CN116874710A - 阻燃聚氨酯硬泡、制备方法及其应用 - Google Patents
阻燃聚氨酯硬泡、制备方法及其应用 Download PDFInfo
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Abstract
本发明涉及一种阻燃聚氨酯硬泡、制备方法及其应用,主要解决现有技术中存在阻燃聚氨酯硬泡中成本高的问题。本发明通过采用一种新的阻燃聚氨酯硬泡,以重量份数计,由以下组分组成:组份A:包括60‑80份聚醚多元醇、20‑40份改性脲醛树脂、0.1‑15份发泡剂、0.01‑5份泡沫稳定剂、0.1‑5份水、0.01‑5份催化剂;组份B:110‑180份的异氰酸酯;及其制备方法的技术方案,较好地解决了该问题,可在建筑保温材料中应用。
Description
技术领域
本发明涉及一种阻燃聚氨酯硬泡、制备方法及其应用。
背景技术
硬质聚氨酯泡沫(RPUF)简称聚氨酯硬泡,主要是由异氰酸酯与多元醇反应生成的一种有机高分子材料。RPUF以其质轻、保温性能好、抗压强度高等优点,广泛应用于建筑、汽车、家具、电子、航天等领域。然而,未经阻燃处理的RPUF是一种高度易燃的材料,且燃烧过程中会产生大量的烟雾和CO、NO、HCN等有毒气体,对人类的生命财产安全产生了巨大隐患。随着RPUF应用领域的不断扩大,潜在的火灾危险性也越来越大。因此,进行RPUF阻燃改性研究具有防患于未然的现实意义。
RPUF的燃烧过程可以简单概括为:(1)RPUF在高温下受热分解产生可燃性气体;(2)可燃性气体在气相中达到一定的浓度和温度时就会在空气环境中燃烧;(3)可燃性气体燃烧产生的热量促使RPUF进一步降解,直至RPUF燃烧完为止。基于其燃烧过程,对RPUF阻燃的机理主要分为凝聚相阻燃机理和气相阻燃机理。凝聚相阻燃机理:(1)阻燃剂受热后分解吸热,降低材料表面温度,阻碍其达到分解温度;(2)阻燃剂受热分解形成难燃多孔炭层覆于材料表面,起到隔热、隔氧作用,从而抑制燃烧的进行。气相阻燃机理:(1)阻燃剂分解产生不燃性气体,降低可燃性气体和氧气的浓度,致使燃烧终止;(2)阻燃剂受热产生的细微粒子能使自由基结合,从而终止燃烧链式反应。
中国专利CN 106046285 B通过合成一种密胺型系列多元醇,也能达到制备阻燃聚氨酯硬泡的要求,但是该密胺型系列多元醇成本较高,因此不是阻燃聚氨酯硬质泡沫塑料的最佳解决方案。
发明内容
本发明所要解决的技术问题之一是,现有技术中存在阻燃聚氨酯硬泡中成本高的问题,提供一种新的阻燃聚氨酯硬泡,该阻燃聚氨酯硬泡具有阻燃性能好且持久、成本低的优点。
为解决上述技术问题之一,本发明采用的技术方案如下:一种阻燃聚氨酯硬泡,以重量份数计,由以下组分组成:(1)组份A:包括60-80份聚醚多元醇、20-40份改性脲醛树脂、0.1-15份发泡剂、0.01-5份泡沫稳定剂、0.1-5份水、0.01-5份催化剂;(2)组份B:110-180份的异氰酸酯。
上述技术方案中,优选地,所述的步骤(1)中聚醚多元醇的官能度为2-6,羟值为200-600mgKOH/g。
上述技术方案中,优选地,所述的聚醚多元醇选自NJ-4110或NJ-8238中的一种;发泡剂为HCFC-141b、CFC-11或环戊烷中的至少一种;泡沫稳定剂为AK8805、UA6001或L6900中的至少一种;催化剂为PC-5、PC-8或PC-41中的至少一种;异氰酸酯为M20S。
上述技术方案中,优选地,所述步骤(1)中改性脲醛树脂的制备方法如下:
(1)将尿素、三聚氰胺、多聚甲醛、多元醇按摩尔比1:0.1~0.3:2~6:2~6加入反应釜中,形成物料Ⅰ;
(2)在搅拌条件下加热升温,当反应釜内物料温度为70~100℃时,调节体系pH为9~11,反应时间为1~3h,得到物料Ⅱ;
(3)在常压下加入pH调节剂,调节pH为3~5,反应温度为70~100℃,反应1~3h后得到物料Ⅲ;
(4)在物料Ⅲ中加入pH调节剂,调节pH为7~8得到物料Ⅳ;
(5)对物料Ⅳ进行减压蒸馏分离出体系中的小分子物质,得到改性脲醛树脂。
上述技术方案中,优选地,所述的步骤(1)中的多元醇选自乙二醇、二甘醇、丙二醇、二丙二醇、丁二醇或甘油中的至少一种;步骤(2)和步骤(4)中pH调节试剂为氢氧化钠、氢氧化钾的水溶液或显碱性的有机胺类中的至少一种;步骤(3)中pH调节试剂为盐酸、硝酸、磷酸、硫酸、对甲苯磺酸、甲酸、草酸中一种或多种的原液或水溶液;步骤(5)中小分子副产物为游离甲醛、水及甲醇的混合物;减压蒸馏温度为70~100℃,压力为-0.08~-0.10Mpa。
为解决上述技术问题之二,本发明采用的技术方案如下:
一种前述的阻燃聚氨酯硬泡的制备方法,包括以下步骤:
(1)将60-80份聚醚多元醇、20-40份改性脲醛树脂、0.1-15份发泡剂、0.01-5份泡沫稳定剂、0.1-5份水、0.01-5份催化剂混合均匀得到组份A;
(2)称量110-180份的异氰酸酯,并控制温度20-25℃,得到组份B;
(3)控制模具温度20-50℃,将组份B加入组份A中,并迅速搅拌均匀得到物料C;
(4)将物料C倒入模具中,使其发泡,泡沫熟化后脱模即得到所述的阻燃聚氨酯硬泡。
为解决上述技术问题之三,本发明采用的技术方案如下:
一种前述的阻燃聚氨酯硬泡在建筑保温材料中应用。
本发明提供一种阻燃聚氨酯硬泡及其制备方法,其有益效果为:采用特殊的改性脲醛树脂,替代常规的添加型含卤阻燃剂作用于聚氨酯泡沫塑料,有效的解决了普通硬质聚氨酯泡沫塑料阻燃性能差、阻燃剂成本高的问题。本发明方法制得的聚氨酯硬质泡沫塑料燃烧氧指数可达26%以上,大大提高了聚氨酯泡沫塑料的阻燃性能,同时保持了聚氨酯泡沫塑料的各种优良性能,满足了聚氨酯泡沫塑料的耐火要求,且制备步骤简单,工艺条件易于控制,对环境友好,原材料成本低廉,适于工业化生产,取得了较好地技术效果。
具体实施方式
以下只是本发明的优选实施方式,并非是对本发明保护范围的限制,凡属于本发明思路下的技术方案应当落入本发明的保护范围之内,对于本技术领域内的专业技术人员,在不脱离本发明原理前提下对本发明进行的细微改进和润饰也应当落入本发明的保护范围内。
【实施例1】
1.阻燃聚氨酯硬泡,其制备方法包含以下步骤:
(1)将60份聚醚多元醇4110、40份改性脲醛树脂、12份发泡剂HCFC-141b、1.5份泡沫稳定剂AK8805、2份水、0.7份催化剂PC-8混合均匀得到组份A;
(2)称量165份的异氰酸酯M20S,并控制温度25℃,得到组份B;
(3)控制模具温度45℃,将组份B加入组份A中,并迅速搅拌均匀得到物料C;
(4)将物料C倒入模具中,使其发泡并熟化后脱模即得到所述的阻燃聚氨酯硬泡。其中改性脲醛树脂的制备方法如下:
(1)将尿素、三聚氰胺、多聚甲醛、多元醇按摩尔比1:0.1:3:3加入反应釜中,形成物料Ⅰ;
(2)在搅拌条件下加热升温,当反应釜内物料温度为75℃时,调节体系pH为9,反应时间为1h,得到物料Ⅱ;
(3)在常压下加入pH调节剂,调节pH为4,反应温度75℃,反应2h后得到物料Ⅲ;
(4)在物料Ⅲ中加入pH调节剂,调节pH为7.5得到物料Ⅳ;
(5)对物料Ⅳ进行减压蒸馏脱除小分子副产物,减压蒸馏温度为75℃,压力为-0.098MPa,以表压计,过滤除去固体盐得到改性脲醛树脂S1。
【实施例2~6】
实施例2~6按照实施例1中的各个步骤进行,各物料配比具体如表1,改性脲醛树脂的制备方法具体见表2,其中pH调节试剂的浓度均为质量百分比浓度;制得的阻燃聚氨酯硬泡的性能指标数据见表3所示。
表1实施例1~6及比较例1中聚氨酯硬泡配方的质量份数
表2实施例1~6中改性脲醛树脂制备中原料摩尔比及反应条件
【比较例1】
1.参照专利CN 106046285 B中实施例1中方案制备丙二醇型密胺多元醇S,添加到本发明的聚氨酯硬质泡沫塑料的配方中,步骤如下:
(1)按重量份数计,将60份聚醚多元醇、15份发泡剂、2份催化剂、2份稳泡剂、1份水以及40份丙二醇型密胺多元醇,用混料机高速搅拌混合均匀制得白料;
(2)将上述白料与135份多异氰酸酯混合后打入发泡设备发泡成型;
(3)脱模,切割制得样条。
制得的聚氨酯泡沫塑料的性能指标数据见表3所示。
表3实施例1~6及比较例1中制备的聚氨酯硬泡的性能数据
由表3中性能数据可知,本发明申请实施例1~6中制备的低成本聚氨酯硬泡的氧指数都达到了23%以上,虽然比较例1的氧指数能达到24.5%,但是其原料成本较高,因为丙二醇型密胺多元醇的原料成本比本发明中尿醛树脂的成本高;比较例2的氧指数达到了23.2%,但是压缩强度也低了18%左右,因为添加了TCPP,属于添加型阻燃剂,不能通过反应接枝到泡沫分子结构中;比较例3的氧指数只有19.9%,基本没有阻燃效果,而本发明采用的改性脲醛树脂为反应型含氮阻燃剂,可以与黑料异氰酸酯发生化学反应,从而可以有效的保持聚氨酯优良的机械强度,阻燃更持久,成本更低,取得了较好的技术效果,可用于聚氨酯硬泡的应用中。
Claims (7)
1.一种阻燃聚氨酯硬泡,以重量份数计,由以下组分组成:
(1)组份A:包括60-80份聚醚多元醇、20-40份改性脲醛树脂、0.1-15份发泡剂、0.01-5份泡沫稳定剂、0.1-5份水、0.01-5份催化剂;
(2)组份B:110-180份的异氰酸酯。
2.根据权利要求1所述的阻燃聚氨酯硬泡,其特征在于,所述的步骤(1)中聚醚多元醇的官能度为2-6,羟值为200-600mgKOH/g。
3.根据权利要求1所述的阻燃聚氨酯硬泡,其特征在于,所述的聚醚多元醇选自NJ-4110或NJ-8238中的一种;发泡剂为HCFC-141b、CFC-11或环戊烷中的至少一种;泡沫稳定剂为AK8805、UA6001或L6900中的至少一种;催化剂为PC-5、PC-8或PC-41中的至少一种;异氰酸酯为M20S。
4.根据权利要求1所述的阻燃聚氨酯硬泡,其特征在于,所述步骤(1)中改性脲醛树脂的制备方法如下:
(1)将尿素、三聚氰胺、多聚甲醛、多元醇按摩尔比1:0.1~0.3:2~6:2~6加入反应釜中,形成物料Ⅰ;
(2)在搅拌条件下加热升温,当反应釜内物料温度为70~100℃时,调节体系pH为9~11,反应时间为1~3h,得到物料Ⅱ;
(3)在常压下加入pH调节剂,调节pH为3~5,反应温度为70~100℃,反应1~3h后得到物料Ⅲ;
(4)在物料Ⅲ中加入pH调节剂,调节pH为7~8得到物料Ⅳ;
(5)对物料Ⅳ进行减压蒸馏分离出体系中的小分子物质,得到改性脲醛树脂。
5.根据权利要求4所述的阻燃聚氨酯硬泡,其特征在于,所述的步骤(1)中的多元醇选自乙二醇、二甘醇、丙二醇、二丙二醇、丁二醇或甘油中的至少一种;步骤(2)和步骤(4)中pH调节试剂为氢氧化钠、氢氧化钾的水溶液或显碱性的有机胺类中的至少一种;步骤(3)中pH调节试剂为盐酸、硝酸、磷酸、硫酸、对甲苯磺酸、甲酸、草酸中一种或多种的原液或水溶液;步骤(5)中小分子副产物为游离甲醛、水及甲醇的混合物;减压蒸馏温度为70~100℃,压力为-0.08~-0.10Mpa。
6.一种权利要求1所述的阻燃聚氨酯硬泡的制备方法,包括以下步骤:
(1)将60-80份聚醚多元醇、20-40份改性脲醛树脂、0.1-15份发泡剂、0.01-5份泡沫稳定剂、0.1-5份水、0.01-5份催化剂混合均匀得到组份A;
(2)称量110-180份的异氰酸酯,并控制温度20-25℃,得到组份B;
(3)控制模具温度20-50℃,将组份B加入组份A中,并迅速搅拌均匀得到物料C;
(4)将物料C倒入模具中,使其发泡,泡沫熟化后脱模即得到所述的阻燃聚氨酯硬泡。
7.一种权利要求1所述的阻燃聚氨酯硬泡在建筑保温材料中应用。
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB858127A (en) * | 1956-06-15 | 1961-01-04 | Scott Paper Co | Polymer foam modification |
US3488310A (en) * | 1967-02-24 | 1970-01-06 | Owens Corning Fiberglass Corp | Urea-melamine-formaldehyde resins |
JPS52152999A (en) * | 1976-06-16 | 1977-12-19 | Mitsubishi Gas Chem Co Inc | Preparation of modified urethane foam |
JPS56133323A (en) * | 1980-03-25 | 1981-10-19 | Asahi Glass Co Ltd | Polyolf for polyurethane and production of polyurethane |
US4435526A (en) * | 1981-11-06 | 1984-03-06 | Abelard Management Services Limited | Process for the manufacture of urea-formaldehyde/polyurethane polymers |
US4579876A (en) * | 1984-02-21 | 1986-04-01 | Mobay Chemical Corporation | Polyols for the production of rigid polyurethane foams |
DE4018764A1 (de) * | 1989-12-29 | 1991-09-05 | Sprela Schichtstoff Gmbh | Verfahren zur herstellung von modifizierten harnstoff-melaminharzloesungen |
JPH05186554A (ja) * | 1991-12-13 | 1993-07-27 | Toyo Tire & Rubber Co Ltd | 難燃性硬質ポリウレタンフオームの製造方法 |
CN1616510A (zh) * | 2003-11-14 | 2005-05-18 | 邵广义 | 改性三聚氰胺尿素甲醛共聚树脂的制造和用于生产浸渍纸 |
CN102120810A (zh) * | 2011-01-25 | 2011-07-13 | 中国林业科学研究院林产化学工业研究所 | 一种高固含可发性三聚氰胺改性脲醛树脂的制备方法 |
WO2012001154A1 (en) * | 2010-07-02 | 2012-01-05 | Societe Anonyme Naicom | Production method of urea-melamine-formaldehyde resin |
-
2022
- 2022-08-29 CN CN202211040368.1A patent/CN116874710A/zh active Pending
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB858127A (en) * | 1956-06-15 | 1961-01-04 | Scott Paper Co | Polymer foam modification |
US3488310A (en) * | 1967-02-24 | 1970-01-06 | Owens Corning Fiberglass Corp | Urea-melamine-formaldehyde resins |
JPS52152999A (en) * | 1976-06-16 | 1977-12-19 | Mitsubishi Gas Chem Co Inc | Preparation of modified urethane foam |
JPS56133323A (en) * | 1980-03-25 | 1981-10-19 | Asahi Glass Co Ltd | Polyolf for polyurethane and production of polyurethane |
US4435526A (en) * | 1981-11-06 | 1984-03-06 | Abelard Management Services Limited | Process for the manufacture of urea-formaldehyde/polyurethane polymers |
US4579876A (en) * | 1984-02-21 | 1986-04-01 | Mobay Chemical Corporation | Polyols for the production of rigid polyurethane foams |
DE4018764A1 (de) * | 1989-12-29 | 1991-09-05 | Sprela Schichtstoff Gmbh | Verfahren zur herstellung von modifizierten harnstoff-melaminharzloesungen |
JPH05186554A (ja) * | 1991-12-13 | 1993-07-27 | Toyo Tire & Rubber Co Ltd | 難燃性硬質ポリウレタンフオームの製造方法 |
CN1616510A (zh) * | 2003-11-14 | 2005-05-18 | 邵广义 | 改性三聚氰胺尿素甲醛共聚树脂的制造和用于生产浸渍纸 |
WO2012001154A1 (en) * | 2010-07-02 | 2012-01-05 | Societe Anonyme Naicom | Production method of urea-melamine-formaldehyde resin |
CN102120810A (zh) * | 2011-01-25 | 2011-07-13 | 中国林业科学研究院林产化学工业研究所 | 一种高固含可发性三聚氰胺改性脲醛树脂的制备方法 |
Non-Patent Citations (4)
Title |
---|
HENG ZHU: "Preparation and fire behavior of rigid polyurethane foams synthesized from modified urea–melamine– formaldehyde resins", 《THE ROYAL SOCIETY OF CHEMISTRY》, no. 8, 31 December 2018 (2018-12-31), pages 17879 - 17887 * |
倪礼忠: "《聚合物基复合材料》", 31 January 2022, 华东理工大学出版社, pages: 180 * |
周维祥: "《塑料测试技术》", 31 January 1997, 化学工业出版社, pages: 285 - 286 * |
荣国斌: "《大学有机化学基础:下册》", 31 August 2006, 华东理工大学出版社, pages: 333 * |
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