CN104070740A - 吸音复合材料及其用途 - Google Patents
吸音复合材料及其用途 Download PDFInfo
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- CN104070740A CN104070740A CN201410112870.8A CN201410112870A CN104070740A CN 104070740 A CN104070740 A CN 104070740A CN 201410112870 A CN201410112870 A CN 201410112870A CN 104070740 A CN104070740 A CN 104070740A
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- component
- foam
- isocyanate
- din
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- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 239000006260 foam Substances 0.000 claims abstract description 78
- 239000012948 isocyanate Substances 0.000 claims abstract description 17
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims description 34
- 239000010410 layer Substances 0.000 claims description 21
- 229920005862 polyol Polymers 0.000 claims description 13
- 150000003077 polyols Chemical class 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 11
- 230000006835 compression Effects 0.000 claims description 10
- 238000007906 compression Methods 0.000 claims description 10
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
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- 239000003054 catalyst Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000004604 Blowing Agent Substances 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000004970 Chain extender Substances 0.000 claims description 2
- 239000012790 adhesive layer Substances 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 24
- -1 isosorbite Chemical compound 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
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- 101000598921 Homo sapiens Orexin Proteins 0.000 description 11
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- 229910052757 nitrogen Inorganic materials 0.000 description 9
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- 239000002253 acid Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 6
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- 239000005056 polyisocyanate Substances 0.000 description 6
- 229920001228 polyisocyanate Polymers 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 4
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- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
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- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- 239000003381 stabilizer Substances 0.000 description 3
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- 241000220317 Rosa Species 0.000 description 2
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- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
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- 239000006096 absorbing agent Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
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- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical class [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- KFYRJJBUHYILSO-YFKPBYRVSA-N (2s)-2-amino-3-dimethylarsanylsulfanyl-3-methylbutanoic acid Chemical compound C[As](C)SC(C)(C)[C@@H](N)C(O)=O KFYRJJBUHYILSO-YFKPBYRVSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- GQEAMFCDHPUBGV-GRHBHMESSA-N (z)-but-2-enedioic acid;dibutyltin Chemical compound OC(=O)\C=C/C(O)=O.CCCC[Sn]CCCC GQEAMFCDHPUBGV-GRHBHMESSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
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- PCXJASANFWPUMO-UHFFFAOYSA-N 1-(methylamino)propan-1-ol Chemical compound CCC(O)NC PCXJASANFWPUMO-UHFFFAOYSA-N 0.000 description 1
- CYLWXTCHTYMIHB-UHFFFAOYSA-N 1-ethoxyimidazole Chemical class CCON1C=CN=C1 CYLWXTCHTYMIHB-UHFFFAOYSA-N 0.000 description 1
- WCDFMPVITAWTGR-UHFFFAOYSA-N 1-imidazol-1-ylpropan-2-ol Chemical class CC(O)CN1C=CN=C1 WCDFMPVITAWTGR-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- GEEGPFGTMRWCID-UHFFFAOYSA-N 1-n,1-n,1-n',1-n'-tetramethylbutane-1,1-diamine Chemical compound CCCC(N(C)C)N(C)C GEEGPFGTMRWCID-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
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- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 description 1
- NCUPDIHWMQEDPR-UHFFFAOYSA-N 2-[2-[2-(dimethylamino)ethoxy]ethyl-methylamino]ethanol Chemical compound CN(C)CCOCCN(C)CCO NCUPDIHWMQEDPR-UHFFFAOYSA-N 0.000 description 1
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 description 1
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明涉及复合材料元件,所述元件包含开孔的硬质异氰酸酯基泡沫层和至少一个另外的异氰酸酯基泡沫层,并涉及其用于声音吸收的用途。
Description
技术领域
本发明涉及包含开孔的硬质异氰酸酯基泡沫层和至少一个另外的异氰酸酯基泡沫层的复合材料元件及其用于声音吸收的用途。
背景技术
为了减小室内区域的环境噪音,如今通常使用吸音壁。目前用于此目的的是常常为多层构造的纤维无纺布或软质泡沫,其常常不是自支撑的且通过内部或外部框架固定。Silence Solutions公司提供了这种类型的吸音隔离壁(DE-A 102007000568)。
框架也会导致相当大的重量。在质弹系统中,质轻软质的层片(也称作层)与更重更硬和无孔的层片结合,同样地形成相应的沉重的构造。
可选地,也有基于脲和甲醛的已知的开孔质轻硬质泡沫,但是生产它们昂贵而复杂,因为需要使散发进入室内空气中的甲醛降到最低。例如当使用聚氨酯时实现低的甲醛放出要容易得多。
机动车辆在其车顶内衬里中常常含有由玻璃纤维/聚脲复合材料支撑的具有不同密度和硬度的聚氨酯泡沫。
另外已知不同材料的组合用于制备声学活性的复合材料。
JP-A 2010184655描述了两层复合材料。在这些复合材料中,一层是基于聚酯多元醇的开孔的硬质或软质的聚氨酯泡沫,在500-1000Hz范围内具有JIS A 1405-1最大吸收。第二层是基于聚苯乙烯树脂、酚醛树脂、聚氨酯树脂和/或三聚氰胺甲醛树脂的泡沫,具有100 ml/cm2/s的透气度。
JP-A 2005193612描述了三层构造形式的硬质整体泡沫,所述泡沫由两个100-300 kg/m3的重质层和密度为10-70kg/m3的硬质聚氨酯泡沫芯组成。重质的外层之一必须随后用额外的工作和花费进行穿孔以便获得有效的声学吸收。
JP-A 2009226675描述了一种两层吸音器,包含泡沫和直接在上面发泡的(foamed-on)纤维无纺布。纤维无纺布在上面发泡从技术角度来说是要求非常多的操作。
JP-A 2005352036描述了一种由三种泡沫构成的三层吸音器,其中第一种泡沫具有60-130kg/m3的密度、1.5-3.5 105 N/m2的杨氏模量和1000-8000 Ns/m3的气流阻力,第二种具有45-80 kg/m3的密度和1-10 105 N/m2的杨氏模量,以及第三种具有100-200 kg/m3的密度和800-6000 Ns/m3的气流阻力。
发明内容
本发明的目的是提供吸音和特别是硬质的复合材料,使用此复合材料可以减少室内区域的环境噪音,从而使与噪音有关的对健康和良好体格(well-being)的有害效应最小化。
已经令人惊讶地发现:用包含基于异氰酸酯的具有不同硬度的至少两个泡沫层的复合材料元件实现了此目的。
本发明提供了复合材料元件,其具有至少两个不同的异氰酸酯基泡沫层,所述泡沫各自的DIN 53420密度为≤130 kg/m3,优选≤100 kg/m3且在10%的压缩率下各自的DIN EN 826压缩强度为5-200 kPa,所述至少两层的密度和压缩强度不同,其中所述至少两层中的至少一层的DIN 53430断裂伸长率大于30%,并且根据DIN ISO 4590-86各自具有平均75-98%的开孔,并且所述复合材料元件在所述至少两层之间任选地具有粘合剂粘合层,其中
A) 所述至少两个泡沫层中的至少一层为至少5mm厚和由不可逆地可热成形的硬质异氰酸酯基泡沫组成,所述泡沫的DIN 53420密度为10-45 kg/m3,优选15-30kg/m3和在10%压缩率下DIN EN 826压缩强度为30-200 kPa,所述泡沫层A)可从由如下组成的各组分的反应获得
i) 由以下物质组成的多元醇组分
a. 基于所述多元醇组分i)的异氰酸酯反应性组分的总量计,15-60重量%的如下聚醚多元醇,其具有10-50重量%环氧乙烷部分,所述聚醚多元醇的数均当量重量(number-average equivalent weight)为500-2500 g/mol和官能度为2-8,优选2-6,
b. 基于所述多元醇组分i)的异氰酸酯反应性组分的总量计,30-70重量%的聚醚多元醇,其数均当量重量为50-480 g/mol和官能度为2-8,优选2-6,
c. 任选地扩链剂和/或交联剂,
d. 基于所述多元醇组分i)的异氰酸酯反应性组分的总量计,1-15重量%的水和任选地另外的发泡剂,
e. 基于所述多元醇组分i)的异氰酸酯反应性组分的总量计,0.3-5重量%的催化剂,
f. 任选地助剂(auxiliaries)和/或辅助剂(adjuvants),
ii) 和异氰酸酯组分,其包含
g. 基于所述异氰酸酯组分ii)计,55-100重量%,优选60-80重量%的二官能二苯基甲烷二异氰酸酯(MDI),其4,4‘-MDI与2,4‘-MDI的异构体重量比为1:1-7:1,优选为2:1-3:1,
h. 基于所述异氰酸酯组分ii)计,0-45重量%,优选20-40重量%的二苯基甲烷二异氰酸酯(MDI)的更高级同系物,
B) 所述至少两个泡沫层在1 cm的层厚度下根据ISO 10543在315-6350 Hz范围内各自具有至少20%的平均吸音率。
特别优选所述至少两层都具有至少5mm的厚度。
具体实施方式
在一个优选的实施方案中,将作为一个层的在10%压缩率下具有30-200kPa的压缩硬度(DIN EN 826)的硬质泡沫A)与作为第二层的在40%压缩率下具有0.5-50kPa的压缩硬度(ISO3386-1-98)的软质泡沫相结合。在所述复合材料中的上述两层的每一层都具有5mm的厚度情况下,所述复合材料已具有足够的声学效率。
在一个特别优选的实施方案中,所述两层都是异氰酸酯基泡沫,所述泡沫的DIN 53420密度为10-45kg/m3,优选15-24kg/m3,其中一层在10%压缩率下具有60-200kPa的DIN EN 826压缩强度,并且密度相对于泡沫层A)相差3-20kg/m3。
本发明的复合材料元件优选这样制造使得一个或两个或更多个泡沫层A)固定在模具壁上。接着将多元醇组分和异氰酸酯组分的混合物引入开放或闭合的模具中。如果适当的话闭合模具,所述混合物在模具内固化形成泡沫层。
本发明的复合材料元件更特别用于制造不需要用于稳定的外部框架的吸音板。特别在重量敏感的移动应用的情况下例如在车辆中这是相当重要的。
用作组分a的是当量重量为500-2500 g/mol的2-8官能的含环氧乙烷聚氧化烯多元醇,其优选通过环氧乙烷和/或环氧丙烷与2-8官能的起始分子反应可获得,所述2-8官能的起始分子例如甘油、三羟甲基丙烷、乙二醇、水、1,2-丙二醇、新戊二醇、双酚A、双酚F、四溴代双酚A、山梨糖醇蔗糖和其它起始剂。
用作组分b的是当量重量为50-480 g/mol的2-8官能的,优选2-6官能的,更优选2-3官能的聚氧化烯多元醇,其优选通过环氧乙烷和/或环氧丙烷与起始剂反应可获得,所述起始剂例如甘油、三羟甲基丙烷、丙二醇类、乙二醇、三乙醇胺、乙二胺、烷基化的二氨基苯、糖和/或山梨糖醇与二醇的混合物、邻苯二甲酸与二醇的单酯等。
用作组分c的可以是本身由聚氨酯化学已知的化合物,例如甘油、丁二醇、乙二醇、二甘醇、异山梨糖醇、三乙醇胺和二乙醇胺。
作为组分d的另外的发泡剂特别可以使用物理发泡剂、甲酸和甲酸酯/盐。
催化剂e包括加速反应的化合物。所考虑的那些包括有机金属化合物,优选有机锡化合物,如有机羧酸的锡(II)盐,例如乙酸锡(II)、辛酸锡(II)、乙基己酸锡(II)、月桂酸锡(II)和有机羧酸的二烷基锡(IV)盐,例如二乙酸二丁基锡、二月桂酸二丁基锡、马来酸二丁基锡、二乙酸二辛基-锡,铋盐和锌盐,以及叔胺如三乙胺、三丁胺、二甲基环己基胺、二甲基苄基胺、N-甲基咪唑、N-甲基-、N-乙基-和N-环己基吗啉、N,N,N′,N′-四甲基乙二胺、N,N,N′,N′-四甲基丁二胺、N,N,N′,N′-四甲基己-1,6-二胺、五甲基--二亚乙基三胺、四甲基二氨基乙基醚、双(二甲基氨基丙基)脲、二甲基哌嗪、1,2-二甲基咪唑、1-氮杂双环[3,3,0]辛烷、1,4-二氮杂双环[2,2,2]辛烷和烷醇胺化合物,如三乙醇胺、三异丙醇胺、N-甲基-和N-乙基二乙醇胺和二甲基乙醇胺以及相应的胺氧化物。另外考虑作为催化剂的如下:三(二烷基氨基)-s-六-氢--三嗪类、尤其是三(N,N-二-甲基氨基)-s-六氢三-嗪,四烷基铵盐,例如N,N,N-三甲基-N-(2-羟丙基)甲酸铵、N,N,N-三甲基-N-(2-羟丙基)2-乙基己酸铵,四烷基氢氧化铵如四甲基氢氧化铵,碱金属氢氧化物如氢氧化钠,碱金属醇盐如甲醇钠和异丙醇钾,以及具有1-20个C原子和任选地具有侧OH基团的脂肪酸的碱金属盐或碱土金属盐。
优选用作催化剂e的还有异氰酸酯反应性叔胺例如N,N-二-甲基-氨基-丙基胺、双(二-甲基-氨基-丙基)胺、N,N-二甲基氨基丙基-N′-甲基乙醇胺、二甲基氨基乙氧基乙醇、双(二-甲基氨基丙基)氨基-2-丙醇、N,N-二甲基氨基丙基二丙醇胺、N,N,N′-三甲基-N′-羟乙基双氨基乙基醚、N,N-二甲基氨基丙基脲、N-(2-羟丙基)咪唑、N-(2-羟乙基)-咪唑、N-(2-氨基丙基-)咪唑、2-((二-甲基-氨基)乙基)甲基-氨基丙醇、1,1‘-((3-(二-甲基-氨基)丙基)亚氨基)双-2-丙醇和/或EP-A 0 629 607中描述的乙酰乙酸乙酯、聚醚多元醇和1-(二甲基氨基)-3-氨基丙烷的反应产物。
用于制备异氰酸酯基泡沫的典型的助剂和/或辅助剂是泡沫稳定剂、乳化剂、着色剂、阻燃剂和开孔剂。
例如,乳化剂包括乙氧基化的烷基酚、脂肪酸的碱金属盐、甜菜碱类、硫酸化脂肪酸的碱金属盐、磺酸的碱金属盐和脂肪酸和胺的盐。
例如,适合的泡沫稳定剂包括硅氧烷-聚氧化烯共聚物、有机聚硅氧烷、乙氧基化的脂肪醇和烷基酚、脂肪酸基的胺氧化物和甜菜碱类以及蓖麻油或蓖麻油酸酯。
例如,活性开孔剂包括石蜡、聚丁二烯类、脂肪醇和任选地聚氧化烯改性的二甲基聚硅氧烷。
任选使用的助剂和/或辅助剂的其它实例为反应缓凝剂、抵抗老化和风化效果的稳定剂、增塑剂、无机阻燃物质、任选地改性的炭黑、石墨和其它碳类、含磷和/或卤素的有机阻燃剂、具有抑真菌活性和抑细菌活性的物质、颜料和染料、以及本身已知的常规有机和无机填料。
关于上述助剂和/或辅助剂的使用方式和作用方式的进一步详情例如在Kunststoff-Handbuch, Polyurethane, 第VII卷, Carl Hanser Verlag, Munich, Vienna,第2版, 1983中进行了描述。
在异氰酸酯组分ii)中,另外可以使用室温下为液态的二苯基甲烷类的二-和/或多异氰酸酯。这些包括4,4'-二异氰酸根合二苯基甲烷、2,4'-和任选地2,2'-二异氰酸根合二苯基甲烷的室温液态且任选相应地改性的混合物。非常适合的还有室温液态的二苯基甲烷类多异氰酸酯混合物,所述二苯基甲烷类多异氰酸酯除了所述的异构体之外还包括其更高级的同系物并且以本身已知的方式通过苯胺/甲醛缩合的光气化作用可获得。具有氨基甲酸酯基团和/或碳二亚胺/脲二酮基团的这些二-和多异氰酸酯的改性产物也是适合的。具有脲基甲酸酯和/或缩二脲基团的所述二-和多异氰酸酯的改性产物同样是适合的。组分ii)中还可存在少量另外的脂族、环脂族或芳族多异氰酸酯。
所述异氰酸酯组分ii)优选具有 2.1-5.0,优选2.5-3.1的平均NCO官能度。
下列实施例意在更详细地说明本发明。
实施例:
实施例I:泡沫A的制备
泡沫A如下制备:首先在0.66 dm3体积的纸烧杯中混合61.86重量份甘油起始的环氧乙烷封端的聚环氧丙烷(6000 g/mol)、0.83重量份甘油起始的环氧乙烷封端的聚环氧丙烷(4550 g/mol)、0.29重量份二乙醇胺、0.54重量份甘油、1.68重量份水、0.17重量份Tegostab B8734LF2、0.13重量份Tegocolor Black HI与1.08重量份PC CAT NP712的混合物, 用Pendraulik搅拌器(6.5 cm搅拌板直径)在200 Hz进行此混合10秒钟,并用空气充填所述混合物。然后加入32.75重量份的2,4‘-MDI、4,4‘-MDI、4,4‘-MDI的缩二脲与更高级MDI同系物的混合物。将所述混合物用相同的搅拌器在700Hz混合5秒钟。加入异氰酸酯并开始混合后5秒钟泡沫开始上升。所述泡沫进一步上升50秒钟。在所述泡沫固化后,在烧杯边缘用刀割去突出的圆顶。减去烧杯重量之后,发现在0.66 dm3烧杯体积中存在28.4g泡沫。这相应于43 kg/m3的密度。为了制备用于声学测量的泡沫薄片,以类似于上述的配方,将208g的多元醇/异氰酸酯混合物导入2*2*0.4 m3体积的铝模具中。锁上盖子以后,泡沫在模具中固化2分钟。从泡沫板的芯部切割用于声学测量的试样。芯部的泡沫密度(DIN53420)为120g/dm3。拉伸强度为315 kPa,断裂伸长率为87%(ISO 1798)。在40%压缩率的压缩硬度为30 kPa(ISO 3386-1-98)。
实施例II:泡沫B的制备
泡沫B如下制备:首先在0.93dm3体积的金属基纸烧杯中混合7.7重量份甘油起始的环氧乙烷封端的聚环氧丙烷(6000 g/mol)、14.64重量份环氧乙烷封端的丙二醇起始的聚环氧丙烷(4000 g/mol)、3.85重量份丙二醇起始的环氧乙烷封端的聚环氧丙烷(2000 g/mol)、3.78重量份邻-甲苯二胺起始的环氧乙烷封端的聚环氧丙烷 (490 g/mol)、1.63重量份乙二胺起始的聚环氧丙烷(350 g/mol)、3.63重量份水、0.54重量份Ortegol 501、0.18重量份Tegostab B8870、0.18重量份Isopur N黑色糊料与0.73重量份Desmorapid 59IF08催化剂的混合物,用Pendraulik搅拌器(6.5 cm搅拌板直径)在200 Hz进行此混合10秒钟,并用空气充填所述混合物。然后加入63.13重量份的2,4‘-MDI、4,4‘-MDI、4,4‘-MDI与更高级MDI同系物 (重量比23:51:26)的混合物。所述混合物用相同的搅拌器在700Hz混合10秒钟并倾倒入衬有Teflon片的体积3*3*3 dm3的木箱中。加入异氰酸酯并开始混合后140秒,第一次可以用火柴从泡沫拉丝。另外2分钟后,将泡沫脱模并放置24小时。然后从芯部切割1dm边长的方块。所述方块重17g。这相应于17 kg/m3的密度。从用于测定总密度的中央方块上方的中部的泡沫切割用于声学测量的试样。拉伸强度为97 kPa,断裂伸长率为20%(DIN 53430)。压缩硬度为64 kPa(EN 826)。开孔含量为95%(DIN ISO 4590-86)。
实施例III:泡沫C的制备
泡沫C如下制备:首先在0.93 dm3体积的金属基纸烧杯中混合12.09重量份甘油/山梨糖醇-共-起始的带有环氧乙烷端部的聚环氧丙烷(6000 g/mol)、3.84重量份聚丙二醇(400 g/mol)、15.93重量份甘油起始的聚环氧丙烷(510 g/mol)、2.3重量份甘油、2.5重量份水、0.58重量份Polyurax SR272、0.19重量份Isopur N黑色糊料、1.15重量份油酸与二甲基氨基丙胺(摩尔比1:1)的反应产物的混合物,用Pendraulik搅拌器(6.5 cm搅拌板直径)在200 Hz进行此混合10秒钟,并用空气充填所述混合物。然后加入61.42重量份的2,4‘-MDI、4,4‘-MDI与更高级MDI同系物(重量比23:51:26)的混合物。所述混合物用相同的搅拌器在700 Hz混合10秒钟并倾倒入衬有Teflon片的体积3*3*3 dm3的木箱中。5分钟后,将泡沫脱模并放置24小时。然后从芯部切割1dm边长的方块。所述方块重24g。这相应于24 kg/m3的密度。从顶部、中部和底部的泡沫芯部切割用于声学测量的试样。所报告的值为这三块板的平均值。拉伸强度为115 kPa,断裂伸长率为14%(DIN 53430)。压缩硬度为96 kPa (EN 826)。开孔含量为84% (DIN ISO 4590-86)。
实施例IV:泡沫D的制备
泡沫D如下制备:首先在0.66 dm3体积的纸烧杯中混合62.8重量份甘油起始的环氧乙烷封端的聚环氧丙烷(6200 g/mol)、0.33重量份甘油、2.33重量份水、0.5重量份Tegostab B8734LF2、0.13重量份Tegocolor Black HI、0.27重量份Jeffcat DMAPA与0.27重量份PC CAT NP712的混合物,用Pendraulik搅拌器(6.5 cm搅拌板直径)在200 Hz进行此混合10秒钟,并用空气充填所述混合物。然后加入33.7重量份的2,4‘-MDI、4,4‘-MDI、4,4‘-MDI的缩二脲与更高级MDI同系物(1:68:20:11)的混合物。将所述混合物用相同的搅拌器在700Hz混合5秒钟。加入异氰酸酯并开始混合后13秒钟泡沫开始上升。所述泡沫进一步上升54秒钟。在所述泡沫固化后,在烧杯边缘用刀割去突出的圆顶。减去烧杯重量之后,发现在0.66 dm3烧杯体积中存在38.9g泡沫。这相应于59 kg/m3的密度。
为了制备用于声学测量的泡沫薄片,以类似于上述的配方,将106g的多元醇/异氰酸酯混合物导入2*2*0.4 m3体积的铝模具中。锁上盖子以后,泡沫在模具中固化2分钟。从泡沫板的芯部切割用于声学测量的试样。芯部的泡沫密度(DIN53420)为64g/dm3。拉伸强度为223 kPa,断裂伸长率为150%(ISO 1798)。在40%压缩率下的压缩硬度为9 kPa(ISO 3386-1-98)。
由所生产的泡沫A、B、C、D和E制备没有粘合剂层的复合材料元件(实施例1-13;见表1),使用机械夹紧。
实施例V:泡沫E以及泡沫E和泡沫C的复合材料元件(实施例14-16;见表1)的制备
泡沫E如下制备:混合60.23重量份丙二醇起始的环氧乙烷封端的聚环氧丙烷(6200 g/mol)、0.49重量份二乙醇胺、2.42重量份水、0.2重量份Tegostab B8734LF2、0.2重量份Isopur N黑色糊料、1.96重量份Mesamoll、0.16重量份Jeffcat ZF10、0.68重量份二甲基氨基己醇与0.04重量份Dabco NE300的混合物,用Pendraulik搅拌器(6.5 cm搅拌板直径)在200 Hz进行此混合10秒钟,并用空气充填所述混合物。然后加入33.45重量份的2,4‘-MDI、4,4‘-MDI与更高级MDI同系物的混合物。将所述混合物用相同的搅拌器在700Hz混合5秒钟。将所述混合物导入1.6 dm3体积的调温折叠盖模具中,其中在底部中或盖中已经预先固定了10 mm 厚的C类泡沫板。一种情况是在每种情况下弄湿插入的泡沫板。三分钟后打开模具。
从所述复合材料上切割用于声学测量的试样以制备5mm的C类泡沫和5mm的E类泡沫。由过量的E类泡沫切割试样用于测定机械性能。芯部的泡沫密度(DIN53420)为53g/dm3。拉伸强度为141 kPa,断裂伸长率为135%(ISO 1798)。在40%压缩率的压缩硬度为4 kPa(ISO 3386-1-98)。
所述复合材料元件的性能及其构造由下表1可见。
表1
*对比例。
实施例8和9(组合CD、DC)显示低密度的硬质泡沫(泡沫C)与非常低密度的硬质泡沫(泡沫D)的组合通常产生声音吸收的提高,即使在密度差仅为7 kg/m3时。
实施例7和11(组合CA、CB)显示:在远离噪音一侧的低密度硬质泡沫(泡沫C)与另一开孔泡沫的组合在噪音吸收上产生了总体提高。如果使用特定质轻的泡沫D代替低密度硬质泡沫(泡沫C),情况也是如此。在BD组合的情况下,声音吸收非常尤其在低频范围内得以提高。在直接发泡法的情况下(实施例14、15),即使当低总密度硬质泡沫(泡沫C)置于面向噪音一侧和软质泡沫在远离噪音一侧时,也实现了吸收性的总体提高。
实施例6和10(组合AC、BC)显示软质泡沫和面向噪音一侧的低密度硬质泡沫的组合在低频范围产生了提高。
实施例8、10、11、12、14和15显示:通过泡沫组合令人惊讶地也可以选择性地在某些频率以选择性过滤功能的形式得到特别高的吸收率。
Claims (2)
1.复合材料元件,其具有至少两个不同的异氰酸酯基泡沫层,每层具有至少5mm的厚度,所述泡沫各自具有≤130 kg/m3的DIN 53420密度且在10%的压缩率下各自具有5-200kPa的DIN EN 826压缩强度,所述至少两层的密度和压缩强度不同,其中所述至少两层中的至少一层的DIN 53430断裂伸长率大于30%,和根据DIN ISO 4590-86各自具有平均75-98%的开孔,并且所述复合材料元件在所述至少两层之间任选地具有粘合剂粘合层,其中
A) 所述至少两个泡沫层中的至少一层由不可逆地可热成形的硬质异氰酸酯基泡沫组成,所述泡沫具有10-45 kg/m3的DIN 53420密度和在10%压缩率下30-200 kPa的DIN EN 826压缩强度,所述泡沫层A)可从由如下组成的各组分的反应获得
i) 由以下物质组成的多元醇组分
a. 基于所述多元醇组分i)的异氰酸酯反应性组分的总量计,15-60重量%的如下聚醚多元醇,其具有10-50重量%环氧乙烷部分,该聚醚多元醇的数均当量重量为500-2500g/mol和官能度为2-8,
b. 基于所述多元醇组分i)的异氰酸酯反应性组分的总量计,30-70重量%的如下聚醚多元醇,其数均当量重量为50-480 g/mol和官能度为2-8,
c. 任选地扩链剂和/或交联剂,
d. 基于所述多元醇组分i)的异氰酸酯反应性组分的总量计,1-15重量%的水和任选地另外的发泡剂,
e. 基于所述多元醇组分i)的异氰酸酯反应性组分的总量计,0.3-5重量%的催化剂,
f) 任选地助剂和/或辅助剂,
ii) 和异氰酸酯组分,其包含
g) 基于所述异氰酸酯组分ii)计,55-100重量%的二官能二苯基甲烷二异氰酸酯(MDI),其4,4‘-MDI与2,4‘-MDI的异构体重量比为1:1-7:1,
h) 基于所述异氰酸酯组分ii)计,0-45重量%的二苯基甲烷二异氰酸酯(MDI)的更高级同系物,
B) 所述至少两个泡沫层在1cm的层厚度下根据ISO 10543 (Kund管)在315-6350 Hz范围内各自至少具有20%的平均吸音率。
2.根据权利要求1的复合材料元件用于制备吸音板的用途。
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CN108263050A (zh) * | 2016-12-30 | 2018-07-10 | 比亚迪股份有限公司 | 一种聚氨酯复合隔音材料及其制备方法与动力装置 |
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TWI744280B (zh) * | 2016-02-04 | 2021-11-01 | 日商三菱化學股份有限公司 | 隔音片材構件、使用其之隔音構造體、及隔音片材構件之製造方法 |
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