CN115386065A - 一种协同阻燃聚氨酯弹性体的制备方法 - Google Patents
一种协同阻燃聚氨酯弹性体的制备方法 Download PDFInfo
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- CN115386065A CN115386065A CN202210866685.2A CN202210866685A CN115386065A CN 115386065 A CN115386065 A CN 115386065A CN 202210866685 A CN202210866685 A CN 202210866685A CN 115386065 A CN115386065 A CN 115386065A
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- Prior art keywords
- diisocyanate
- flame retardant
- terminated
- polyurethane elastomer
- prepared
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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 48
- 239000003063 flame retardant Substances 0.000 title claims abstract description 47
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 30
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 36
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 19
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- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims abstract description 7
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
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- BEJQXBXPRXFJDP-UHFFFAOYSA-N 3-(3,3-dihydroxypropoxy)propane-1,1-diol Chemical compound OC(O)CCOCCC(O)O BEJQXBXPRXFJDP-UHFFFAOYSA-N 0.000 claims description 2
- VIOMIGLBMQVNLY-UHFFFAOYSA-N 4-[(4-amino-2-chloro-3,5-diethylphenyl)methyl]-3-chloro-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C(=C(CC)C(N)=C(CC)C=2)Cl)=C1Cl VIOMIGLBMQVNLY-UHFFFAOYSA-N 0.000 claims description 2
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 2
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- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
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- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 2
- TWLCPLJMACDPFF-UHFFFAOYSA-N cyclohexane;1,2-diisocyanatoethane Chemical compound C1CCCCC1.O=C=NCCN=C=O TWLCPLJMACDPFF-UHFFFAOYSA-N 0.000 claims description 2
- GMAYNBHUHYFCPZ-UHFFFAOYSA-N cyclohexyl-(4,4-dimethylcyclohexyl)methanediamine Chemical compound C1CC(C)(C)CCC1C(N)(N)C1CCCCC1 GMAYNBHUHYFCPZ-UHFFFAOYSA-N 0.000 claims description 2
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
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- 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 2
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Images
Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
本发明涉及聚氨酯的合成及加工技术领域,公开了一种协同阻燃聚氨酯弹性体的制备方法,包括以下步骤:1)制备异氰酸酯基团封端的聚氨酯预聚体;2)聚氨酯预聚体的扩链。本发明在经Si和P改性的基体中加入了膨胀型阻燃体系。经化学嵌段加入的含磷聚醚降低了膨胀型阻燃体系中酸源的用量,这也改善了优于填料的加入对于机械性能的破坏。同时,对于阻燃作用所存在的烟雾增加现象,使用硼酸锌可降低该烟雾的释放。
Description
技术领域
本发明涉及聚氨酯的合成及加工技术领域,具体涉及一种协同阻燃聚氨酯弹性体的制备方法。
背景技术
聚氨酯弹性体(PUE)具有橡胶的高弹性,其原料的多变性和特殊的微观结构使PUE的性能具有广泛的调节性,促使它广泛应用于生活的各个方面。但是PUE在应用中也存在一些缺点,如易黄变、耐候性差、耐热性差、阻燃性差且熔滴剧烈。硅基聚合物由较高键能的Si-O键(420kJ/mol)组成主链,这赋予其较高的热稳定性,低表面张力,疏水性优,耐候性能优越,化学惰性和使用温度范围广等优点。此外,硅基材料在燃烧过程中会形成致密的硅氧碳层对于内部材料有着很好的保护作用。但是硅基材料也表现为非常差的实用性,其中尤以力学性能最差,如低拉伸强度、撕裂和耐磨性。因此,对于二者优势性能的互补是一种比较重要的研究方向。
对于聚合物的阻燃常用的有两种方法:添加型和反应型。添加型即将含有阻燃能力的填料填充进聚合物中,这种方法的优势在于简单方便、便于生产和成本低廉。缺点在于要达到要求的阻燃级别往往需要大量的填料,而各种相容性不同的填料的添加会导致聚合物原有优异性能的损失。但是,反应型阻燃便不存在该缺陷,它是通过化学反应将含有阻燃元素的基团加入到聚合物的分子链上。该方法避免了大量阻燃填料的添加导致的材料性能的损失,并从根本上解决了填料存在的析出和相容性的问题。但是,该法的缺陷在于化学改性一般使用溶剂法,这会对环境和人类产生危害。并且含有阻燃元素的反应原料价格昂贵,且生产工艺不成熟,分子量难以控制,催化剂难以尽除。
在PUE的微观结构中存在一对相互作用:微相分离和微相混合。这主要由于构成PUE的硬段(异氰酸酯和扩链剂,HS)和软段(低聚物多元醇,SS)之间存在热力学不相容性。热力学不相容性导致HS与SS的聚集形成硬段相(HD)和软段相(SD),两相之间的极性不相容性和HS间的相互作用导致微相分离,而两相之间的相互作用导致微相混合。这两种相互作用主要为HS间的氢键作用和HS与SS之间的氢键作用。硅基材料作为一种非极性材料其与硬段之间几乎不存在氢键化作用。而其他软段如聚己内酯二醇分子链上含有酯基,他们能够和硬段上的-NH形成氢键。这种HS间形成的氢键,HS与SS间形成的氢键分别会促进微相分离和微相混合。这作为一对相互作用力,唯有处于一定的平衡之下才会使PUE具有最佳的性能。
发明内容
本发明的目的在于克服现有技术存在的缺点,提供一种结合膨胀型阻燃体系(IFR)的有机硅、含磷聚醚改性的阻燃型聚氨酯弹性体,在满足阻燃要求的情况下,增加相容性、降低成本和对力学性能的高保持率;并使得手感爽滑、疏水性好、耐热性优、环保阻燃和不产生有害成分。
为了实现上述目的,本发明的技术方案是:一种协同阻燃聚氨酯弹性体的制备方法,其特征在于,包括以下步骤:
1)制备异氰酸酯基团封端的聚氨酯预聚体:在50~60℃条件下,将液体状二异氰酸酯与端羟烃基聚二甲基硅氧烷、低分子量二元醇按质量比2.43:3:1混合搅拌均匀,升温至80℃,在N2的气氛下反应2h,然后继续在80℃下,负压抽真空得异氰酸酯封端的聚氨酯预聚体;
2)聚氨酯预聚体的扩链:根据扩链系数f=1.05对异氰酸酯封端的聚氨酯预聚体进行扩链,向异氰酸酯封端的聚氨酯预聚体中加入扩链剂、交联剂、含磷聚醚、催化剂和IFR,所述异氰酸酯封端的聚氨酯预聚体、扩链剂、交联剂、含磷聚醚、催化剂、IFR的质量比为10:0.2:0.4:1.22:0.01:1.18~1.54,混合均匀后在100℃下反应定型10min,然后冷压成型得到聚氨酯,然后将得到的聚氨酯在80℃下熟化10h,得到协同阻燃聚氨酯弹性体。
进一步地;所述端羟烃基聚二甲基硅氧烷分子量为1000~3000g/mol,结构式如下:
式中n为聚合度;R为烷烃分子链,其主链C的个数为3~5个。
进一步地;所述端羟烃基聚二甲基硅氧烷为端羟丁基聚二甲基硅氧烷。
进一步地;所述二异氰酸酯选自4,4'-亚甲基二苯基二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、对苯二异氰酸酯、萘二异氰酸酯、苯二亚甲基二异氰酸酯、环己烷二亚甲基二异氰酸酯、二甲基联苯二异氰酸酯、甲基环己基二异氰酸酯、二甲基二苯基甲烷二异氰酸酯中的一种或几种。
进一步地;所述低分子量二元醇选自聚醚型二醇、聚酯型二醇、聚己内酯型二醇、端羟基聚丁二烯、聚碳酸酯二醇、端羟基蓖麻油中的一种或几种;所述扩链剂选自乙二醇、1,4-丁二醇、1,2-丙二醇、1,6-己二醇、1,3-丙二醇、1,4-环己二醇、4-羟乙基氧乙基-1-羟乙基苯二醚、3-羟乙基氧乙基-1-羟乙基苯二醚、双酚A二羟乙基醚、双酚A二羟丙基醚、二甲基二氨基二环己基甲烷、1,4-环己烷二胺中的一种或几种。
进一步地;所述交联剂选自3,3'-二氯-4,4'-二苯基甲烷二胺、3,5-二甲硫基甲苯二胺、3,5-二乙基甲苯二胺、4,4'-亚甲基双(2-乙基)苯胺、3-氯-4,4'-二氨基二苯甲烷、和4,4'-亚甲基双(3-氯-2,6-二乙基苯胺)中的一种或几种。
进一步地;所述含磷聚醚为主链含有P元素的聚醚,结构式如下:
式中n为聚合度。
进一步地;所述催化剂选自二月桂酸二丁基锡、二醋酸二丁基锡、辛酸铅中一种或几种。
进一步地;所述IFR包括酸源、气源和碳源,所述酸源、气源和碳源的质量比为3:2:5,所述碳源选自季戊四醇、双季戊四醇、可膨胀石墨的一种或几种;所述气源选自三聚氰胺、三聚氰胺尿酸盐、三聚氰胺聚磷酸盐的一种或几种;所述酸源选自聚磷酸铵、二乙基磷酸铝、红磷的一种或几种。
进一步地;所述IFR还包括硼酸锌,所述酸源、气源、碳源和硼酸锌的质量比为3:2:5:3。
本发明的有益效果:
1)本发明基于本体法,使用预聚体法制备副反应少、结构规整度好的聚氨酯弹性体。制备的有机硅、含磷聚醚改性聚氨酯弹性体在保持优异机械性能的同时,手感爽滑,具有较优的疏水性、热稳定性和阻燃性,在聚氨酯基体中实现了Si-P的协同阻燃。
2)本发明在经Si和P改性的基体中加入了膨胀型阻燃体系。经化学嵌段加入的含磷聚醚降低了膨胀型阻燃体系中酸源的用量,这也改善了由于大量填料的加入对于机械性能的破坏。同时,对于阻燃作用所存在的烟雾增加现象,使用硼酸锌可降低该烟雾的释放。
3)在制备的协同阻燃聚氨酯弹性体之中,膨胀性阻燃体系经过燃烧形成隔热、氧的膨胀碳层;硅基材料在于降低基体的热值,且在燃烧中形成致密的硅氧碳层。两者在燃烧中形成复合的硅氧-膨胀碳层对内部具有极佳的保护作用。
附图说明
图1是对比例1-对比例3制备的测试样品的全FTIR图谱;
图2是测试样品的静态接触角。
具体实施方式
下面结合具体实施例对本发明进行详细说明,但保护范围并不仅限于此。
实施例1:
一种协同阻燃聚氨酯弹性体的制备方法,包括以下步骤:
1)将分子量为1750g/mol的端羟丁基聚二甲基硅氧烷(PDMS)和分子量为1000g/mol的聚己内酯二醇(PCL)在使用前在120℃条件下真空脱水2h,待冷却至室温后备用;向配备有搅拌器和氮气装置的三颈烧瓶中加入10g 4,4'-亚甲基二苯基二异氰酸酯(MDI),在60℃的条件下,经搅拌融化为无色透明液体,然后再加入真空脱水的12.37g PCL和4.12gPDMS混合均匀,升温至80℃,在N2的气氛下反应2h,然后继续在80℃下负压抽真空0.5h祛除反应产物中的气体,得聚氨酯预聚体(PUP),使用二正丁胺法测定PUP的NCO基团的质量分数(NCO%)为8%,其中理论值为5%,相对误差为0.5%;
2)根据扩链系数f=1.05对制备的PUP进行扩链,将步骤1)制备的PUP与1.06g 3,5-二甲硫基甲苯二胺(E-300)、0.53g 1,4-丁二醇(BDO)、3.23g含磷聚醚、0.1g二月桂酸二丁基锡、3.13g IFR混合均匀后,在100℃下模压成型10min,然后冷压2min得到聚氨酯,然后将聚氨酯在80℃下熟化10h使得内部完全反应得协同阻燃聚氨酯弹性体,用于表征和测试;
所述IFR由0.93g密胺包覆聚磷酸铵(MAPP)、0.64g三聚氰胺聚磷酸盐(MPP)和1.56g可膨胀石墨(EG)组成。
实施例2:
一种协同阻燃聚氨酯弹性体的制备方法,包括以下步骤:
1)将分子量为1750g/mol的PDMS和分子量为1000g/mol的PCL在使用前在120℃条件下真空脱水2h,待冷却至室温后备用;向配备有搅拌器和氮气装置的三颈烧瓶中加入10gMDI,在60℃的条件下,经搅拌融化为无色透明液体,然后再加入真空脱水的12.37g PCL和4.12g PDMS混合均匀,升温至80℃,在N2的气氛下反应2h,然后继续在80℃下负压抽真空0.5h祛除反应产物中的气体得PUP,使用二正丁胺法测定PUP的NCO%为8%,其中理论值为5%,相对误差为0.5%;
2)根据扩链系数f=1.05对制备的PUP进行扩链,将步骤1)制备的PUP与1.06g E-300、0.53g BDO、3.23g含磷聚醚、0.1g二月桂酸二丁基锡、4.06g IFR混合均匀后,在100℃下模压成型10min,然后冷压2min得到聚氨酯,然后将聚氨酯在80℃下熟化10h使得内部完全反应得协同阻燃聚氨酯弹性体,用于表征和测试;
所述IFR由0.93g MAPP、0.64g MPP、1.56g EG和0.93g硼酸锌组成。
对比例1:
一种聚氨酯的制备方法,包括以下步骤:
1)将分子量为1000g/mol的PCL在使用前在120℃条件下真空脱水2h,待冷却到室温后备用;向配备有搅拌器和氮气装置的三颈烧瓶中加入10g MDI,在60℃的条件下,经搅拌融化为无色透明液体,然后再加入真空脱水的21.32g PCL混合均匀,升温至80℃,在N2的气氛下反应2h,然后继续在80℃下负压抽真空0.5h祛除反应产物中的气体得PUP,使用二正丁胺法测定PUP的NCO%为8%,其中理论值为5%,相对误差为0.5%;
2)根据扩链系数f=1.05对制备的PUP进行扩链,将步骤1)制备的PUP与1.25g E-300,1.20g BDO和0.1g二月桂酸二丁基锡混合均匀后,在100℃下模压成型10min,然后冷压2min得到聚氨酯,然后将得到的聚氨酯在80℃下熟化10h使得聚氨酯内部完全反应,用于表征和测试。
对比例2:
一种聚氨酯的制备方法,包括以下步骤:
1)将分子量为1750g/mol的PDMS和1000g/mol的PCL在使用前在120℃条件下真空脱水2h,待冷却到室温后备用;向配备有搅拌器和氮气装置的三颈烧瓶中加入10g MDI,在60℃的条件下,经搅拌融化为无色透明液体,然后再加入真空脱水的21.37g PCL和4.12gPDMS混合均匀,升温至80℃,在N2的气氛下反应2h,然后继续在80℃下负压抽真空0.5h祛除反应产物中的气体得PUP,使用二正丁胺法测定PUP的NCO%为8%,其中理论值为5%,相对误差为0.5%;
2)根据扩链系数f=1.05对制备的PUP进行扩链,将步骤1)制备的PUP与1.06g E-300,1.83g BDO和0.1g二月桂酸二丁基锡混合均匀后,在100℃下模压成型10min,然后冷压2min得到聚氨酯,然后将得到的聚氨酯在80℃下熟化10h使得聚氨酯内部完全反应,用于表征和测试。
对比例3:
一种聚氨酯的制备方法,包括以下步骤:
1)将分子量为1750g/mol的PDMS和1000g/mol的PCL在使用前在120℃条件下真空脱水2h,待冷却到室温后备用;向配备有搅拌器和氮气装置的三颈烧瓶中加入10g MDI,在60℃的条件下,经搅拌融化为无色透明液体,然后再加入真空脱水的12.37g PCL和4.12gPDMS混合均匀,升温至80℃,在N2的气氛下反应2h,然后继续在80℃下负压抽真空0.5h祛除反应产物中的气体得PUP,使用二正丁胺法测定PUP的NCO%为8%,其中理论值为5%,相对误差为0.5%;
2)根据扩链系数f=1.05对制备的PUP进行扩链,将步骤1)制备的PUP与1.06g E-300,0.53g BDO、3.23g含磷聚醚和0.1g二月桂酸二丁基锡混合均匀后,在100℃下模压成型10min,然后冷压2min得到聚氨酯,然后将得到的聚氨酯在80℃下熟化10h使得聚氨酯内部完全反应,用于表征和测试。
测试实验:
将对比例1-3制备的测试样品利用FTIR分析内部是否完全反应,如图1所示,对比例1、对比例2、对比例3制备的测试样品均不存在2260~2270cm-1处的NCO基团的吸收峰,说明样品已经完全反应。对比例1为不加有机硅改性的PCL基聚氨酯,对比例2为混合软段的PDMS嵌段的PCL基聚氨酯,对比例3为混合软段的PDMS、含磷聚醚嵌段的PCL基聚氨酯,因此本发明可以合成有机硅、含磷聚醚改性的聚氨酯。
分别将实施例1、实施例2、对比例1-3制备的测试样品依据测试标准GB/T 528-2009,测试机械性能,使用接触角测试仪测试静态接触角并区分样品的手感爽滑等级,测试结果见表1;其中样品的静态接触角的变化趋势如图2所示;
样品的表面评价标准如下:手感爽滑度分为1、2、3、4、5五级,1为最差,5为最好。1级:手感滞涩,试片完全粘于模腔;2级:手感滞涩,试片有2/3粘于模腔;3级:手感一般,试片1/2以下粘于模腔:4级:手感爽滑,试片不粘于磨腔;5级:手感爽滑,试片在开模时自然脱落。
表1样品的机械性能、静态接触角和手感爽滑
对比例1为PCL基聚氨酯的水静态接触角较小为91.5°,在主链嵌段硅氧烷之后对比例2的静态接触角急剧增大到104.3°,对比例3在对比例2基础上嵌段含磷聚醚会进一步降低接触角,实施例1和2添加阻燃剂会导致静态接触角的持续降低,但是仍高于未改性的对比例1。
测量(130mm/6.5mm/3.2mm)棒状试样保持最低的燃烧时的氧浓度,根据氧指数测试的国标ASTMD2863来测定材料的极限氧指数(LOI),根据国标ASTMD3801-2010对(130mm/13mm/3.2mm)棒材试样进行测试;材料的垂直燃烧等级根据试样的燃烧时间、是否有熔化和滴落、脱脂棉是否被点燃来确定垂直燃烧UL-94等级;测试结果参见表2。
表2样品的LOI、熔滴和UL-94测试结果
表1显示样品机械性能、静态接触角和手感爽滑等级。对比例1为单一的PCL基聚氨酯,其机械性能为最优,对比例2为有机硅改性的PCL基聚氨酯,在加入硅基材料之后,表面疏水性、手感爽滑等级会增加,但是力学性能会相应降低。对比例3为加入有机硅、含磷聚醚改性的PCL基聚氨酯,含磷聚醚相当于软段嵌段组分的加入,会降低硬段含量,整体上降低力学性能。实施例1、实施例2是在对比例3基础上加入阻燃填料,填充体系的加入会对微观结构具有破坏作用,间接降低机械性能。但是,由于前面对于基体的阻燃处理,会降低整体的阻燃填料的用量。
表2显示了样品的LOI、掉落和UL-94测试结果。在阻燃处理的不断累积下材料的LOI会呈现不断增加的趋势,并且在膨胀型阻燃体系与主链中有机硅、含磷聚醚的配合之下,在实施例1中,将基体(指聚氨酯预聚体与扩链剂、交联剂反应生成的聚合物)作为100重量份计时,仅使用10重量份的阻燃填料(3份酸源,2份气源和5份碳源)便消除了燃烧的掉落现象,达到了离火即熄的V-0阻燃级别。
以上所述的实施例只是本发明较佳的方案,并非对本发明作任何形式上的限制,在不超出权利要求所记载的技术方案的前提下还有其它的变体及改型。
Claims (10)
1.一种协同阻燃聚氨酯弹性体的制备方法,其特征在于,包括以下步骤:
1)制备异氰酸酯基团封端的聚氨酯预聚体:在50~60℃条件下,将液体状二异氰酸酯与端羟烃基聚二甲基硅氧烷、低分子量二元醇按质量比2.43:3:1混合搅拌均匀,升温至80℃,在N2的气氛下反应2h,然后继续在80℃下,负压抽真空得异氰酸酯封端的聚氨酯预聚体;
2)聚氨酯预聚体的扩链:根据扩链系数f=1.05对异氰酸酯封端的聚氨酯预聚体进行扩链,向异氰酸酯封端的聚氨酯预聚体中加入扩链剂、交联剂、含磷聚醚、催化剂和膨胀型阻燃体系,所述异氰酸酯封端的聚氨酯预聚体、扩链剂、交联剂、含磷聚醚、催化剂、膨胀型阻燃体系的质量比为10:0.2:0.4:1.22:0.01:1.18~1.54,混合均匀后在100℃下反应定型10min,然后冷压成型得到聚氨酯,然后将得到的聚氨酯在80℃下熟化10h,得到协同阻燃聚氨酯弹性体。
3.根据权利要求2所述的协同阻燃聚氨酯弹性体的制备方法,其特征在于:所述端羟烃基聚二甲基硅氧烷为端羟丁基聚二甲基硅氧烷。
4.根据权利要求1所述的协同阻燃聚氨酯弹性体的制备方法,其特征在于:所述二异氰酸酯选自4,4'-亚甲基二苯基二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、对苯二异氰酸酯、萘二异氰酸酯、苯二亚甲基二异氰酸酯、环己烷二亚甲基二异氰酸酯、二甲基联苯二异氰酸酯、甲基环己基二异氰酸酯、二甲基二苯基甲烷二异氰酸酯中的一种或几种。
5.根据权利要求1所述的协同阻燃聚氨酯弹性体的制备方法,其特征在于:所述低分子量二元醇选自聚醚型二醇、聚酯型二醇、聚己内酯型二醇、端羟基聚丁二烯、聚碳酸酯二醇、端羟基蓖麻油中的一种或几种;所述扩链剂选自乙二醇、1,4-丁二醇、1,2-丙二醇、1,6-己二醇、1,3-丙二醇、1,4-环己二醇、4-羟乙基氧乙基-1-羟乙基苯二醚、3-羟乙基氧乙基-1-羟乙基苯二醚、双酚A二羟乙基醚、双酚A二羟丙基醚、二甲基二氨基二环己基甲烷、1,4-环己烷二胺中的一种或几种。
6.根据权利要求1所述的协同阻燃聚氨酯弹性体的制备方法,其特征在于:所述交联剂选自3,3'-二氯-4,4'-二苯基甲烷二胺、3,5-二甲硫基甲苯二胺、3,5-二乙基甲苯二胺、4,4'-亚甲基双(2-乙基)苯胺、3-氯-4,4'-二氨基二苯甲烷、和4,4'-亚甲基双(3-氯-2,6-二乙基苯胺)中的一种或几种。
8.根据权利要求1所述的协同阻燃聚氨酯弹性体的制备方法,其特征在于:所述催化剂选自二月桂酸二丁基锡、二醋酸二丁基锡、辛酸铅中一种或几种。
9.根据权利要求1所述的协同阻燃聚氨酯弹性体的制备方法,其特征在于:所述膨胀型阻燃体系包括酸源、气源和碳源,所述酸源、气源和碳源的质量比为3:2:5,所述碳源选自季戊四醇、双季戊四醇、可膨胀石墨的一种或几种;所述气源选自三聚氰胺、三聚氰胺尿酸盐、三聚氰胺聚磷酸盐的一种或几种;所述酸源选自聚磷酸铵、二乙基磷酸铝、红磷的一种或几种。
10.根据权利要求9所述的协同阻燃聚氨酯弹性体的制备方法,其特征在于:所述膨胀型阻燃体系还包括硼酸锌,所述酸源、气源、碳源和硼酸锌的质量比为3:2:5:3。
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