CN108676195A - 一种轻质隔音酚醛树脂 - Google Patents
一种轻质隔音酚醛树脂 Download PDFInfo
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- CN108676195A CN108676195A CN201810335159.7A CN201810335159A CN108676195A CN 108676195 A CN108676195 A CN 108676195A CN 201810335159 A CN201810335159 A CN 201810335159A CN 108676195 A CN108676195 A CN 108676195A
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- phenolic resin
- component
- lotion
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 65
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 65
- 239000006210 lotion Substances 0.000 claims abstract description 43
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000004088 foaming agent Substances 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000004970 Chain extender Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000000839 emulsion Substances 0.000 claims description 30
- -1 polyethylene terephthalate Polymers 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001299 aldehydes Chemical class 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001230 polyarylate Polymers 0.000 claims description 8
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 7
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 7
- 239000011118 polyvinyl acetate Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
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- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 4
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 4
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
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- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
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- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
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- 239000000178 monomer Substances 0.000 claims description 3
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- 239000001103 potassium chloride Substances 0.000 claims description 3
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- XPIJMQVLTXAGME-UHFFFAOYSA-N 1,1-dimethoxycyclohexane Chemical compound COC1(OC)CCCCC1 XPIJMQVLTXAGME-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- MEJAPGGFIJZHEJ-UHFFFAOYSA-N 5-acetamido-1,3,4-thiadiazole-2-sulfonyl chloride Chemical compound CC(=O)NC1=NN=C(S(Cl)(=O)=O)S1 MEJAPGGFIJZHEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004156 Azodicarbonamide Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 235000019439 ethyl acetate Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
- 150000001896 cresols Chemical class 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 86
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 33
- 239000011248 coating agent Substances 0.000 description 32
- 238000000576 coating method Methods 0.000 description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
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- 238000004080 punching Methods 0.000 description 13
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- 150000004985 diamines Chemical class 0.000 description 9
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- 229910021645 metal ion Inorganic materials 0.000 description 8
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical class OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
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- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 150000002883 o-cresols Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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Abstract
本发明涉及增强树脂技术领域,具体涉及一种轻质隔音酚醛树脂,所述轻质隔音酚醛树脂包括相互独立包装的组分A、组分B、组分C和组分D;以酚原料为100重量份计,所述组份A包括:第一聚合物乳液10~30重量份、发泡剂0.6~10重量份;所组份B包括:第二聚合物乳液18~56重量份、可溶性金属盐1~6重量份、扩链剂10~30重量份;所组份C包括:酚原料100重量份、醛原料40~120、催化剂10~30重量份;所组份D包括:有机溶剂200~400重量份。本发明通过在酚醛树脂中加入具有多重孔结构的复合纤维,既可以降低体系的质量,又阻挡声音的传播,起到隔音的作用。此外,由于该复合纤维由内芯和外壁双重结构构成,具有较高的强度和高韧性,起到增强酚醛树脂的作用。
Description
技术领域
本发明涉及增强树脂技术领域,具体涉及一种轻质隔音酚醛树脂。
背景技术
近年来,汽车轻量化已经成为当下汽车领域发展的重点方向,轻量化技术不仅能够有效的解决其环境污染的问题,实现节能减排的目标,还很大程度上降低了汽车制造的成本,相比于现在的所使用的汽车而言具有很大的经济效益。
目前,汽车轻量化的方法主要包括采用轻质材料和降低门板的截面。降低门板的截面也就是降低门板的厚度,虽然能够降低汽车的整体重量,但是也会导致汽车门板的强度降低,在碰撞时,会产生严重形变,降低了汽车的安全性。采用轻质材料是指采用质量轻、强度大的材料替代目前车门的的钢制材料,目前,常用的轻质材料有铝合金型材、高强度复合树脂和碳纤维材料。其中,高强度树脂凭借自身比重小、隔音隔热、耐腐蚀、吸收冲击能量、比强度高、成本低、易加工、装饰效果好等诸多优点,已然成为汽车轻量化中轻质材料的发展趋势。
酚醛树脂原料易得,价格低廉,生产工艺和设备简单,而且产品具有优异的机械性、耐热性、耐寒性、电绝缘性、尺寸稳定性、成型加工性、阻燃性及烟雾性,具有广泛的用途,但是,传统未改性的酚醛树脂脆性大、韧性差,很大程度上限制了高性能材料的开发。
发明内容
本发明的目的是为了克服现有技术存在的问题,提供一种轻质隔音酚醛树脂,该轻质隔音酚醛树脂具有强度高、韧性好、质量轻的特点,在汽车发动机盖板上具有广阔的应用前景。
为了实现上述目的,本发明提供一种轻质隔音酚醛树脂,所述轻质隔音酚醛树脂包括相互独立包装的组分A、组分B、组分C和组分D;以酚原料为100重量份计,所述组份A包括:第一聚合物乳液10~30重量份、发泡剂0.6~10重量份;
所组份B包括:第二聚合物乳液18~56重量份、可溶性金属盐1~6重量份、扩链剂10~30重量份;
所组份C包括:酚原料100重量份、醛原料40~120、催化剂10~30重量份;
所组份D包括:有机溶剂200~400重量份。
通过上述技术方案,本发明通过在酚醛树脂中加入具有多重孔结构的复合纤维,多孔结构一方面可以降低体系的质量,另一方面还可以阻挡声音的传播,起到隔音的作用。此外,由于该复合纤维由内芯和外壁双重结构构成,具有较高的强度和高韧性,能够增强酚醛树脂的强度和韧性。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。
为了提高酚醛树脂的强度和韧性,降低酚醛树脂的质量,本发明提供一种轻质隔音酚醛树脂,包括酚醛树脂和分散在酚醛树脂内部的复合纤维,所述复合纤维包括具有大孔的内芯和含有介孔的外壁。
本发明中,通过在酚醛树脂中加入具有多重孔结构的复合纤维,一方面可以降低体系的质量,另一方面还可以阻挡声音的传播,起到隔音的作用。此外,由于该复合纤维由内芯和外壁双重结构构成,具有较高的强度和高韧性,能够增强酚醛树脂的强度和韧性。
为了进一步优化复合纤维的韧性,优选情况下,所述内芯中大孔的孔径范围为50~100nm,所述外壁上介孔的孔径范围为10~45nm。
为了进一步优化复合纤维的韧性,优选情况下,所述内芯的直径为0.5~2μm,所述外壁的厚度为50~150nm。
本发明中,酚醛树脂与复合纤维的配比是影响酚醛树脂性能的重要因素,为了优化酚醛树脂的强度和韧性,优选情况下,所述酚醛树脂与所述复合纤维的质量比为1:(0.1~0.25)。
根据本发明,优选情况下,所述内芯选自多孔聚偏氟乙烯纤维、多孔聚对苯二甲酸乙二酯纤维、多孔聚对苯二甲酸乙二酯纤维、多孔聚芳酯纤维、多孔聚醋酸乙烯纤维、多孔尼龙6纤维、多孔聚甲基丙烯酸甲酯纤维、多孔聚苯胺纤维纤维、多孔聚氧化乙烯纤维、多孔聚乙烯吡咯烷酮纤维中的至少一种。
根据本发明,优选情况下,所述外壁的材料选自聚偏氟乙烯、聚对苯二甲酸乙二酯、聚对苯二甲酸乙二酯、聚芳酯、聚醋酸乙烯、尼龙6、聚甲基丙烯酸甲酯、聚苯胺、聚氧化乙烯、聚乙烯吡咯烷酮中的至少一种。
在本发明的另一个优选实施方式中,所述轻质隔音酚醛树脂包括相互独立包装的组分A、组分B、组分C和组分D;以酚原料为100重量份计,所述组份A包括:第一聚合物乳液10~30重量份、发泡剂0.6~10重量份;所组份B包括:第二聚合物乳液18~56重量份、可溶性金属盐1~6重量份、扩链剂10~30重量份;所组份C包括:酚原料100重量份、醛原料40~120重量份、催化剂10~30重量份;所组份D包括:有机溶剂200~400重量份。
为了优化酚醛树脂的强度和韧性,优选情况下,所述轻质隔音酚醛树脂包括相互独立包装的组分A、组分B、组分C和组分D;以酚原料为100重量份计,所述组份A包括:第一聚合物乳液20~24重量份、发泡剂2~6重量份;所组份B包括:第二聚合物乳液18~22重量份、可溶性金属盐2~4重量份、扩链剂20~24重量份;所组份C包括:酚原料100重量份、醛原料110~120、催化剂16~24重量份;所组份D包括:有机溶剂240~360重量份。
本发明还提供一种轻质隔音酚醛树脂的制备方法,包括以下步骤:
(1)将第一聚合物乳液和发泡剂混合均匀后进行纺丝,得到聚合物纤维;
(2)将聚合物纤维、扩链剂和可溶性金属盐置于第二聚合物乳液中,在60~100℃下反应15~60min,然后在酸性溶液中浸泡,然后在150~200℃下处理15~30min,得到复合纤维;
(3)将酚醛树脂单体、催化剂和复合纤维在有机溶剂中混合均匀后,在80~120℃下回流3~5h,得到轻质隔音酚醛树脂。
根据本发明,本发明中通过将发泡剂与第一聚合物乳液混合,并进行静电纺丝,生成含有发泡剂的聚合物纤维,发泡剂经高温分解后,在聚合物纤维内部形成孔隙,因此,发泡剂是形成聚合物内部空隙的重要成分之一,优选情况下,所述发泡剂选自4,4-氧代双苯磺酰肼、偶氮二甲酰胺、N,N’-二亚硝基五次甲基四胺中的至少一种。
根据本发明,优选情况下,所述聚合物乳液选自聚偏氟乙烯乳液、聚对苯二甲酸乙二酯乳液、聚对苯二甲酸乙二酯乳液、聚芳酯乳液、聚醋酸乙烯乳液、尼龙6乳液、聚甲基丙烯酸甲酯乳液、聚苯胺乳液、聚氧化乙烯乳液、聚乙烯吡咯烷酮乳液中的至少一种。
根据本发明,优选情况下,所述第一聚合物乳液的固含量为23~75%。根据本发明,优选情况下,所述第二聚合物乳液的固含量为16~63%。
根据本发明,本发明对酸性溶液的种类没有特殊的要求,可以为盐酸、硫酸、硝酸等中的至少一种。
根据本发明,将聚合物纤维在含有可溶性金属盐和扩链剂的第二聚合物乳液中反应,可以在聚合物纤维的表面生成含有金属离子的聚合物外壁,聚合物外壁中的金属离子能够在酸性溶液中发生迁移,从聚合物外壁上迁移至溶液中,从而在聚合物外壁上形成微孔结构。
可溶性金属盐是形成外壁上介孔结构的重要因素,优选情况下,所述可溶性金属盐选自钠盐、钾盐、可溶性铜盐、可溶性锌盐、可溶性铁盐、可溶性镍盐、可溶性钴盐和可溶性锰盐中的至少一种,更具体的,所述可溶性金属盐选自氯化钠、硫酸钠、硝酸钠、氯化钾、硫酸钾、硝酸钾、氯化铁、硫酸铜、硝酸锌、氯化锌、氯化铁、硫酸镍、硝酸镍、醋酸镍、氯化镍、硫酸钴、硝酸钴、醋酸钴、氯化钴、硫酸锰、硝酸锰、醋酸锰、氯化锰中的至少一种。
根据本发明,优选情况下,所述酚原料选自苯酚、邻甲苯酚、间甲苯酚、对甲苯酚、对羟甲基苯酚、邻苯二酚、间苯二酚和对苯二酚中的至少一种。进一步优选的,所述醛原料自甲醛、乙醛、丙醛、丁醛、丙烯醛、环己酮二甲基缩醛、苯甲醛、糠醛、杂环醛、多聚甲醛、三聚甲醛中的至少一种。
根据本发明,本发明中,通过添加催化剂,催化酚原料和醛原料进行聚合反应,优选情况下,所述催化剂选自碱金属氢氧化物、碱土金属氢氧化物、碳酸盐和碳酸氢盐中的至少一种。
根据本发明,优选情况下,所述扩链剂选自脂肪族二醇、芳香族二醇中的至少一种。其中所述脂肪族二醇选自乙二醇、1,3-丁二醇、1,10-葵二醇、1,4-环己二醇、1,8-辛二醇、新戊二醇、2-甲基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇和3-甲基-1,5-戊二醇中的至少一种;其中所述芳香族二醇选自对苯二酚双羟乙基醚和/或间苯二酚双羟乙基醚。
根据本发明,其中对有机溶剂的种类没有特殊的要求,优选情况下,所述有机溶剂选自丙酮、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、N,N-二甲基乙酰胺、二甲基乙酰胺、二氯甲烷、磷酸三乙酯、三氯甲烷、甲苯、乙醇、醋酸、乙酸乙酯、甲酸、氯仿、四氢呋喃、液体石蜡和二甲基亚砜中的至少一种。
本发明中,将聚合物乳液与发泡剂进行混合后进行纺丝,及得到含有发泡剂的聚合物纤维,再将聚合物纤维与可溶性金属盐在聚合物乳液中进行聚合反应,在聚合物纤维表面生成含有金属离子的外壁,得到复合纤维A,再将其置于酸性溶液中浸泡,对金属离子进行洗脱,形成含有介孔结构的外壁,得到复合纤维B,将复合纤维B在高温下热处理,使发泡剂分解,在内芯中形成大孔,即得到复合纤维。
通过在酚醛树脂中加入具有多重孔结构的复合纤维,多孔结构一方面可以降低体系的质量,另一方面还可以阻挡声音的传播,起到隔音的作用。此外,由于该复合纤维由内芯和外壁双重结构构成,具有较高的强度和高韧性,起到增强酚醛树脂的作用。本发明在酚醛树脂的合成过程中加入复合纤维,能够提高酚醛树脂与复合纤维间的结合力,从而提高复合纤维在酚醛树脂中的稳定性。
根据本发明,优选情况下,所述纺丝的工艺为:电源电压10~60KV,纺丝环境条件为温度15~35℃,相对湿度25~90%;多针头喷丝单元针头间距2~30cm,喷丝单元针头数量为6~90个。
根据本发明,本发明通过控制发泡剂与第一部分聚合物乳液的比例,调节内芯中大孔的含量,优选情况下,在步骤(1)中,所述发泡剂与所述聚合物乳液的质量比为1:(5~10)。
根据本发明,本发明通过控制可溶性金属盐与第二部分聚合物乳液的比例,调节外壁中介孔的含量,优选情况下,在步骤(2)中,所述可溶性金属盐与第二部分聚合物乳液的质量比为1:(5~7.5)。
根据本发明,本发明通过将复合纤维A在酸性溶液中浸泡,对金属离子进行洗脱,从而形成含有介孔结构的外壁,优选情况下,在步骤(2)中,所述酸性溶液的pH值为1~5。为了提高金属离子的洗脱效率,进一步优选的,在浸泡过程中,每隔30min换一次浸泡液,至浸泡液的pH值不再发生变化。
本发明还提供了一种轻质隔音发动机盖板,所述轻质隔音发动机盖板由发动机骨架和包覆在骨架外的涂层,所述发动机骨架采用根据本发明所述的轻质隔音酚醛树脂冲压成型制得。
在本发明的一个优选情况下实施方式中,以环氧树脂的重量为100计,所述涂层包括以下重量份的物质:环氧树脂100份、甲基丙烯酸丁酯30~58份、还原氧化石墨烯5~15份、流平剂2~6份。
优选的,所述流平剂选自聚二甲基硅氧烷和/或聚甲基苯基硅氧烷;所述固化剂可以采用乙二胺、己二胺、甲基环已二胺、1,4-丁二胺、1,5-戊二胺、2-甲基-1,5-戊二胺、2-丁基-2-乙基-1,5-戊二胺、1,6-己二胺、2,2,4-三甲基己二胺、2,4,4-三甲基己二胺、1,8-辛二胺、2-甲基-1,8-辛二胺、1,9-壬二胺、1,10-癸二胺、1,11-十一烷二胺、1,12-十二烷二胺、1,13-十三烷二胺、1,14-十四烷二胺、1,15-十五烷二胺、2-甲基-2,4-戊二醇、1,16-十六烷二胺及1,18-1,14-十八烷二胺、二甲硫基甲苯二胺中的至少一种。
本发明还提供一种轻质隔音发动机盖板的制备方法,包括以下步骤:
(1)发动机骨架的制备:所述发动机骨架采用根据本发明所述的轻质隔音酚醛树脂冲压成型制得,所述轻质隔音酚醛树脂的制备方法参见本发明前述关于轻质隔音酚醛树脂的制备方法的描述。
(2)涂层喷涂:将环氧树脂、甲基丙烯酸丁酯、还原氧化石墨烯、流平剂、润湿剂、固化剂在有机溶剂中混合均匀,形成涂层乳液,然后将涂层乳液喷涂在芯材表面,固化后,形成涂层。
本发明涂层乳液的固化工艺可以为环氧树脂的常用固化工艺,例如可以是在120℃下固化45min。
本发明中,在发动机骨架的制备过程中,所述发动机骨架的冲压成型可以为现有技术中常用的冲压工艺,例如可以为:将轻质隔音酚醛树脂在温度为80℃,压强为10MPa的条件下冲压时间为15min,冲压结束后,在10min以内将冲压模具和制件的温度降低至室温。
本发明中,将聚合物乳液与发泡剂进行混合后进行纺丝,及得到含有发泡剂的聚合物纤维,再将聚合物纤维与可溶性金属盐在聚合物乳液中进行聚合反应,在聚合物纤维表面生成含有金属离子的外壁,得到复合纤维A,再将其置于酸性溶液中浸泡,对金属离子进行洗脱,形成含有介孔结构的外壁,得到复合纤维B,将复合纤维B在高温下热处理,使发泡剂分解,在内芯中形成大孔,即得到复合纤维。
通过在酚醛树脂中加入具有多重孔结构的复合纤维,多孔结构一方面可以降低体系的质量,另一方面还可以阻挡声音的传播,起到隔音的作用。此外,由于该复合纤维由内芯和外壁双重结构构成,具有较高的强度和高韧性,起到增强酚醛树脂的作用。本发明在酚醛树脂的合成过程中加入复合纤维,能够提高酚醛树脂与复合纤维间的结合力,从而提高复合纤维在酚醛树脂中的稳定性,即提高发动机盖板的稳定性。
以下将通过实施例对本发明进行详细描述。以下实施例中,采用排水法测试各样品的密度。按照GB/T1447-2005的方法测试各样品的拉伸性能。按照GB/T1040.1-2006的方法测试各样品的断裂伸长率。按照GB/T1451-2005的方法测试各样品的冲击韧性。按照GB/T18696.2-2002的方法测试各样品的吸声系数。测试样品是直径为7.8cm,厚度为1.2cm的圆片,测试频率范围为100~2500Hz。
实施例1
(1)发动机骨架的制备:
A、将24g聚对苯二甲酸乙二酯乳液、6g4,4-氧代双苯磺酰肼混合均匀后进行纺丝,得到聚对苯二甲酸乙二酯纤维,纺丝工艺为:电源电压30KV,纺丝环境条件为温度25℃,相对湿度60%;多针头喷丝单元针头间距15cm,喷丝单元针头数量为45个;
B、取22g聚对苯二甲酸乙二酯纤维、20g乙二醇和3g硝酸锌置于12g聚对苯二甲酸乙二酯乳液中,在80℃下反应45min,得到复合纤维A,然后将复合纤维A在pH为3的盐酸溶液中浸泡2h,其中每15min更换一次盐酸溶液,得到复合纤维B,将复合纤维B在180℃下处理15min,得到复合纤维C;
所述复合纤维C由具有大孔的内芯和含有介孔的外壁组成,其中内芯中大孔的孔径范围为80nm;外壁上介孔的孔径范围为15nm;内芯的直径为1μm;所述外壁的厚度为60nm。
C、将100g邻甲苯酚、120g三聚甲醛、20g氢氧化钾和复合纤维C在300gN-甲基吡咯烷酮中混合均匀后,在100℃下回流3.5h,得到轻质隔音酚醛树脂;
D、将轻质隔音酚醛树脂在温度为80℃,为10MPa的条件下冲压15min,冲压结束后,在10min以内将冲压模具和制件的温度降低至室温,得到发动机骨架。
(2)轻质隔音发动机盖板:
在发动机骨架表面喷涂涂层,喷涂涂层的步骤包括:将100g三聚氰胺环氧树脂、45g甲基丙烯酸丁酯、8g还原氧化石墨烯、4g聚甲基苯基硅氧烷、15g二甲硫基甲苯二胺在N,N-二甲基甲酰胺中混合均匀,形成涂层乳液,然后将涂层乳液喷涂在芯材表面,在120℃下固化45min,形成涂层。
实施例2
(1)发动机骨架的制备:
A、将20g尼龙6乳液和2g4,4-氧代双苯磺酰肼混合均匀后进行纺丝,得到尼龙6纤维,纺丝工艺为:电源电压30KV,纺丝环境条件为温度25℃,相对湿度60%;多针头喷丝单元针头间距15cm,喷丝单元针头数量为45个;
B、取18g尼龙6纤维、24g1,3-丁二醇和2g醋酸钴置于10g尼龙6乳液中,在80℃下反应30min,得到复合纤维A,然后将复合纤维A在pH为2的盐酸溶液中浸泡1.5h,其中每15min更换一次盐酸溶液,得到复合纤维B,将复合纤维B在150℃下处理30min,得到复合纤维C;
所述复合纤维C由具有大孔的内芯和含有介孔的外壁组成,其中内芯中大孔的孔径范围为60nm;外壁上介孔的孔径范围为20nm;内芯的直径为1.5μm;所述外壁的厚度为100nm。
C、将100g间甲苯酚、135g多聚甲醛、16g氢氧化钾和复合纤维C在240gN-甲基吡咯烷酮中混合均匀后,在110℃下回流3.5h,得到轻质隔音酚醛树脂;
D、将轻质隔音酚醛树脂在温度为80℃,压强为10MPa的条件下,冲压15min,冲压结束后,在10min以内将冲压模具和制件的温度降低至室温。
(2)轻质隔音发动机盖板:
在发动机骨架表面喷涂涂层,喷涂涂层的步骤包括:将100g三聚氰胺环氧树脂、45g甲基丙烯酸丁酯、8g还原氧化石墨烯、4g聚甲基苯基硅氧烷、15g二甲硫基甲苯二胺在N,N-二甲基甲酰胺中混合均匀,形成涂层乳液,然后将涂层乳液喷涂在芯材表面,在120℃下固化45min,形成涂层。
实施例3
(1)发动机骨架的制备:
A、将10g聚醋酸乙烯乳液和2g偶氮二甲酰胺混合均匀后进行纺丝,得到聚醋酸乙烯纤维,纺丝工艺为:电源电压30KV,纺丝环境条件为温度25℃,相对湿度60%;多针头喷丝单元针头间距15cm,喷丝单元针头数量为45个;
B、取9g聚醋酸乙烯纤维、24g新戊二醇和4g硫酸锰置于30g聚醋酸乙烯乳液中,在75℃下反应45min,得到复合纤维A,然后将复合纤维A在pH为4.2的盐酸溶液中浸泡2h,其中每10min更换一次盐酸溶液,得到复合纤维B,将复合纤维B在200℃下处理25min,得到复合纤维C;
所述复合纤维C由具有大孔的内芯和含有介孔的外壁组成,其中内芯中大孔的孔径范围为80nm;外壁上介孔的孔径范围为30nm;内芯的直径为0.8μm;所述外壁的厚度为120nm。
C、将100g对苯二酚、40g甲醛、24g氢氧化钾和复合纤维C在360g二甲基乙酰胺中混合均匀后,在100℃下回流4h,得到轻质隔音酚醛树脂;
D、将轻质隔音酚醛树脂在温度为80℃,压强为10MPa的条件下,冲压15min,冲压结束后,在10min以内将冲压模具和制件的温度降低至室温。
(2)轻质隔音发动机盖板:
在发动机骨架表面喷涂涂层,喷涂涂层的步骤包括:将100g三聚氰胺环氧树脂、45g甲基丙烯酸丁酯、8g还原氧化石墨烯、4g聚甲基苯基硅氧烷、15g二甲硫基甲苯二胺在N,N-二甲基甲酰胺中混合均匀,形成涂层乳液,然后将涂层乳液喷涂在芯材表面,在120℃下固化45min,形成涂层。
实施例4
(1)发动机骨架的制备:
A、将30g聚芳酯乳液、2-甲基-1,3-丙二醇和10g偶氮二甲酰胺混合均匀后进行纺丝,得到聚芳酯纤维,纺丝工艺为:电源电压60KV,纺丝环境条件为温度35℃,相对湿度90%;多针头喷丝单元针头间距30cm,喷丝单元针头数量为90个;
B、取28g聚芳酯纤维、30g2-甲基-1,3-丙二醇和6g硫酸钾置于20g聚芳酯乳液中,在100℃下反应15min,得到复合纤维A,然后将复合纤维A在pH为1的盐酸溶液中浸泡1h,其中每10min更换一次盐酸溶液,得到复合纤维B,将复合纤维B在200℃下处理30min,得到复合纤维C;
所述复合纤维C由具有大孔的内芯和含有介孔的外壁组成,其中内芯中大孔的孔径范围为50nm;外壁上介孔的孔径范围为10nm;内芯的直径为0.5μm;所述外壁的厚度为50nm。
C、将100g对甲基苯酚、65g甲醛、10g氢氧化钾和复合纤维C在200g二甲基乙酰胺中混合均匀后,在120℃下回流3h,得到轻质隔音酚醛树脂;
D、将轻质隔音酚醛树脂在温度为80℃,压强为10MPa的条件下冲压15min,冲压结束后,在10min以内将冲压模具和制件的温度降低至室温。
(2)轻质隔音发动机盖板:
在发动机骨架表面喷涂涂层,喷涂涂层的步骤包括:将100g三聚氰胺环氧树脂、45g甲基丙烯酸丁酯、8g还原氧化石墨烯、4g聚甲基苯基硅氧烷、15g二甲硫基甲苯二胺在N,N-二甲基甲酰胺中混合均匀,形成涂层乳液,然后将涂层乳液喷涂在芯材表面,在120℃下固化45min,形成涂层。
实施例5
(1)发动机骨架的制备:
A、将15g聚甲基丙烯酸甲酯乳液和0.6g4,4-氧代双苯磺酰肼混合均匀后进行纺丝,得到聚甲基丙烯酸甲酯纤维,纺丝工艺为:电源电压10KV,纺丝环境条件为温度15℃,相对湿度25%;多针头喷丝单元针头间距2cm,喷丝单元针头数量为6个;
B、取13g聚甲基丙烯酸甲酯纤维、10g1,8-辛二醇和1g氯化钠置于5g聚甲基丙烯酸甲酯乳液中,在60℃下反应60min,得到复合纤维A,然后将复合纤维A在pH为5的盐酸溶液中浸泡3h,其中每15min更换一次盐酸溶液,得到复合纤维B,将复合纤维B在150℃下处理20min,得到复合纤维C;
所述复合纤维C由具有大孔的内芯和含有介孔的外壁组成,其中内芯中大孔的孔径范围为100nm;外壁上介孔的孔径范围为45nm;内芯的直径为2μm;所述外壁的厚度为150nm。
C、将100g对苯二酚、65g乙醛、30g氢氧化钾和复合纤维C在400g乙酸乙酯中混合均匀后,在80℃下回流5h,得到轻质隔音酚醛树脂;
D、将轻质隔音酚醛树脂在冲压温度为80℃,压强为10MPa的条件下,冲压15min,冲压结束后,在10min以内将冲压模具和制件的温度降低至室温。
(2)轻质隔音发动机盖板:
在发动机骨架表面喷涂涂层,喷涂涂层的步骤包括:将100g三聚氰胺环氧树脂、45g甲基丙烯酸丁酯、8g还原氧化石墨烯、4g聚甲基苯基硅氧烷、15g二甲硫基甲苯二胺在N,N-二甲基甲酰胺中混合均匀,形成涂层乳液,然后将涂层乳液喷涂在芯材表面,在120℃下固化45min,形成涂层。
对比例1
按照实施例1的方法,不同的是,在轻质隔音酚醛树脂的制备中不添加发泡剂。
对比例2
按照实施例1的方法,不同的是,在轻质隔音酚醛树脂的制备中不含有步骤B。
对比例3
按照实施例1的方法,不同的是,在轻质隔音酚醛树脂的制备中不添加可溶性金属盐。
对比例4
按照实施例1的方法,不同的是,直接在酚醛树脂中添加聚对苯二甲酸乙二酯纤维。
表1实施例1~5和对比例1~4中各阻燃高强度轻质树脂的的性能表
以上详细描述了本发明的优选实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的内容,均属于本发明的保护范围。
Claims (10)
1.一种轻质隔音酚醛树脂,其特征在于,所述轻质隔音酚醛树脂包括相互独立包装的组分A、组分B、组分C和组分D;以酚原料为100重量份计,所述组份A包括:第一聚合物乳液10~30重量份、发泡剂0.6~10重量份;
所组份B包括:第二聚合物乳液18~56重量份、可溶性金属盐1~6重量份、扩链剂10~30重量份;
所组份C包括:酚原料100重量份、醛原料40~120重量份、催化剂10~30重量份;
所组份D包括:有机溶剂200~400重量份。
2.根据权利要求1所述的轻质隔音酚醛树脂,其中,以酚原料为100重量份计,所述组份A包括:第一聚合物乳液20~24重量份、发泡剂2~6重量份;
所组份B包括:第二聚合物乳液18~22重量份、可溶性金属盐2~4重量份、扩链剂20~24重量份;
所组份C包括:酚原料100重量份、醛原料110~120重量份、催化剂16~24重量份;
所组份D包括:有机溶剂240~360重量份。
3.根据权利要求1或2所述的轻质隔音酚醛树脂,其中,所述发泡剂选自4,4-氧代双苯磺酰肼、偶氮二甲酰胺、N,N’-二亚硝基五次甲基四胺中的至少一种。
4.根据权利要求1所述的轻质隔音酚醛树脂,其中,所述第一聚合物乳液和第二聚合物乳液各自独立的选自聚偏氟乙烯乳液、聚对苯二甲酸乙二酯乳液、聚芳酯乳液、聚醋酸乙烯乳液、尼龙6乳液、聚甲基丙烯酸甲酯乳液、聚苯胺乳液、聚氧化乙烯乳液、聚乙烯吡咯烷酮乳液中的至少一种。
5.根据权利要求4所述的轻质隔音酚醛树脂,其中,所述第一聚合物乳液的固含量为23~75%;和/或
所述第二聚合物乳液的固含量为16~63%。
6.根据权利要求1所述的轻质隔音酚醛树脂,其中,所述可溶性金属盐选自钠盐、钾盐、可溶性铜盐、可溶性锌盐、可溶性铁盐、可溶性镍盐、可溶性钴盐和可溶性锰盐中的至少一种。
7.根据权利要求1所述的轻质隔音酚醛树脂,其中,所述酚单体选自苯酚、邻甲苯酚、间甲苯酚、对甲苯酚、对羟甲基苯酚、邻苯二酚、间苯二酚和对苯二酚中的至少一种;
所述醛单体选自甲醛、乙醛、丙醛、丁醛、丙烯醛、环己酮二甲基缩醛、苯甲醛、糠醛、杂环醛、多聚甲醛、三聚甲醛中的至少一种。
8.根据权利要求1所述的轻质隔音酚醛树脂,其中,所述催化剂选自碱金属氢氧化物、碱土金属氢氧化物、碳酸盐和碳酸氢盐中的至少一种。
9.根据权利要求1所述的轻质隔音酚醛树脂,其中,所述扩链剂选自所述扩链剂选自脂肪族二醇和/或芳香族二醇。
10.根据权利要求1所述的轻质隔音酚醛树脂,其中,所述有机溶剂选自丙酮、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、N,N-二甲基乙酰胺、二甲基乙酰胺、二氯甲烷、磷酸三乙酯、三氯甲烷、甲苯、乙醇、醋酸、乙酸乙酯、甲酸、氯仿、四氢呋喃、液体石蜡和二甲基亚砜中的至少一种。
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