CN107955124A - 含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫及其制法 - Google Patents
含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫及其制法 Download PDFInfo
- Publication number
- CN107955124A CN107955124A CN201610899197.6A CN201610899197A CN107955124A CN 107955124 A CN107955124 A CN 107955124A CN 201610899197 A CN201610899197 A CN 201610899197A CN 107955124 A CN107955124 A CN 107955124A
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- Prior art keywords
- polyether polyol
- parts
- component
- polyol
- flaming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920000570 polyether Polymers 0.000 title claims abstract description 102
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 100
- 150000003077 polyols Chemical class 0.000 title claims abstract description 97
- 229920005862 polyol Polymers 0.000 title claims abstract description 92
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 46
- 239000006260 foam Substances 0.000 title claims abstract description 41
- 239000004814 polyurethane Substances 0.000 title claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000003063 flame retardant Substances 0.000 claims abstract description 51
- -1 poly methylene Polymers 0.000 claims abstract description 22
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 18
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical compound B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 10
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- 239000004088 foaming agent Substances 0.000 claims abstract description 8
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 7
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 7
- 229920006389 polyphenyl polymer Polymers 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 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 claims description 42
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 10
- 238000005829 trimerization reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- GNDMWRNTJIARLO-UHFFFAOYSA-N ClC(C)Cl.[F] Chemical group ClC(C)Cl.[F] GNDMWRNTJIARLO-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 125000002785 azepinyl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- DPXFJZGPVUNVOT-UHFFFAOYSA-N 3-[1,3-bis[3-(dimethylamino)propyl]triazinan-5-yl]-n,n-dimethylpropan-1-amine Chemical class CN(C)CCCC1CN(CCCN(C)C)NN(CCCN(C)C)C1 DPXFJZGPVUNVOT-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043237 diethanolamine Drugs 0.000 claims description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 229920003232 aliphatic polyester Polymers 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005187 foaming Methods 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 53
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 28
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 22
- 239000000463 material Substances 0.000 description 21
- 238000006254 arylation reaction Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- 229920000877 Melamine resin Polymers 0.000 description 14
- SIAVMDKGVRXFAX-UHFFFAOYSA-N 4-carboxyphenylboronic acid Chemical class OB(O)C1=CC=C(C(O)=O)C=C1 SIAVMDKGVRXFAX-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- CYMHIEKFNUNIBB-UHFFFAOYSA-N N1C=CC=CC=C1.[B] Chemical group N1C=CC=CC=C1.[B] CYMHIEKFNUNIBB-UHFFFAOYSA-N 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 5
- 238000011938 amidation process Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000013557 residual solvent Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
本发明公开了一种含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫及其制备方法。本发明在聚氨酯硬质泡沫的制备工艺中引进一种含硼氧六环、芳环、氮杂环的阻燃聚醚多元醇,其与聚醚多元醇、聚酯多元醇、匀泡剂、催化剂、交联剂、发泡剂组成A组份,B组份为多亚甲基多苯基多异氰酸酯。A、B组份在一定条件下混匀发泡,经固化熟化后得到高强度阻燃聚氨酯硬质泡沫。本发明制备出的聚氨酯硬质泡沫具有较高的力学性能和阻燃性能,密度42.5‑45.0kg/m3,压缩强度0.45‑0.58MPa,极限氧指数27.5‑30.0%。
Description
技术领域
本发明涉及阻燃聚氨酯材料,具体涉及一种基于硼氮多元环结构的聚醚多元醇制得的高强度阻燃聚氨酯硬质泡沫及其制备方法。
背景技术
聚氨酯材料是目前世界上使用最广泛的高分子材料之一,具有低密度,高比强度,优异耐磨性能,低导热系数,以及优良减震吸音性能等,已经应用在工业和生活中的各个领域。但是纯聚氨酯材料的缺点是易燃和耐高温性能差,接触火源会立即产生火焰,给人类的生命财产带来了巨大的威胁,引起的火灾造成的损失触目惊心。
目前,用于提高聚氨酯硬质泡沫材料阻燃性能的方法是向聚氨酯原料中加入阻燃剂,可分为添加型和反应型两种,添加型阻燃剂与聚氨酯原料间不发生化学反应,仅以物理形式填充分散到聚氨酯基体中,但添加型阻燃剂与聚氨酯基体相容性差,填充量较大时难免会导致阻燃剂浸出和材料机械性能下降等问题;反应型阻燃剂在聚氨酯合成过程中参加聚合反应并将阻燃元素结合到材料分子主链或侧链上,从而使制备出的聚氨酯材料具有阻燃性能,此类阻燃剂与基体材料相容性好,阻燃效率高。如磷酸酯类的聚醚多元醇,含氮杂环系聚醚多元醇等。由于卤系阻燃剂燃烧时会产生有毒气体,已经逐渐被限制使用。而磷系类阻燃聚醚多元醇本身也存在着一些缺点,如含磷化合物本身的毒性,挥发性大,而且燃烧时会产生比较大的烟雾,这也是发生火灾时对人产生致命的主要原因。
虽然反应型阻燃剂的使用使聚氨酯材料的阻燃性能得到大幅度提升,但是在一定密度范围内,同时兼顾到材料的力学性能和阻燃性能存在一定的困难。中国公开专利CN101906248A公开了一种高压缩强度刚性增强型硬质聚氨酯泡沫塑料,以芳香族化合物为增强聚氨酯泡沫塑料压缩强度的刚性结构组分,此芳香族化合物仅仅增强材料的力学性能,却对材料的阻燃性能没有改善,还需额外加入一定份数的添加型阻燃剂来提高材料的阻燃效果,势必会影响聚氨酯硬质泡沫塑料的整体性能。
本发明将阻燃元素硼、氮引入到聚醚多元醇分子结构中,同时利用刚性结构硼氧六环和苯环,耐热结构氮杂环的特性,同时增强聚氨酯材料的阻燃性能和力学性能。由于硼元素的加入,阻燃过程主要发生在凝聚相,在燃烧过程中产生玻璃状粘稠物质,起到物理覆盖隔绝作用,氮元素阻燃过程发生在气相,燃烧过程中产生不燃气体,稀释材料周围的空气浓度;而且含硼、氮阻燃剂与其它如含磷、卤系阻燃剂相比,前者的毒性要远远小于后者,而且前者具有良好的抑烟性。
发明内容
针对聚氨酯硬质泡沫塑料的防火性能差,添加阻燃剂后又影响泡沫塑料的力学性能等问题,本发明主要目的是提供了一种基于硼氮多元环结构的高强度阻燃聚氨酯硬质泡沫及其制备方法。本发明既提高了硬质塑料的阻燃性能,同时利用化学分子结构的特殊性大大增强材料整体的力学性能。由于硼、氮阻燃元素的存在,材料的极限氧指数达到30以上,由于阻燃聚醚多元醇结构上的特殊性,存在硼氧六元环结构和芳环结构,使聚氨酯材料的力学性能和热稳定性有很大的增强。
为了实现以上发明目的,本发明采用的技术方案如下:
一种含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫,它包含A、B两种组份,其中A组份由以下质量份数的原料组成:聚醚多元醇:25-45份,聚酯多元醇:10-15份,含硼氮多元环结构的阻燃聚醚多元醇:25-45份,匀泡剂:2-4份,凝胶型催化剂:0.5-2份,三聚催化剂:1-3份,交联剂:0.5-1.5份,发泡剂:25-40份;B组分的质量份为:多亚甲基多苯基多异氰酸酯:100-180份;所述的含硼氮多元环结构的阻燃聚醚多元醇其结构为:
其中R为聚醚基团:
聚合度n为25‐106。
上述的高强度阻燃聚氨酯硬泡沫,所述的A组份中聚醚多元醇为聚四氢呋喃多元醇或聚氧化丙烯多元醇的一种或几种,羟值为420-480mgKOH/g,粘度为2000-3500mPa.s(25℃),优选的为聚醚多元醇403、聚醚多元醇380、聚醚多元醇4110、聚醚多元醇635C的一种或几种;所述聚酯多元醇为脂肪族聚酯多元醇或芳香族聚酯多元醇的一种或几种,羟值为400-440mgKOH/g,粘度为4000-6000mPa.s(25℃),优选的为聚酯多元醇P-455N、聚酯多元醇SKR-400E、聚酯多元醇3152的一种或几种。
上述的高强度阻燃聚氨酯硬泡沫,所述A组份中催化剂包括凝胶型催化剂和三聚催化剂,其中凝胶型催化剂优选的为二月桂酸二丁基锡、辛酸亚锡的一种或两种,三聚催化剂优选的为N,N-二甲基环己胺、N,N-二甲基苄胺、1,3,5-三(二甲氨基丙基)六氢三嗪、五甲基二乙烯三胺的一种或几种的任意组合;所述A组份中匀泡剂为聚硅氧烷、聚醚硅氧烷或聚醚改性硅氧烷的一种或几种。优选的为匀泡剂AK-8801、AK-8805、AK8812或聚醚改性硅油HK-102的一种或几种;所述A组份中发泡剂为一氟二氯乙烷;所述的交联剂为三羟甲基丙烷、三乙醇胺、二乙醇胺或甘油的一种或几种的组合。
上述的高强度阻燃聚氨酯硬泡沫,A组份中所述的含硼氮多元环结构的阻燃聚醚多元醇具有刚性结构硼氧六环、耐热结构苯环和氮杂环结构,羟值为260-400mgKOH/g,粘度为1500-2500mPa.s(25℃)。;
一种制备上述的含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫的方法,它是将A组分中多元醇及各种助剂混合搅拌均匀后加入发泡剂,与B组分通过高压发泡机设备进行充分混合,充分混合后的A、B组份经发泡机枪头注入恒温铸钢模具中,经发泡、熟化、脱模得到高强度阻燃聚氨酯硬质泡沫。
上述的制备上述的含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫的方法,所述A组份中含硼氮多元环结构的阻燃聚醚多元醇,其制备方法包括下列步骤:
1)4-羧基苯硼酸和氯化亚砜在60-90℃下反应5-10h后,脱除水分和剩余溶剂,得到白色粉末芳基化的硼氧六环;
2)以三聚氰胺为起始原料,将三聚氰胺溶解在质量浓度10%-25%的NaOH水溶液中,芳基化硼氧六环溶于二氯甲烷溶液中,将两溶液快速混合,反应温度0-5℃,搅拌时间10-20min,搅拌转速150-250转/分,两溶液进行快速界面酰胺化反应,然后过滤,用80-95℃蒸馏水洗涤3-5次,干燥即得三聚氰胺改性的芳基化硼氧六环化合物;
3)以聚醚多元醇为主体介质,将三聚氰胺改性的芳基化硼氧六环化合物、甲醛混合,搅拌后加入碳酸氢钠,调节pH为7-10,升温到60-100℃,反应5-10h,脱除水分和溶剂,即得到主链上含有硼氮杂环结构的阻燃聚醚多元醇;
所述A组份中的含硼氮杂环结构阻燃聚醚多元醇,其合成原料及质量份数如下:
4-羧基苯硼酸:5-10份,氯化亚砜:25-50份,三聚氰胺:6-12份,NaOH:5-8份,二氯甲烷:9-15份,甲醛:20-35份,聚醚多元醇:10-20份;
所述甲醛为质量浓度35%-40%的甲醛水溶液。
本发明在合成一种含硼氮杂环结构阻燃聚醚多元醇的基础上,制备出一种含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫。利用阻燃聚醚多元醇中的苯环结构、刚性结构硼氧六元环和阻燃氮杂环三聚氰胺结构,最终将其引入到聚氨酯主链结构中,苯环结构和硼氧六元环结构都为刚性对称结构,它们的加入使材料的力学性能,尤其是抗压强度大大增强,三聚氰胺结构的高含氮量以及硼元素的存在,同时也提高了材料的阻燃性能。
本发明的有益效果如下:
1)本发明制备出的阻燃聚醚多元醇,性能稳定流动性好,且不含卤素、磷等有害元素,避免在燃烧过程中产生有毒气体和大量烟雾,并且含有热稳定性好的苯环结构、刚性结构硼氧六元环和阻燃氮杂环结构,增强聚醚多元醇的热稳定性和阻燃性能;
2)本发明的含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫及其制备方法,所得高强度阻燃聚氨酯硬质泡沫具有较高的力学性能和阻燃性能,密度42.5-45.0kg/m3,压缩强度0.45-0.58MPa,极限氧指数27.5-30.0%。
具体实施方式
以下采用实施例具体说明本发明的一种含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫及其制备方法。实施例是对本发明作进一步的详细说明,但它们不对本发明构成限定。
本发明一种含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫按照如下方法制备而成:
按配方量称取A组分中多元醇及各种助剂,混合搅拌均匀后加入发泡剂,与B组分通过高压发泡机设备进行充分混合,充分混合后的A、B组份经发泡机枪头注入恒温铸钢模具中,经发泡、熟化、脱模得到高强度阻燃聚氨酯硬质泡沫。
实施例1:
一种含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫,它包含A、B两种组份,由以下质量份数的原料组成:
聚醚多元醇403:15份
聚醚多元醇4110:10份
聚酯多元醇3152:10份
含硼氮多元环结构的阻燃聚醚多元醇:25份
匀泡剂AK-8801:2份
二月桂酸二丁基锡:0.5份
N,N-二甲基环己胺:1份
三乙醇胺:0.5份
一氟二氯乙烷HCFC-141B:25份
多亚甲基多苯基多异氰酸酯:100份
所述自制的含硼氮多元环结构的阻燃聚醚多元醇,由以下质量份数的原料组成,均为分析纯,市售:
4-羧基苯硼酸:5份
氯化亚砜:25份
三聚氰胺:6份
NaOH:5份
二氯甲烷:9份
甲醛:20份
聚醚多元醇:10份
所述甲醛为质量浓度35%的甲醛水溶液,
所述聚醚多元醇为聚醚多元醇380(羟值440mgKOH/g,粘度为3000mPa.s(25℃))
一种含硼氮多元环结构的阻燃聚醚多元醇制备方法,具体包含以下步骤:
4-羧基苯硼酸和氯化亚砜在60℃下反应5h后,脱除水分和剩余溶剂,得到白色粉末芳基化的硼氧六环;以三聚氰胺为起始原料,将三聚氰胺溶解在质量浓度10%的NaOH水溶液中,芳基化硼氧六环溶于二氯甲烷溶液中,将两溶液快速混合,反应温度0℃,搅拌时间10min,搅拌转速150转/分,两溶液进行快速界面酰胺化反应,然后过滤,用80℃蒸馏水洗涤3次,干燥即得三聚氰胺改性的芳基化硼氧六环化合物;以聚醚多元醇为主体介质,将三聚氰胺改性的芳基化硼氧六环化合物、甲醛混合,搅拌后加入碳酸氢钠,调节pH为7,升温到60℃,反应5h,脱除水分和溶剂,即得到主链上含有硼氮杂环结构的阻燃聚醚多元醇,该含硼氮杂环结构的阻燃聚醚多元醇,测定其羟值为羟值260mgKOH/g,粘度为1500mPa.s(25℃)。
实施例2:
一种含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫,它包含A、B两种组份,由以下质量份数的原料组成:
聚醚多元醇380:45份
聚酯多元醇P-455N:15份
含硼氮多元环结构的阻燃聚醚多元醇:45份
聚醚改性硅油HK-102:4份
辛酸亚锡:2份
1,3,5-三(二甲氨基丙基)六氢三嗪:3份
二乙醇胺:1.5份
一氟二氯乙烷HCFC-141B:40份
多亚甲基多苯基多异氰酸酯:180份
所述自制的含硼氮多元环结构的阻燃聚醚多元醇,由以下质量份数的原料组成,均为分析纯,市售:
4-羧基苯硼酸:10份
氯化亚砜:50份
三聚氰胺:12份
NaOH:8份
二氯甲烷:15份
甲醛:35份
聚醚多元醇:20份
所述甲醛为质量浓度40%的甲醛水溶液,
所述聚醚多元醇为聚醚多元醇4110(羟值480mgKOH/g,粘度为3500mPa.s(25℃))
一种含硼氮多元环结构的阻燃聚醚多元醇制备方法,具体包含以下步骤:
4-羧基苯硼酸和氯化亚砜在90℃下反应10h后,脱除水分和剩余溶剂,得到白色粉末芳基化的硼氧六环;以三聚氰胺为起始原料,将三聚氰胺溶解在质量浓度25%的NaOH水溶液中,芳基化硼氧六环溶于二氯甲烷溶液中,将两溶液快速混合,反应温度5℃,搅拌时间20min,搅拌转速250转/分,两溶液进行快速界面酰胺化反应,然后过滤,用95℃蒸馏水洗涤5次,干燥即得三聚氰胺改性的芳基化硼氧六环化合物;以聚醚多元醇为主体介质,将三聚氰胺改性的芳基化硼氧六环化合物、甲醛混合,搅拌后加入碳酸氢钠,调节pH为10,升温到100℃,反应10h,脱除水分和溶剂,即得到主链上含有硼氮杂环结构的阻燃聚醚多元醇,该含硼氮多元环结构的阻燃聚醚多元醇,测定其羟值为羟值400mgKOH/g,粘度为2500mPa.s(25℃)。
实施例3:
一种含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫,它包含A、B两种组份,由以下质量份数的原料组成:
聚醚多元醇635C:15份
聚醚多元醇4110:15份
聚酯多元醇P-455N:12份
含硼氮多元环结构的阻燃聚醚多元醇:35份
匀泡剂AK-8805:3份
二月桂酸二丁基锡:1份
五甲基二乙烯三胺:2份
三羟甲基丙烷:1.0份
一氟二氯乙烷HCFC-141B:32份
多亚甲基多苯基多异氰酸酯:150份
所述自制的含硼氮多元环结构的阻燃聚醚多元醇,由以下质量份数的原料组成,均为分析纯,市售:
4-羧基苯硼酸:8份
氯化亚砜:35份
三聚氰胺:10份
NaOH:6.5份
二氯甲烷:12份
甲醛:30份
聚醚多元醇:15份
所述甲醛为质量浓度38%的甲醛水溶液,
所述聚醚多元醇为聚醚多元醇4110(羟值430mgKOH/g,粘度为3000mPa.s(25℃))
一种含硼氮多元环结构的阻燃聚醚多元醇制备方法,具体包含以下步骤:
4-羧基苯硼酸和氯化亚砜在70℃下反应7h后,脱除水分和剩余溶剂,得到白色粉末芳基化的硼氧六环;以三聚氰胺为起始原料,将三聚氰胺溶解在质量浓度15%的NaOH水溶液中,芳基化硼氧六环溶于二氯甲烷溶液中,将两溶液快速混合,反应温度2℃,搅拌时间15min,搅拌转速200转/分,两溶液进行快速界面酰胺化反应,然后过滤,用85℃蒸馏水洗涤4次,干燥即得三聚氰胺改性的芳基化硼氧六环化合物;以聚醚多元醇为主体介质,将三聚氰胺改性的芳基化硼氧六环化合物、甲醛混合,搅拌后加入碳酸氢钠,调节pH为9,升温到80℃,反应8h,脱除水分和溶剂,即得到主链上含有硼氮杂环结构的阻燃聚醚多元醇,该含硼氮多元环结构的阻燃聚醚多元醇,测定其羟值为羟值300mgKOH/g,粘度为2000mPa.s(25℃)。
实施例4:
一种含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫,它包含A、B两种组份,由以下质量份数的原料组成:
聚醚多元醇4110:25份
聚酯多元醇P-455N:15份
含硼氮多元环结构的阻燃聚醚多元醇:45份
匀泡剂AK-8812:3份
二月桂酸二丁基锡:1份
N,N-二甲基环己胺:1份
N,N-二甲基苄胺:0.5份
甘油:0.5份
一氟二氯乙烷HCFC-141B:35份
多亚甲基多苯基多异氰酸酯:100份
所述自制的含硼氮多元环结构的阻燃聚醚多元醇,由以下质量份数的原料组成,均为分析纯,市售:
4-羧基苯硼酸:10份
氯化亚砜:25份
三聚氰胺:10份
NaOH:5份
二氯甲烷:10份
甲醛:35份
聚醚多元醇:18份
所述甲醛为质量浓度36%的甲醛水溶液,
所述聚醚多元醇为聚醚多元醇4110(羟值480mgKOH/g,粘度为3500mPa.s(25℃))
一种含硼氮多元环结构的阻燃聚醚多元醇制备方法,具体包含以下步骤:
4-羧基苯硼酸和氯化亚砜在60℃下反应10h后,脱除水分和剩余溶剂,得到白色粉末芳基化的硼氧六环;以三聚氰胺为起始原料,将三聚氰胺溶解在质量浓度25%的NaOH水溶液中,芳基化硼氧六环溶于二氯甲烷溶液中,将两溶液快速混合,反应温度3℃,搅拌时间10min,搅拌转速200转/分,两溶液进行快速界面酰胺化反应,然后过滤,用95℃蒸馏水洗涤3次,干燥即得三聚氰胺改性的芳基化硼氧六环化合物;以聚醚多元醇为主体介质,将三聚氰胺改性的芳基化硼氧六环化合物、甲醛混合,搅拌后加入碳酸氢钠,调节pH为8,升温到80℃,反应5h,脱除水分和溶剂,即得到主链上含有硼氮杂环结构的阻燃聚醚多元醇,该含硼氮多元环结构的阻燃聚醚多元醇,测定其羟值为羟值300mgKOH/g,粘度为2000mPa.s(25℃)。
上述实施例中含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫的相关性能测试结果如表1所示
表1
Claims (7)
1.一种含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫,其特征是:它包含A、B两种组份,其中A组份由以下质量份数的原料组成:聚醚多元醇:25-45份,聚酯多元醇:10-15份,含硼氮多元环结构的阻燃聚醚多元醇:25-45份,匀泡剂:2-4份,凝胶型催化剂:0.5-2份,三聚催化剂:1-3份,交联剂:0.5-1.5份,发泡剂:25-40份;B组分的质量份为:多亚甲基多苯基多异氰酸酯:100-180份;所述的含硼氮多元环结构的阻燃聚醚多元醇其结构为:
其中R为聚醚基团:
R:
聚合度n为25‐106。
2.根据权利要求1所述的高强度阻燃聚氨酯硬泡沫,其特征是:所述的A组份中聚醚多元醇为聚四氢呋喃多元醇或聚氧化丙烯多元醇的一种或几种,羟值为420-480mgKOH/g,粘度为2000-3500mPa.s(25℃);所述的聚酯多元醇为脂肪族聚酯多元醇或芳香族聚酯多元醇的一种或几种,羟值为400-440mgKOH/g,粘度为4000-6000mPa.s(25℃)。
3.根据权利要求2所述的高强度阻燃聚氨酯硬泡沫,其特征是:所述的A组份中聚醚多元醇为聚醚多元醇403、聚醚多元醇380、聚醚多元醇4110、聚醚多元醇635C的一种或几种;所述的聚酯多元醇为聚酯多元醇P-455N、聚酯多元醇SKR-400E、聚酯多元醇3152的一种或几种。
4.根据权利要求1所述的高强度阻燃聚氨酯硬泡沫,其特征是:所述A组 份中催化剂包括凝胶型催化剂和三聚催化剂;所述A组份中匀泡剂为聚硅氧烷、聚醚硅氧烷或聚醚改性硅氧烷的一种或几种;所述A组份中发泡剂为一氟二氯乙烷;所述的交联剂为三羟甲基丙烷、三乙醇胺、二乙醇胺或甘油的一种或几种的组合。
5.根据权利要求4所述的高强度阻燃聚氨酯硬泡沫,其特征是:所述的凝胶型催化剂为二月桂酸二丁基锡、辛酸亚锡的一种或两种;所述的三聚催化剂为N,N-二甲基环己胺、N,N-二甲基苄胺、1,3,5-三(二甲氨基丙基)六氢三嗪或五甲基二乙烯三胺的一种或几种的任意组合;所述的匀泡剂为AK-8801、AK-8805、AK8812或聚醚改性硅油HK-102的一种或几种。
6.根据权利要求1所述的高强度阻燃聚氨酯硬泡沫,其特征是:A组份中所述的含硼氮多元环结构的阻燃聚醚多元醇具有刚性结构硼氧六环、耐热结构苯环和氮杂环结构,羟值为260-400mgKOH/g,粘度为1500-2500mPa.s(25℃)。
7.一种制备权利要求1所述的含硼氮多元环的聚醚多元醇制得的高强度阻燃聚氨酯硬泡沫的方法,其特征是它是将权利要求1所述的A组分中多元醇及各种助剂混合搅拌均匀后加入发泡剂,与B组分通过高压发泡机设备进行充分混合,充分混合后的A、B组份经发泡机枪头注入恒温铸钢模具中,经发泡、熟化、脱模得到高强度阻燃聚氨酯硬质泡沫。
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