CN104870514B - 适用于环氧树脂的硬化剂或增塑剂的苯乙烯酚 - Google Patents
适用于环氧树脂的硬化剂或增塑剂的苯乙烯酚 Download PDFInfo
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- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 25
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 24
- 239000004014 plasticizer Substances 0.000 title claims abstract description 18
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims abstract description 28
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims description 31
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- BOLQUPOXTWHXIX-UHFFFAOYSA-N OC1=CC=CC=C1.C=1C=CC=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound OC1=CC=CC=C1.C=1C=CC=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 BOLQUPOXTWHXIX-UHFFFAOYSA-N 0.000 claims description 3
- 229920006334 epoxy coating Polymers 0.000 abstract description 11
- 150000002989 phenols Chemical class 0.000 abstract description 2
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- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
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- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
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- 238000005804 alkylation reaction Methods 0.000 description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- -1 1- phenethyl Chemical group 0.000 description 1
- NYPMHOYLEBBBGY-UHFFFAOYSA-N 2,6-bis(1-phenylethyl)phenol Chemical compound C=1C=CC(C(C)C=2C=CC=CC=2)=C(O)C=1C(C)C1=CC=CC=C1 NYPMHOYLEBBBGY-UHFFFAOYSA-N 0.000 description 1
- WYZIVNCBUWDCOZ-UHFFFAOYSA-N 2-(1-phenylethyl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)C1=CC=CC=C1 WYZIVNCBUWDCOZ-UHFFFAOYSA-N 0.000 description 1
- HBMHZKUEKASKNY-UHFFFAOYSA-N 2-nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O.CCCCCCCCCC1=CC=CC=C1O HBMHZKUEKASKNY-UHFFFAOYSA-N 0.000 description 1
- XHASMJXNUHCHBL-UHFFFAOYSA-N 4-(1-phenylethyl)phenol Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=CC=C1 XHASMJXNUHCHBL-UHFFFAOYSA-N 0.000 description 1
- 101000705294 Arabidopsis thaliana Oxygen-evolving enhancer protein 1-2, chloroplastic Proteins 0.000 description 1
- 101100249009 Bacillus subtilis (strain 168) rplK gene Proteins 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
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- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
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- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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Abstract
本发明涉及适用于环氧树脂的硬化剂或增塑剂的苯乙烯酚,更详细地说,涉及苯乙烯酚具有与壬基酚近似的粘度特性及硬化特性,特别是,对于环氧树脂的硬化特性优异而将苯乙烯酚用作为环氧硬化涂料用硬化剂或增塑剂。
Description
技术领域
本发明涉及适用于环氧树脂的硬化剂或增塑剂的苯乙烯酚。
背景技术
由于环氧树脂在其硬化物的机械特性、电学特性、热特性、耐化学性、粘接性等方面有优异的性能,所以广泛用于涂料、电用绝缘材料、粘接剂等的用途。
此外,环氧树脂的硬化应力、硬度、耐日光性、加工性等物理属性优异,并且不用担心在硬化时产生挥发性物质或体积的收缩,因此有时将合适的硬化剂混合到环氧树脂而用作为适用于混凝土原料的涂料。与用于混凝土保护的其它类型的涂料相比,环氧硬化型涂料收缩性小、抗机械化学性大而适合作为高性能涂料。
另一方面,壬基酚(Nonylphenol)因其固有的物理化学特性而在环氧硬化型涂料领域中用作为硬化剂或增塑剂,从而在各种产业领域中以广泛的用途加以使用。然而,自传出壬基酚为对肾脏有毒性以及使内分泌***的荷尔蒙混乱物质之后,业界禁止使用或逐渐限制了使用范围。特别是,在欧洲于2003年已经在一部分领域中全面禁止使用壬基酚或者限制在产品中壬基酚不超载0.1%以上。在“EU Directive 2003/53/EC”或EU REACH中也一致限定并管理。关于“REACH法令集Annex17限制物质”,在国内也通告了壬基酚的危险性并加强了使用规定,并且从2010年1月起对一部分产品进行了全面禁止。
然而,壬基酚的替代物尚未得到开发而给业界带来了很大的困难。要作为壬基酚的替代物使用,首先要具有与壬基酚同等乃至近似的物理化学特性。
于是,本发明人们考虑到苯乙烯酚的粘度特性及硬化特性近似于壬基酚这一点,作为替代用作为环氧树脂的硬化剂或增塑剂的壬基酚的物质,研究适用苯乙烯酚的可能性。
苯乙烯酚是通过苯酚与苯乙烯的烃化反应来制造的。作为苯乙烯酚可以存在以下三种化合物,即,在苯酚的苯环键合一个苯乙烯的单苯乙烯酚(MSP);键合两个苯乙烯的双苯乙烯酚(DSP);以及键合三个苯乙烯的三苯乙烯酚(TSP)。这种苯乙烯酚主要作为合成橡胶或树脂的防氧化剂使用,到目前为止还没有将苯乙烯酚用作为环氧树脂的硬化剂或增塑剂的报告文献。
发明内容
本发明的目的在于提供将苯乙烯酚用作为环氧树脂的硬化剂的用途。
此外,本发明的目的在于提供将苯乙烯酚用作为环氧树脂的增塑剂的用途。
此外,本发明的目的在于提供作为硬化剂或增塑剂包含苯乙烯酚的环氧树脂涂料。
为了解决上述课题,本发明的环氧树脂的硬化剂或增塑剂,其特征在于:包含由以下化学式1表示的苯乙烯酚。
[化学式1]
(上述化学式1中,n为1、2或3)。
此外,本发明的环氧涂料,其特征在于,包括:包含环氧树脂的主要成分、和包含以上述化学式1表示的苯乙烯酚的硬化剂部分。
发明效果
苯乙烯酚不仅具有近似于壬基酚的物理化学特性,而且因为壬基酚拥有的固有的适用性而同时保存着粘度改善及硬化促进性能,因此可作为壬基酚的替代物适用。即,苯乙烯酚可作为环氧树脂的硬化剂或增塑剂适用。
此外,在作为包括包含环氧树脂的主要成分、和包含以上述化学式1表示的苯乙烯酚的硬化剂部分的环氧涂料适用时,对混凝土原料的附着性优异,在硬化时涂膜的收缩性小,硬化涂膜的抗机械/化学性优异,因此可作为厚膜型涂料适用。
具体实施方式
本发明涉及通过确认苯乙烯酚拥有的粘度特性及硬化特性近似于壬基酚,在制造环氧硬化型涂料时将苯乙烯酚用作为硬化剂或增塑剂的情形。
本发明中的苯乙烯酚可由以下化学式1表示:
[化学式1]
(上述化学式1中n为1、2或3)。
本发明中关于以上述化学式1表示的苯乙烯酚的命名,将n=1的化合物简称为“MSP”,将n=2的化合物简称为“DSP”,将n=3的化合物简称为“TSP”。
对于以上述化学式1表示的苯乙烯酚,NSP具体能包含2-(1-苯乙基)苯酚(MSP-1)和4-(1-苯乙基)苯酚(MSP-2)。
此外,对于以上述化学式1表示的苯乙烯酚,DSP具体能包含2,4-二(1-苯乙基)苯酚(DSP-1)和2,6-二(1-苯乙基)苯酚(DSP-2)。
此外,对于以上述化学式1表示的苯乙烯酚,TSP具体能包含2,4,6-三(1-苯乙基)苯酚(TSP-1)。
以上述化学式1表示的苯乙烯酚,通过在氧催化剂下将苯酚与苯乙烯加热到100-150℃温度的条件下使之烃化反应来制造。具体地说,对于1mol的苯酚使1-1.5mol 的苯乙烯反应,则生成以MSP:DSP:TSP = 50-75:15-35:1-8 重量%的含量比包含MSP、DSP、TSP的化合物。
MSP、DSP、TSP的重量比取决于用作为反应物质的苯酚与苯乙烯的反应物比。适合于本发明的苯乙烯酚,MSP的含量最好在50重量%以上,优选调整在50-75重量%。如此,在本发明中使用MSP的含量较高的苯乙烯酚,理由在于MSP的含量越高粘度越低,在与环氧树脂混合使用时会赋予增塑性,使作业性提高,羟基值(OH value)维持为与壬基酚(240-250)相同,从而促进硬化反应。
在下述表1中比较以产品Kumanox-3110商用的苯乙烯酚和分类为使用限制物质的壬基酚的物理属性并加以示出。
[表1]
如上述表1所示,可知苯乙烯酚为非毒性物质而具有环境亲和性优异的优点,并且重量平均分子量、OH值、粘度、颜色值、水分含量几乎与壬基酚近似。特别是,苯乙烯酚的粘度被维持为比壬基酚低,因此具有在与环氧树脂混合使用时进一步提高塑性而作业性优异的特殊的优点。
因而,以上述化学式1表示的苯乙烯酚,可作为壬基酚的替代物使用,而且是非毒性物质,因此环境亲和性优异。
另一方面,本发明的特征在于,将以上述化学式1表示的苯乙烯酚用作为包含环氧树脂作为主要成分的环氧涂料用硬化剂的用途。
上述环氧涂料可具体分为环氧主要成分和硬化剂部分。构成环氧涂料主要成分中包含环氧树脂、非反应性稀释剂、增塑剂等,硬化剂部分硬化促进剂、增塑剂等。关于环氧涂料的组成成分及成分比,迄今为止进行多方面研究,在本发明中并不特别限制这些组成成分及成分比。本发明中环氧涂料的特征在于:作为构成硬化剂部分的硬化剂或增塑剂适用以上述化学式1表示的苯乙烯酚。包含苯乙烯酚的硬化剂部分,具体作为硬化剂或增塑剂包含1-40重量%的苯乙烯酚和60-99重量%的普通环氧硬化剂。本发明的实施例中具体列举了作为普通的环氧硬化剂使用聚醚二胺类硬化剂的例子,但是本发明并不对普通的环氧硬化剂成分的选择特别做限制。
包含这样的苯乙烯酚的硬化剂部分,在作为2液型环氧涂料使用时由于涂料的粘度低而易于作业,并且缩短硬化时间而改善作业性,涂敷表面的硬度增加而具有提高耐久性的效果。
相对于环氧主要成分100重量份,硬化剂部分通常在1-40重量份的范围内混合而形成硬化涂膜。
通过以下实施例进一步详细说明如以上说明的本发明,但本发明并不局限于此。
此外,下面的实施例中测定的物理属性是通过以下方法来测定的。
[物理属性测定方法]
1)粘度
粘度是用旋转粘度计测定设备(Brookfield HAT viscometer或Brookfield LVDVE 230 viscometer)在25℃下测定的。
2)色相
色相是用颜色测定设备(Nippon Denshoku OME 2000)来测定的。
3)胺值
胺值是利用0.1N-HCl滴定法来测定的。
4)硬化时间
硬化时间是以100g为量级并以25℃(50℃(0.1)泵温度计)为起点在常温下测定。
5)肖氏硬度
硬度是用硬度测定设备(e-Asker Durometer Super EX Type-D)来测定的。最终硬度指的是在80℃下加热2小时硬化后的试样的硬度,在常温下每日测定常温硬化的试样的硬度变化。
[实施例]
实施例1:苯乙烯酚的制造
加入苯酚(300 g)、磷酸(H3PO4)催化剂(1.876 g,0.006 eq)并加热到140℃,徐徐地滴下苯乙烯(381.6 g,1.15 eq)120分钟。随着苯乙烯的滴下,反应温度从140℃上升至170℃。在完成苯乙烯的滴下后,在同一反应温度下使之进一步反应1小时。为了除去未反应物,将反应温度降低到110℃,向反应物添加硫酸(H2SO4)催化剂(0.02 g,相比磷酸催化剂为1-3重量%),随着硫酸的添加,反应温度上升至125℃,以此状态使之进一步反应30分钟。设反应物的温度为80℃,在此以与上述使用硫酸相同的当量比添加碳酸钠水溶液,中和30分钟。生成的中和盐通过减压浓缩来除去水分后过滤而除去,从而得到苯乙烯酚(反应转换率97%,纯度97%以上)。
GC分析以上获得的苯乙烯酚的结果,确认了呈MSP67重量%、DSP27重量%、TSP6重量%的比率。
实验例:环氧涂料用硬化剂部分的制造
2-1)包含苯乙烯酚的硬化剂部分(A)
向聚醚原料的500 mL容量的容器投入D-230(Jeffamine,Kukdo Chemical,聚醚二胺类)198g和在上述制造例中制造的苯乙烯酚102g,用磁性搅拌器进行搅拌。当发热现象结束后升温至70℃并再搅拌30分钟,然后用100筛孔(100Mesh)分子筛来过滤而得到了300g的硬化剂部分(A)。
2-2)包含壬基酚的硬化剂部分(B)
向聚醚原料的500 mL容量的容器投入D-230(Jeffamine,Kukdo Chemical,聚醚二胺类)198g和在上述制造例中制造的壬基酚102g,用磁性搅拌器进行搅拌。当发热现象结束后升温至70℃并再搅拌30分钟,然后用100筛孔分子筛来过滤而得到了300g的硬化剂部分(B)。
对于在上述实施例2中制造的硬化剂部分(A)、(B)的第一个测定了粘度及胺值,并示于以下表2中。
[表2]
实验例:环氧涂料的物理属性比较
向包含KER-828(Kumho P&B Chemical,环氧树脂)90重量%和苯甲醇10重量%的环氧主要成分100重量份,混合在上述2-1)或2-2)中制造的各个硬化剂部分40重量份,进行了硬化。
[表3]
产业上的可利用性
综上所述,苯乙烯酚具有粘度及胺值等的物理属性与壬基酚同等乃至近似的物理化学性质,即便包含在环氧涂料的硬化剂部分,包含苯乙烯酚的硬化剂部分的硬化时间也比包含壬基酚的硬化剂部分的硬化时间短,得到硬化涂膜的硬度高且物理属性优异而改善作业性的效果以及提高耐久性的改善效果。
因而,苯乙烯酚可作为环氧树脂的硬化剂或增塑剂适用。
Claims (2)
1.以下述化学式1表示的苯乙烯酚作为壬基酚的替代物的用途,所述壬基酚作为用于环氧树脂的硬化剂:
[化学式1]
上述化学式1中n为1、2或3,
其中上述苯乙烯酚中,n=1的单苯乙烯酚MSP的含量为50-75重量%,n=2的双苯乙烯酚DSP的含量为15-35重量%,n=3的三苯乙烯酚TSP的含量为1-8重量%。
2.以下述化学式1表示的苯乙烯酚作为壬基酚的替代物的用途,所述壬基酚作为用于环氧树脂的增塑剂:
[化学式1]
上述化学式1中n为1、2或3,
其中上述苯乙烯酚中,n=1的单苯乙烯酚MSP的含量为50-75重量%,n=2的双苯乙烯酚DSP的含量为15-35重量%,n=3的三苯乙烯酚TSP的含量为1-8重量%。
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0335674A2 (en) * | 1988-03-30 | 1989-10-04 | Yoshitomi Pharmaceutical Industries, Ltd. | Selective process for preparing 2,4- or 3,6-di-substituted phenol compounds |
CN102549041A (zh) * | 2009-09-25 | 2012-07-04 | 陶氏环球技术有限责任公司 | 可固化环氧树脂组合物及由其制备的复合材料 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS578221A (en) * | 1980-06-20 | 1982-01-16 | Asahi Denka Kogyo Kk | Curable epoxy resin composition |
JPH01238549A (ja) | 1987-11-24 | 1989-09-22 | Kawasaki Steel Corp | モノアラルキル化フェノール類の製造方法 |
JP3196141B2 (ja) | 1991-11-14 | 2001-08-06 | 東都化成株式会社 | エポキシ樹脂組成物 |
JP3633673B2 (ja) | 1995-07-11 | 2005-03-30 | 三菱瓦斯化学株式会社 | プリプレグ及び積層板 |
JP3819254B2 (ja) | 2001-05-23 | 2006-09-06 | 新日鐵化学株式会社 | 熱硬化型塗料用硬化剤及び塗料組成物 |
JP3850726B2 (ja) | 2001-12-27 | 2006-11-29 | 新日鐵化学株式会社 | 制振材 |
AU2005261704B2 (en) * | 2004-07-09 | 2010-04-08 | Huntsman Advanced Materials Licensing (Switzerland) Gmbh | Amine compositions |
JP2008088348A (ja) * | 2006-10-04 | 2008-04-17 | Aica Kogyo Co Ltd | エポキシ樹脂組成物 |
US8980979B2 (en) * | 2009-03-17 | 2015-03-17 | Dow Global Technologies Llc | Curable compositions containing cyclic diamine and cured products therefrom |
KR101111248B1 (ko) * | 2009-12-18 | 2012-02-22 | 금호석유화학 주식회사 | 스티렌네이티드 페놀의 제조방법 |
CN103140523B (zh) | 2010-09-27 | 2014-07-23 | 新日铁住金化学株式会社 | 多羟基树脂、环氧树脂、它们的制造方法、环氧树脂组合物及其固化物 |
CN104245780B (zh) * | 2012-04-09 | 2017-08-08 | 陶氏环球技术有限责任公司 | 用于冷固化环氧体系的硬化剂 |
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0335674A2 (en) * | 1988-03-30 | 1989-10-04 | Yoshitomi Pharmaceutical Industries, Ltd. | Selective process for preparing 2,4- or 3,6-di-substituted phenol compounds |
CN102549041A (zh) * | 2009-09-25 | 2012-07-04 | 陶氏环球技术有限责任公司 | 可固化环氧树脂组合物及由其制备的复合材料 |
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