CN109651584B - 一种反应型含磷类阻燃剂及其制备方法和在聚氨酯泡沫中的应用 - Google Patents
一种反应型含磷类阻燃剂及其制备方法和在聚氨酯泡沫中的应用 Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 66
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 65
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 22
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 22
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- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 21
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- 239000004814 polyurethane Substances 0.000 claims abstract description 21
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- 239000000376 reactant Substances 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 125000004104 aryloxy group Chemical class 0.000 claims abstract description 5
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- 238000006243 chemical reaction Methods 0.000 claims description 31
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- 150000003077 polyols Chemical class 0.000 claims description 18
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- 238000000034 method Methods 0.000 claims description 7
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- VWBYXJRDIQCSLW-UHFFFAOYSA-N O=[P](c1ccccc1)c1ccccc1 Chemical compound O=[P](c1ccccc1)c1ccccc1 VWBYXJRDIQCSLW-UHFFFAOYSA-N 0.000 claims description 3
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- KGNCPCNAWUTBGB-UHFFFAOYSA-N [P].C1(=CC=CC=C1)OC1=CC=CC=C1 Chemical compound [P].C1(=CC=CC=C1)OC1=CC=CC=C1 KGNCPCNAWUTBGB-UHFFFAOYSA-N 0.000 claims 1
- 150000001879 copper Chemical class 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 abstract description 8
- 150000002367 halogens Chemical class 0.000 abstract description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 5
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- 230000000694 effects Effects 0.000 abstract description 4
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- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- 229920013708 Dow VORANOL™ CP 1421 Polyol Polymers 0.000 description 1
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- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
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Abstract
Description
技术领域
本发明属于聚氨酯领域,具体涉及阻燃环保型聚氨酯高回弹泡沫及其制备方法。
背景技术
聚氨酯高回弹泡沫是一种综合性能优良的垫材,广泛应用于家具如床和沙发,和各种交通工具的座椅、地垫及吸音减震垫块等。普通的未作阻燃处理的聚氨酯高回弹泡沫具有多孔结构,比表面积大且开孔率高,在空气中极易被引燃。同时,聚氨酯高回弹泡沫的使用环境多为密闭空间,特别是作为公共交通工具的客车、火车、飞机等,这就要求提高聚氨酯高回弹泡沫的阻燃性能。国家也提出了相应的技术标准,JT/T 1095-2016《营运客车内饰材料阻燃特性》已于2017年4月1日实施。标准要求营运客车内弹性软垫材料(坐垫、座椅靠背、头枕用弹性软垫)水平燃烧为A-0mm/min、垂直燃烧≤100mm/min、氧指数≥22%。
已有的提高聚氨酯高回弹泡沫阻燃性能的方法有,添加阻燃剂和使用阻燃聚醚多元醇。含卤素阻燃剂在燃烧时会生成大量卤化氢有毒气体,已被逐渐淘汰;非反应型磷酸酯类阻燃剂在聚氨酯泡沫中易发生迁移,降低其阻燃性能,同时使聚氨酯泡沫的VOC和气味严重变差;阻燃聚醚多元醇如接枝三聚氰胺的聚醚多元醇会导致聚氨酯泡沫甲醛含量严重超标。
发明内容
本发明要解决的第一个技术问题是提供一种反应型含磷类阻燃剂,该阻燃剂不含卤素,改善聚氨酯泡沫阻燃性能的同时,不会对泡沫的环保性能(包括VOC和气味)产生不良影响。
本发明要解决的第二个技术问题是提供一种该反应型含磷类阻燃剂的制备方法。
本发明要解决的第三个技术问题是提供一种该反应型含磷类阻燃剂在聚氨酯泡沫中的应用。
为解决第一个技术问题,本发明提供一种反应型含磷类阻燃剂,结构式如下:
其中,R1和R2相互独立地为C1~C10烷氧基、苯基取代烷氧基、苯基、苯氧基、烷基取代芳氧基、或R1和R2共同形成环,所述环为5~7元环。优选R1和R2相同,为乙氧基或异丙氧基;R3和R4相互独立地为C1~C8羟烷基。优选R3和R4相同,为羟乙基或羟异丙基。
所述反应型含磷类阻燃剂分子结构含有羟基个数≥2,由三种反应物制备而成,第一反应物为H-亚磷酸酯或二苯基氧化磷、第二反应物为醇胺、第三反应物为原甲酸三甲酯、原甲酸三乙酯、原甲酸三丁酯,优选原甲酸三乙酯。
第一反应物H-亚磷酸酯或二苯基氧化磷具有以下结构通式:
其中,R1和R2相互独立地为C1-C10烷氧基、苯基取代烷氧基、苯基、苯氧基、烷基取代芳氧基、或R1和R2共同形成环,所述环为5-7元环。优选R1和R2相同,为乙氧基或异丙氧基。
第二反应物醇胺具有以下结构通式:
其中,R3和R4相互独立地为C1-C8羟烷基。优选R3和R4相同,为羟乙基或羟异丙基。
反应方程式为:
其中,R5为甲氧基、乙氧基、丁氧基,优选乙氧基。
为解决第二个技术问题,本发明提供一种制备反应型含磷类阻燃剂的方法,包括以下步骤:
(1)将第一反应物H-亚磷酸酯或二苯基氧化磷、第二反应物醇胺和第三反应物加入微波反应瓶中,然后加入催化剂一价铜盐。所述催化剂一价铜盐为CuI、CuBr、CuCl,优选CuI。将反应瓶置于微波反应器中进行反应。反应条件为微波条件下温度110℃-130℃,反应时间0.5-3h。
(2)反应结束,旋蒸法除去副产物小分子醇。
(3)水洗、干燥后得所述阻燃剂。
本发明提供的反应型含磷类阻燃剂分子结构不含卤素,含有羟基个数≥2,含有膦酸酯基团,添加于组合聚醚组分中,能有效改善聚氨酯高回弹泡沫的阻燃性,同时不会对其环保性能(包括VOC和气味)产生不良影响。
为解决第三个技术问题,本发明提供一种阻燃环保型聚氨酯高回弹泡沫组合物,包括组合聚醚组分(A组分)和异氰酸酯组分(B组分),其特征是组合聚醚组分(A组分)中添加有反应型含磷类阻燃剂。
本发明进一步提供一种阻燃环保型聚氨酯高回弹泡沫组合物具体配方,原料由A、B两组分组成,按质量份计包括:
A组分(组合聚醚组分):聚醚多元醇50~100份;聚合物多元醇0~50份;催化剂0.2~5份;发泡剂1~8份;泡沫稳定剂0.2~3;交联剂0.2~6份;开孔剂0~10;反应型含磷类阻燃剂0.1~20份。
B组分(异氰酸酯组分):多异氰酸酯。包括TDI、MDI、聚合MDI或改性MDI等及其混合物。
A∶B质量比为100∶30~100∶80。
优选的聚醚多元醇官能度为3,相对分子质量为4500~8000,端羟基中伯羟基含量大于70%。
所述聚合物多元醇优选聚醚多元醇与苯乙烯丙烯腈的接枝共聚物。
所述催化剂优选叔胺类;所述发泡剂优选去离子水;所述泡沫稳定剂优选聚硅氧烷聚醚共聚物;所述交联剂优选醇胺类化合物;所述开孔剂优选EO含量≥50%的聚醚多元醇。
本发明配方合理,制备聚氨酯高回弹泡沫的原料A、B组分均有良好的储存稳定性。本发明所制备的聚氨酯高回弹泡沫具有良好的阻燃性,与现有技术普遍使用的阻燃剂制备的高回弹泡沫相比,具有更好的环保性能(包括气味和VOC)。
具体实施方式
下面结合实施例进一步说明本发明的作用和效果,但并不局限于以下实施例。
反应型含磷类阻燃剂的制备:
实施例1
将138g H-亚磷酸二乙酯、55g二乙醇胺和74g原甲酸三乙酯加入微波反应瓶中,然后加入4.8g CuI。将反应瓶置于微波反应器中进行反应。反应条件为微波条件下温度110℃-130℃,反应时间1.5h。
反应结束后,旋蒸法除去副产物乙醇。水洗、干燥后得阻燃剂FR-01,所述阻燃剂分子结构不含卤素,含有羟基个数为2,含有2个膦酸酯基团。
实施例2
将202g结构式为的物质、55g二乙醇胺和74g原甲酸三乙酯加入微波反应瓶中,然后加入4.8g CuI。将反应瓶置于微波反应器中进行反应。反应条件为微波条件下温度110℃-130℃,反应时间1.5h。
反应结束后,旋蒸除去副产物乙醇。水洗、干燥后得阻燃剂FR-02,所述阻燃剂分子结构不含卤素,含有羟基个数为2,含有2个膦酸酯基团。
实施例3
将186g结构式为的物质、55g二乙醇胺和74g原甲酸三乙酯加入微波反应瓶中,然后加入4.8g CuI。将反应瓶置于微波反应器中进行反应。反应条件为微波条件下温度110℃-130℃,反应时间1.5h。
反应结束后,旋蒸除去副产物乙醇。水洗、干燥后得阻燃剂FR-03,所述阻燃剂分子结构不含卤素,含有羟基个数为2,含有2个膦酸酯基团。
实施例4
将136g结构式为的物质、55g二乙醇胺和74g原甲酸三乙酯加入微波反应瓶中,然后加入4.8g CuI。将反应瓶置于微波反应器中进行反应。反应条件为微波条件下温度110℃-130℃,反应时间1.5h。
反应结束后,旋蒸除去副产物乙醇。水洗、干燥后得阻燃剂FR-04,所述阻燃剂分子结构不含卤素,含有羟基个数为2,含有2个膦酸酯基团。
阻燃环保型聚氨酯高回弹泡沫的制备:
(1)将聚醚多元醇、催化剂、发泡剂、泡沫稳定剂、交联剂、开孔剂、阻燃剂按表1所示质量份加入容器中,充分搅拌混合分散均匀,得A组分。
表1 A组分中各原料质量份数
其中聚醚多元醇为可利亚多元醇(南京)有限公司生产的KPX KE-810,催化剂为迈图高新材料集团的Niax EF-700,发泡剂为去离子水,泡沫稳定剂为美国空气产品公司的DC2525,交联剂为扬子石化-巴斯夫有限责任公司的二乙醇胺,开孔剂为陶氏化学品公司的Voranol CP1421。
B组分为烟台万华聚氨酯股份有限公司的Wannate 8018。
(2)将A组分和B组分按比例快速充分混合均匀并均匀注入模温为65℃模具中,模具内腔尺寸380mm*380mm*100mm。所述比例为使A组分中活性氢的物质的量n(H)与B组分中NCO的物质的量n(NCO)相同。熟化6min即得聚氨酯高回弹泡沫。自然熟化72h后对所制备聚氨酯高回弹泡沫进行性能测试,测试结果见表2。
表2 聚氨酯高回弹泡沫的性能
氧指数按GB/T2406.2-2009测试,气味等级按VDA270测试,TVOC按VDA277测试。
由表2可知:本发明实施例B、C、D、E与无阻燃剂的对比例A相比,阻燃性能明显改善,达到JT/T 1095-2016标准要求,同时气味和VOC没有变差。而使用非反应型阻燃剂的对比例F与无阻燃剂的对比例A相比,阻燃性能虽有提高,但气味和VOC明显变差。
以上实施例仅用于说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (10)
2.根据权利要求1所述的反应型含磷类阻燃剂,R1和R2相同,为乙氧基或异丙氧基;R3和R4相同,为羟乙基或羟异丙基。
3.根据权利要求1所述的反应型含磷类阻燃剂,所述反应型含磷类阻燃剂分子结构含有羟基个数≥2,由三种反应物制备而成,第一反应物为H-亚磷酸酯或二苯基氧化磷、第二反应物为醇胺、第三反应物为原甲酸三甲酯、原甲酸三乙酯、原甲酸三丁酯中的一种或其混合物。
5.一种制备权利要求3或4所述的反应型含磷类阻燃剂的方法,包括以下步骤:
(1)将第一反应物H-亚磷酸酯或二苯基氧化磷、第二反应物醇胺和第三反应物加入微波反应瓶中,然后加入催化剂一价铜盐;将反应瓶置于微波反应器中进行反应,反应条件为微波条件下温度110℃~130℃,反应时间0.5~3h;
(2)反应结束,旋蒸法除去副产物小分子醇;
(3)水洗、干燥后得所述阻燃剂。
6.根据权利要求5所述的制备反应型含磷类阻燃剂的方法,所述催化剂一价铜盐为CuI、CuBr、CuCl中的一种或其混合物。
7.一种权利要求1~4之一所述的反应型含磷类阻燃剂在阻燃环保型聚氨酯高回弹泡沫组合物中的应用。
8.根据权利要求7所述的应用,其特征是所述的阻燃环保型聚氨酯高回弹泡沫组合物的原料由A、B两组分组成,按质量份计包括:
A组分(组合聚醚组分):聚醚多元醇50~100份;聚合物多元醇0~50份;催化剂0.2~5份;发泡剂1~8份;泡沫稳定剂0.2~3;交联剂0.2~6份;开孔剂0~10;反应型含磷类阻燃剂0.1~20份;
B组分(异氰酸酯组分):多异氰酸酯;
A∶B质量比为100∶30~100∶80。
9.根据权利要求8所述的应用,其特征是,多异氰酸酯是指TDI、MDI、聚合MDI或改性MDI及其混合物。
10.根据权利要求8所述的应用,其特征是,聚醚多元醇官能度为3,相对分子质量为4500~8000,端羟基中伯羟基含量大于70%;聚合物多元醇为聚醚多元醇与苯乙烯、丙烯腈的接枝共聚物;所述催化剂为叔胺类;所述发泡剂为去离子水;所述泡沫稳定剂为聚硅氧烷聚醚共聚物;所述交联剂为醇胺类化合物;所述开孔剂为EO含量≥50%的聚醚多元醇。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4100067A (en) * | 1976-04-09 | 1978-07-11 | Benckiser-Knapsack Gmbh. | Method for sequestering metal ions |
DE3133308A1 (de) * | 1981-08-22 | 1983-03-17 | Chemische Fabrik Budenheim Rudolf A. Oetker, 6501 Budenheim | Verfahren zur herstellung von n-alkyl-aminomethandiphosphonsaeuren |
US4609616A (en) * | 1984-03-15 | 1986-09-02 | Agfa Gevaert Aktiengesellschaft | Bath composition for bleaching photographic recording materials and bleaching process |
CN1583768A (zh) * | 2004-06-04 | 2005-02-23 | 河南大学 | N,n-双(2-羟乙基)氨甲基膦酸二乙酯制备方法 |
CN102391403A (zh) * | 2011-09-06 | 2012-03-28 | 中国科学技术大学苏州研究院 | 一种含磷氮阻燃聚合物及其制备方法 |
CN102504751A (zh) * | 2011-11-22 | 2012-06-20 | 东莞市普赛达密封粘胶有限公司 | 一种阻燃聚氨酯密封胶及其制备方法 |
CN103435646A (zh) * | 2013-08-21 | 2013-12-11 | 合肥安聚达新材料科技有限公司 | 一种亚磷酸酯类含磷、氮的可紫外光固化阻燃剂及其制备方法 |
CN105131226A (zh) * | 2015-09-29 | 2015-12-09 | 上海应用技术学院 | 一种难燃b1级聚氨酯硬质泡沫及其制备方法 |
-
2018
- 2018-11-20 CN CN201811462133.5A patent/CN109651584B/zh active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4100067A (en) * | 1976-04-09 | 1978-07-11 | Benckiser-Knapsack Gmbh. | Method for sequestering metal ions |
DE3133308A1 (de) * | 1981-08-22 | 1983-03-17 | Chemische Fabrik Budenheim Rudolf A. Oetker, 6501 Budenheim | Verfahren zur herstellung von n-alkyl-aminomethandiphosphonsaeuren |
US4609616A (en) * | 1984-03-15 | 1986-09-02 | Agfa Gevaert Aktiengesellschaft | Bath composition for bleaching photographic recording materials and bleaching process |
CN1583768A (zh) * | 2004-06-04 | 2005-02-23 | 河南大学 | N,n-双(2-羟乙基)氨甲基膦酸二乙酯制备方法 |
CN102391403A (zh) * | 2011-09-06 | 2012-03-28 | 中国科学技术大学苏州研究院 | 一种含磷氮阻燃聚合物及其制备方法 |
CN102504751A (zh) * | 2011-11-22 | 2012-06-20 | 东莞市普赛达密封粘胶有限公司 | 一种阻燃聚氨酯密封胶及其制备方法 |
CN103435646A (zh) * | 2013-08-21 | 2013-12-11 | 合肥安聚达新材料科技有限公司 | 一种亚磷酸酯类含磷、氮的可紫外光固化阻燃剂及其制备方法 |
CN105131226A (zh) * | 2015-09-29 | 2015-12-09 | 上海应用技术学院 | 一种难燃b1级聚氨酯硬质泡沫及其制备方法 |
Non-Patent Citations (3)
Title |
---|
Formation of compounds with P-C-N moiety by microwave-assisted condensations;Ádám Tajti等;《21st International Conference on Phosphorus Chemistry (ICPC)》;20160729;第191卷(第11-12期);第1541-1542页 * |
Nano ZnO catalyzed green synthesis and cytotoxic assay of pyridinyl and pyrimidinyl bisphosphonates;Gundluru Mohan等;《Monatsh Chem》;20170713;第148卷;第1843–1851页 * |
有机磷系阻燃剂的合成及其在尼龙中的应用;杨敏芬;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20160715(第07期);第B016-85页 * |
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