的含磷氮植物油多元醇时,氧指数达25.6%,同时,硬质聚氨酯泡沫塑料样品的导热系数没有明显的变化;
4)纯聚氨酯(硬质聚氨酯泡沫塑料样品1)没有通过垂直燃烧等级测试,而随着含磷氮植物油多元醇的添加量增加,硬质聚氨酯泡沫塑料样品的UL-94等级由V-1级提高到V-0级,硬质聚氨酯泡沫塑料样品4~6均能达到离火自熄的级别。
此外,采用同样的方法对实施例1~2和实施例4~7的含磷氮植物油多元醇进行性能测试,测试发现实施例1~2和实施例4~7的含磷氮植物油多元醇的各方面性能与实施例3的含磷氮植物油多元醇十分接近。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (8)
1.一种含磷氮植物油多元醇的制备方法,其特征在于,包括以下步骤:
1)将环氧大豆油、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物和酸性/碱性催化剂混合,进行反应,得到含磷植物油多元醇;
2)将含磷植物油多元醇和胺类化合物混合,进行反应,即得含磷氮植物油多元醇;
所述环氧大豆油、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物、胺类化合物的质量比为1:0.2~0.6:0.1~0.7;
步骤2)所述胺类化合物为氨水、乙二胺、苯胺、2,6-甲苯二胺、对甲基苯胺中的一种。
2.根据权利要求1所述的含磷氮植物油多元醇的制备方法,其特征在于:步骤1)所述环氧大豆油的环氧值≥6.2%。
3.根据权利要求1所述的含磷氮植物油多元醇的制备方法,其特征在于:步骤1)所述酸催化剂为盐酸、硫酸、磷酸、氟硼酸、对甲苯磺酸中的至少一种。
4.根据权利要求1所述的含磷氮植物油多元醇的制备方法,其特征在于:步骤1)所述碱催化剂为氢氧化钾、氢氧化钠、甲醇钠、乙醇钠、甲醇钾、乙醇钾中的至少一种。
5.根据权利要求1所述的含磷氮植物油多元醇的制备方法,其特征在于:步骤1)所述反应在120℃~170℃下进行,反应时间为2h~5h。
6.根据权利要求1所述的含磷氮植物油多元醇的制备方法,其特征在于:步骤2)所述反应在40℃~70℃下进行,反应时间为3h~6h。
7.一种含磷氮植物油多元醇,其特征在于,其由权利要求1~6中任意一项所述的方法制备得到。
8.权利要求7所述的含磷氮植物油多元醇在制备硬质聚氨酯泡沫塑料中的应用。
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