CN115073700B - 一种本质阻燃水性聚氨酯树脂及其制备方法 - Google Patents
一种本质阻燃水性聚氨酯树脂及其制备方法 Download PDFInfo
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- 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 67
- 239000003063 flame retardant Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 17
- 150000003077 polyols Chemical class 0.000 claims abstract description 49
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- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
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- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000004945 emulsification Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- MRVZORUPSXTRHD-UHFFFAOYSA-N bis(hydroxymethyl)phosphorylmethanol Chemical compound OCP(=O)(CO)CO MRVZORUPSXTRHD-UHFFFAOYSA-N 0.000 claims abstract description 12
- JSPBAVGTJNAVBJ-UHFFFAOYSA-N ethyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCC)OC1=CC=CC=C1 JSPBAVGTJNAVBJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 12
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000006386 neutralization reaction Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
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- 238000006116 polymerization reaction Methods 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
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- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 7
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical group CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
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- VSZRSZSSCAXDQV-UHFFFAOYSA-N 2,3-bis(hydroxymethyl)butanedioic acid Chemical compound OCC(C(O)=O)C(CO)C(O)=O VSZRSZSSCAXDQV-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
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- 125000003827 glycol group Chemical group 0.000 claims 1
- NKZQKINFDLZVRY-UHFFFAOYSA-N n-butylbutan-1-amine;toluene Chemical compound CC1=CC=CC=C1.CCCCNCCCC NKZQKINFDLZVRY-UHFFFAOYSA-N 0.000 abstract description 10
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- 238000001816 cooling Methods 0.000 description 10
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- 229910052757 nitrogen Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
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- 238000011056 performance test Methods 0.000 description 2
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Abstract
本发明涉及水性聚氨酯材料技术领域,尤其是涉及一种本质阻燃水性聚氨酯树脂及其制备方法。本发明首先将二苯基磷酸乙酯和三羟甲基氧化磷混匀,反应后经后处理得到有机磷多元醇阻燃剂;将低聚物多元醇与亲水扩链剂混匀后后处理,然后将多异氰酸酯与催化剂加入其中,保温反应至‑NCO含量达到用二正丁胺‑甲苯溶液滴定所规定的理论值,得到聚氨酯预聚体,并对其进行中和;最后将中和后的聚氨酯预聚体进行一次乳化;然后将有机磷多元醇阻燃剂与小分子多元醇扩链剂加入体系,二次乳化后后处理,得到本质阻燃水性聚氨酯乳液。
Description
技术领域
本发明涉及水性聚氨酯材料技术领域,尤其是涉及一种本质阻燃水性聚氨酯树脂及其制备方法。
背景技术
水性聚氨酯(WPU)是指以水为分散介质的聚氨酯,具有良好的综合性能,又具有无污染、安全可靠、相容性好、易于改性以及成本低廉等优点。现已广泛应用于涂料、胶粘剂、织物涂层整理剂、皮革涂饰剂、纸张表面处理剂和纤维表面处理剂等领域。然而,作为一种高分子材料,绝大多数水性聚氨酯是可以燃烧的,其极限氧指数仅有18%左右,且燃烧速度快,放出热量高,燃烧时还伴随着可燃性熔滴,使火焰迅速传播。所以,为了减少火灾的危险并能更好的保护人们的生命财产安全,赋予水性聚氨酯阻燃性能已成为水性聚氨酯功能化的重要方向之一。
添加型阻燃水性聚氨酯是通过将阻燃剂与水性聚氨酯材料进行物理共混来实现对其阻燃的目的。但目前市场上进行阻燃整理的添加型阻燃水性聚氨酯,存在着阻燃剂添加量大、易迁移、影响产品外观、对力学性能产生不良影响等缺点。并且卤系阻燃剂占有机阻燃剂的80%左右,其在燃烧时生成较多的烟、腐蚀性气体和有毒气体,会对环境和人体造成危害,达不到无卤的环保要求。
发明内容
为了解决上述问题,本发明目的在于提供一种本质阻燃水性聚氨酯树脂和制备方法。本发明首先将二苯基磷酸乙酯和三羟甲基氧化磷混匀,反应后经后处理得到有机磷多元醇阻燃剂;将低聚物多元醇与亲水扩链剂混匀后后处理,然后将多异氰酸酯与催化剂加入其中,保温反应至-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值,得到聚氨酯预聚体,并对其进行中和;最后将中和后的聚氨酯预聚体进行一次乳化;然后将有机磷多元醇阻燃剂与小分子多元醇扩链剂加入体系,二次乳化后后处理,得到本质阻燃水性聚氨酯乳液。本发明方法简单,自制的有机磷多元醇中含有苯环且磷含量较高,用其作为后扩链剂进行反应合成出水性聚氨酯。直接将阻燃结构和元素引入聚氨酯分子中,使得阻燃剂用量大为减少,阻燃效率更高、更持久。负面影响也大幅降低,不存在阻燃剂易挥发、溶出、迁移和渗出问题。并且还具有不含卤素,环保、低烟的优点。
本发明的目的可以通过以下技术方案来实现:
本发明的第一个目的是提供一种本质阻燃水性聚氨酯树脂的制备方法,包括以下步骤:
(1)有机磷多元醇阻燃剂的制备:将二苯基磷酸乙酯和三羟甲基氧化磷混匀,经酯交换反应与后处理得到有机磷多元醇阻燃剂;
(2)二元醇扩链剂的制备:将低聚物多元醇与亲水扩链剂混匀后后处理,得到二元醇扩链剂;
(3)预聚体的制备:将多异氰酸酯加入步骤(2)得到的二元醇扩链剂中混匀,在催化剂催化下,聚合反应至-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值,期间根据粘度变化加入丙酮降低粘度,得到聚氨酯预聚体;
(4)预聚体的中和:在步骤(3)得到的聚氨酯预聚体中加入中和剂对其进行中和;
(5)乳化及后扩链:在中和后的聚氨酯预聚体中加入去离子水,进行一次乳化;然后将步骤(1)制备得到的有机磷多元醇阻燃剂与小分子扩链剂加入体系,二次乳化后后处理,得到本质阻燃水性聚氨酯乳液;
其中,有机磷多元醇阻燃剂的化学结构式如下式所示:
在本发明的一个实施方式中,步骤(1)中,二苯基磷酸乙酯和三羟甲基氧化磷的摩尔比为1:1-1:1.2;
反应过程中,反应时间为3-6h;反应温度为100-120℃。
在本发明的一个实施方式中,步骤(1)中,所述后处理为冷凝分离除乙醇。
在本发明的一个实施方式中,步骤(1)中,反应中加入催化剂进行催化;
所述催化剂选自NaOH、KOH、NaHCO3中的一种。
在本发明的一个实施方式中,步骤(2)中,低聚物多元醇与亲水扩链剂的摩尔比为1:1.6-1:2.2;
所述低聚物多元醇选自聚乙二醇、聚丙二醇、聚四氢呋喃醚二醇、聚碳酸酯多元醇或聚己内酯多元醇中的一种或几种;
所述亲水扩链剂选自二羟甲基丙酸、2,3-二羟甲基丁二酸、二羟基半酯中的一种或几种。
在本发明的一个实施方式中,步骤(2)所述后处理为真空除水。
在本发明的一个实施方式中,步骤(3)中,所述多异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、1,6-己基二异氰酸酯、六亚甲基二异氰酸酯、二环己基二异氰酸酯、四甲基环己基甲烷二异氰酸酯或二苯基甲烷二异氰酸酯中的一种或几种。
在本发明的一个实施方式中,步骤(3)中,反应中加入催化剂进行催化;
所述催化剂为二月桂酸二丁基锡;
催化剂的添加量为多异氰酸酯的质量的0.4%-0.6%;
在本发明的一个实施方式中,步骤(3)中,聚合反应过程中,反应温度为60-90℃,反应时间为2-3h。
在本发明的一个实施方式中,步骤(3)中,二正丁胺-甲苯溶液滴定所规定的理论值为聚合反应后剩余-NCO基团质量占加料总质量的百分数。
在本发明的一个实施方式中,步骤(3)中,反应在干燥的氮气保护下进行。
在本发明的一个实施方式中,步骤(4)中,中和剂的添加量为聚氨酯预聚体的质量的2.98-3.8%;
所述中和剂选自三乙胺、氨水、氢氧化钠中的一种或几种;
中和过程中,中和温度为40-50℃;中和时间为30min。
在本发明的一个实施方式中,步骤(5)中,去离子水的加入量为聚氨酯预聚体的质量的230%-235%。
在本发明的一个实施方式中,步骤(5)中,所述小分子扩链剂为异佛尔酮二胺。
在本发明的一个实施方式中,步骤(5)中,小分子扩链剂与有机磷多元醇阻燃剂的摩尔比为1:0.43-1:1.5。
在本发明的一个实施方式中,步骤(5)中,一次乳化过程中,乳化温度为30℃,乳化时间为30min。
在本发明的一个实施方式中,步骤(5)中,二次乳化过程中,乳化温度为30℃,乳化时间为1-1.5h。
在本发明的一个实施方式中,所述后处理为减压蒸馏除溶剂丙酮。
本发明的第二个目的是提供一种通过上述方法制备得到的本质阻燃水性聚氨酯树脂。
与现有技术相比,本发明具有以下有益效果:
(1)本发明中的本质阻燃水性聚氨酯属于反应型水性聚氨酯,阻燃效果持久,不含卤素,安全环保,低烟,无毒。
(2)本发明的制备方法简单易操作。
具体实施方式
本发明提供一种本质阻燃水性聚氨酯树脂的制备方法,包括以下步骤:
(1)有机磷多元醇阻燃剂的制备:将二苯基磷酸乙酯和三羟甲基氧化磷混匀,经酯交换反应与后处理得到有机磷多元醇阻燃剂;
(2)二元醇扩链剂的制备:将低聚物多元醇与亲水扩链剂混匀后后处理,得到二元醇扩链剂;
(3)预聚体的制备:将多异氰酸酯加入步骤(2)得到的二元醇扩链剂中混匀,在催化剂催化下,聚合反应至-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值,期间根据粘度变化加入丙酮降低粘度,得到聚氨酯预聚体;
(4)预聚体的中和:在步骤(3)得到的聚氨酯预聚体中加入中和剂对其进行中和;
(5)乳化及后扩链:在中和后的聚氨酯预聚体中加入去离子水,进行一次乳化;然后将步骤(1)制备得到的有机磷多元醇阻燃剂与小分子扩链剂加入体系,二次乳化后后处理,得到本质阻燃水性聚氨酯乳液;
其中,有机磷多元醇阻燃剂的化学结构式如下式所示:
在本发明的一个实施方式中,步骤(1)中,二苯基磷酸乙酯和三羟甲基氧化磷的摩尔比为1:1-1:1.2;
反应过程中,反应时间为3-6h;反应温度为100-120℃。
在本发明的一个实施方式中,步骤(1)中,所述后处理为冷凝分离除乙醇。
在本发明的一个实施方式中,步骤(1)中,反应中加入催化剂进行催化;
所述催化剂选自NaOH、KOH、NaHCO3中的一种。
在本发明的一个实施方式中,步骤(2)中,低聚物多元醇与亲水扩链剂的摩尔比为1:1.6-1:2.2;
所述低聚物多元醇选自聚乙二醇、聚丙二醇、聚四氢呋喃醚二醇、聚碳酸酯多元醇或聚己内酯多元醇中的一种或几种;
所述亲水扩链剂选自二羟甲基丙酸、2,3-二羟甲基丁二酸、二羟基半酯中的一种或几种。
在本发明的一个实施方式中,步骤(2)所述后处理为真空除水。
在本发明的一个实施方式中,步骤(3)中,所述多异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、1,6-己基二异氰酸酯、六亚甲基二异氰酸酯、二环己基二异氰酸酯、四甲基环己基甲烷二异氰酸酯或二苯基甲烷二异氰酸酯中的一种或几种。
在本发明的一个实施方式中,步骤(3)中,反应中加入催化剂进行催化;
所述催化剂为二月桂酸二丁基锡;
催化剂的添加量为多异氰酸酯的质量的0.4%-0.6%;
在本发明的一个实施方式中,步骤(3)中,聚合反应过程中,反应温度为60-90℃,反应时间为2-3h。
在本发明的一个实施方式中,步骤(3)中,二正丁胺-甲苯溶液滴定所规定的理论值为聚合反应后剩余-NCO基团质量占加料总质量的百分数。
在本发明的一个实施方式中,步骤(3)中,反应在干燥的氮气保护下进行。
在本发明的一个实施方式中,步骤(4)中,中和剂的添加量为聚氨酯预聚体的质量的2.98-3.8%;
所述中和剂选自三乙胺、氨水、氢氧化钠中的一种或几种;
中和过程中,中和温度为40-50℃;中和时间为30min。
在本发明的一个实施方式中,步骤(5)中,去离子水的加入量为聚氨酯预聚体的质量的230%-235%。
在本发明的一个实施方式中,步骤(5)中,所述小分子扩链剂为异佛尔酮二胺。
在本发明的一个实施方式中,步骤(5)中,小分子扩链剂与有机磷多元醇阻燃剂的摩尔比为1:0.43-1:1.5。
在本发明的一个实施方式中,步骤(5)中,一次乳化过程中,乳化温度为30℃,乳化时间为30min。
在本发明的一个实施方式中,步骤(5)中,二次乳化过程中,乳化温度为30℃,乳化时间为1-1.5h。
在本发明的一个实施方式中,所述后处理为减压蒸馏除溶剂丙酮。
本发明提供一种通过上述方法制备得到的本质阻燃水性聚氨酯树脂。
下面结合具体实施例对本发明进行详细说明。
下述实施例中,若无特殊说明,所用试剂均为市售试剂;所用检测手段及方法均为本领域常规检测手段及方法。
实施例1
(1)称取10g二苯基磷酸乙酯和6.83g三羟甲基氧化磷于三口烧瓶中,并加入催化剂NaOH。升温至110℃,搅拌,冷凝分离出乙醇,反应5h。得自制有机磷多元醇阻燃剂,备用。
(2)称取3.6g聚乙二醇-1000、14.4g聚丙二醇-1000、1.08g二羟甲基丙酸于四口烧瓶中,在80r/min的搅拌转速下,缓慢升温至120℃,抽真空,保证真空度在-0.09Mpa以下,除水2h,得到二元醇扩链剂;
(3)称取8.11g异佛尔酮二异氰酸酯及0.04g二月桂酸二丁基锡加入步骤(2)制备得到的二元醇扩链剂中,在120r/min的转速下,在氮气保护下,70℃反应,期间视粘度增大情况加入8g丙酮降低粘度反应2.5h,测得-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值2.5%-3.1%时降温,得到聚氨酯预聚体。
(4)降温至40℃,称取0.81g三乙胺加入其中,中和30min。
(5)降温至30℃,在2000r/min的转速下,向上述预聚体中加入67.6g去离子水,乳化30min。将0.52g的异佛尔酮二胺和0.44g的自制有机磷多元醇加入反应体系,在乳化的同时进行后扩链1.5h。减压蒸馏出丙酮,得本质阻燃水性聚氨酯乳液。
实施例2
(1)称取10g二苯基磷酸乙酯和6.26g三羟甲基氧化磷于三口烧瓶中,并加入催化剂NaOH。升温至110℃,搅拌,冷凝分离出乙醇,反应5h。得自制有机磷多元醇阻燃剂,备用。
(2)称取3.4g聚乙二醇-1000、13.6g聚四氢呋喃醚二醇、1.21g二羟甲基丙酸于四口烧瓶中,在80r/min的搅拌转速下,缓慢升温至120℃,抽真空,保证真空度在-0.09Mpa以下,除水2h,得到二元醇扩链剂;
(3)称取8.69g异佛尔酮二异氰酸酯及0.04g二月桂酸二丁基锡加入步骤(2)制备得到的二元醇扩链剂中,在120r/min的转速下,在氮气保护下,70℃反应,期间视粘度增大情况加入6g丙酮降低粘度反应2.5h,测得-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值3.3%-4%时降温,得到聚氨酯预聚体。
(4)降温至40℃,称取0.91g三乙胺加入其中,中和30min。
(5)降温至30℃,在2000r/min的转速下,向上述预聚体中加入68.5g去离子水,乳化30min。将0.67g的异佛尔酮二胺和0.91g的自制有机磷多元醇加入反应体系,在乳化的同时进行后扩链1.5h。减压蒸馏出丙酮,得本质阻燃水性聚氨酯乳液。
实施例3
(1)称取10g二苯基磷酸乙酯和5.69g三羟甲基氧化磷于三口烧瓶中,并加入催化剂NaOH。升温至110℃,搅拌,冷凝分离出乙醇,反应5h。得自制有机磷多元醇阻燃剂,备用。
(2)称取10g聚四氢呋喃醚二醇-1000、6g聚己内酯二醇-1000、1.35g二羟甲基丙酸于四口烧瓶中,在76r/min的搅拌转速下,缓慢升温至120℃,抽真空,保证真空度在-0.09Mpa以下,除水2h,得到二元醇扩链剂;
(3)称取9.27g异佛尔酮二异氰酸酯及0.04g二月桂酸二丁基锡加入步骤(2)制备得到的二元醇扩链剂中,在120r/min的转速下,在氮气保护下,70℃反应,期间视粘度增大情况加入5g丙酮降低粘度反应2.5h,测得-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值4.1-4.9%时降温,得到聚氨酯预聚体。
(4)降温至40℃,称取1.02g三乙胺加入其中,中和30min。
(5)降温至30℃,在2000r/min的转速下,向上述预聚体中加入69.7g去离子水,乳化30min。将0.74g的异佛尔酮二胺和1.48g的自制有机磷多元醇加入反应体系,后扩链1.5h。减压蒸馏出丙酮,得本质阻燃水性聚氨酯乳液。
实施例4
(1)称取10g二苯基磷酸乙酯和5.69g三羟甲基氧化磷于三口烧瓶中,并加入催化剂NaOH。升温至110℃,搅拌,冷凝分离出乙醇,反应5h。得自制有机磷多元醇阻燃剂,备用。
(2)称取10g聚四氢呋喃醚二醇-1000、6g聚己内酯二醇-1000、1.35g二羟甲基丙酸于四口烧瓶中,在76r/min的搅拌转速下,缓慢升温至120℃,抽真空,保证真空度在-0.09Mpa以下,除水2h,得到二元醇扩链剂;
(3)称取9.85异佛尔酮二异氰酸酯及0.04g二月桂酸二丁基锡加入步骤(2)制备得到的二元醇扩链剂中,在120r/min的转速下,在氮气保护下,70℃反应,期间视粘度增大情况加入4g丙酮降低粘度反应2.5h,测得-NCO含量达到用二正丁胺-甲苯溶液滴定所规定的理论值4.9%-5.6%时降温,得到聚氨酯预聚体。
(4)降温至40℃,称取1.02g三乙胺加入其中,中和30min。
(5)降温至30℃,在2000r/min的转速下,向上述预聚体中加入72.7g去离子水,乳化30min。将0.74g的异佛尔酮二胺和2.21g的自制有机磷多元醇加入反应体系,后扩链1.5h。减压蒸馏出丙酮,得本质阻燃水性聚氨酯乳液。
力学和阻燃性能测试:将上述实施例中样品制备成聚氨酯膜,按GB/T1040-92标准测试胶膜的拉伸强度和断裂伸长率,按ASTM 02863标准测试极限氧指数。实验结果如下表所示:
表1本质阻燃水性聚氨酯性能测试
注:单体占比指的是自制有机磷多元醇占乳液固体分的比值
从表1中可以看出,随着单体占比的增加,水性聚氨酯胶膜的力学性能和阻燃性能逐渐提高。并且极限氧指数达到30%左右,这表明水性聚氨酯已具有优越的阻燃效果。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (8)
1.一种本质阻燃水性聚氨酯树脂的制备方法,其特征在于,包括以下步骤:
(1)有机磷多元醇阻燃剂的制备:将二苯基磷酸乙酯和三羟甲基氧化磷混匀,经酯交换反应与后处理得到有机磷多元醇阻燃剂;
(2)二元醇扩链剂的制备:将低聚物多元醇与亲水扩链剂混匀后后处理,得到二元醇扩链剂;
(3)预聚体的制备:将多异氰酸酯加入步骤(2)得到的二元醇扩链剂中混匀,聚合反应得到聚氨酯预聚体;
(4)预聚体的中和:在步骤(3)得到的聚氨酯预聚体中加入中和剂对其进行中和;
(5)乳化及后扩链:在中和后的聚氨酯预聚体中加入去离子水,进行一次乳化;然后将步骤(1)制备得到的有机磷多元醇阻燃剂与小分子扩链剂加入体系,二次乳化后后处理,得到本质阻燃水性聚氨酯乳液;
其中,有机磷多元醇阻燃剂的化学结构式如下式所示:
步骤(1)中,二苯基磷酸乙酯和三羟甲基氧化磷的摩尔比为1:1-1:1.2;
酯交换反应过程中,反应时间为3-6h;反应温度为100-120℃;
步骤(2)中,所述低聚物多元醇选自聚乙二醇、聚丙二醇、聚四氢呋喃醚二醇、聚碳酸酯多元醇或聚己内酯多元醇中的一种或几种;
所述亲水扩链剂选自二羟甲基丙酸、2,3-二羟甲基丁二酸、二羟基半酯中的一种或几种;
步骤(5)中,所述小分子扩链剂为异佛尔酮二胺。
2.根据权利要求1所述的一种本质阻燃水性聚氨酯树脂的制备方法,其特征在于,步骤(2)中,低聚物多元醇与亲水扩链剂的摩尔比为1:1.6-1:2.2。
3.根据权利要求1所述的一种本质阻燃水性聚氨酯树脂的制备方法,其特征在于,步骤(3)中,二元醇扩链剂与多异氰酸酯的摩尔比为1:1.4-1:1.7;
所述多异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、1,6-己基二异氰酸酯、六亚甲基二异氰酸酯、二环己基二异氰酸酯、四甲基环己基甲烷二异氰酸酯或二苯基甲烷二异氰酸酯中的一种或几种;
聚合反应过程中,反应温度为60-90℃,反应时间为2-3h。
4.根据权利要求1所述的一种本质阻燃水性聚氨酯树脂的制备方法,其特征在于,步骤(3)中,聚合反应过程中加入催化剂进行催化,所述的催化剂的添加量为多异氰酸酯质量的0.4%-0.6%;
催化剂为二月桂酸二丁基锡。
5.根据权利要求1所述的一种本质阻燃水性聚氨酯树脂的制备方法,其特征在于,步骤(4)中,中和剂的添加量为聚氨酯预聚体的质量的2.98-3.8%;
所述中和剂选自三乙胺、氨水、氢氧化钠中的一种或几种;
中和过程中,中和温度为40-50℃;中和时间为30min。
6.根据权利要求1所述的一种本质阻燃水性聚氨酯树脂的制备方法,其特征在于,步骤(5)中,去离子水的加入量为聚氨酯预聚体的质量的230%-235%。
7.根据权利要求1所述的一种本质阻燃水性聚氨酯树脂的制备方法,其特征在于,步骤(5)中,小分子扩链剂与有机磷多元醇阻燃剂的摩尔比为1:0.43-1:1.5。
8.一种通过权利要求1-7任一所述方法制备得到的本质阻燃水性聚氨酯树脂。
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