CN101591511B - 用于结合复合材料的粘合制剂 - Google Patents
用于结合复合材料的粘合制剂 Download PDFInfo
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- CN101591511B CN101591511B CN200910134655.7A CN200910134655A CN101591511B CN 101591511 B CN101591511 B CN 101591511B CN 200910134655 A CN200910134655 A CN 200910134655A CN 101591511 B CN101591511 B CN 101591511B
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- adhesive formulations
- acrylate
- monomer
- resin
- dimethacrylate
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- 238000000034 method Methods 0.000 claims abstract description 25
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 15
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- 238000005470 impregnation Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 16
- BGPDZUTXTIWAQM-UHFFFAOYSA-N 2-methylprop-2-enoic acid 2-phenoxyethyl prop-2-enoate Chemical compound O(C1=CC=CC=C1)CCOC(C=C)=O.CC(C(=O)O)=C BGPDZUTXTIWAQM-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 230000007704 transition Effects 0.000 claims description 8
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 7
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 claims description 4
- 238000007046 ethoxylation reaction Methods 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- MHCLJIVVJQQNKQ-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O MHCLJIVVJQQNKQ-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
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- -1 hydroxy alkylidene Chemical group 0.000 description 8
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 230000003245 working effect Effects 0.000 description 4
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 description 1
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
- ONPJWQSDZCGSQM-UHFFFAOYSA-N 2-phenylprop-2-enoic acid Chemical compound OC(=O)C(=C)C1=CC=CC=C1 ONPJWQSDZCGSQM-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 0.000 description 1
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- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/024—Woven fabric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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Abstract
本发明涉及用于结合复合材料的粘合制剂,其通常包括丙烯酸酯和/或甲基丙烯酸酯单体、重均分子量为约450至约3000的乙烯基酯树脂和催化剂。还公开了用该粘合制剂粘合复合材料的方法,及采用该粘合制剂的树脂浸渍层压法。
Description
技术领域
本发明涉及用于结合复合材料的粘合制剂。
背景技术
近十年来,许多新型复合材料得到了研发,其中有些具有非常有价值的性质。先进复合材料由于高强度、轻重量、高刚度和耐尺寸变化稳定性而在工业生产中得到了广泛应用。通过仔细选择增强体、基体和将二者结合在一起的制造方法,工程师们能够通过选择合适的基体材料定制性能,从而满足特定需求,如耐热性、耐化学稳定性、耐候性。复合材料最大的优点是与轻重量结合的强度和刚度。通过选择合适的增强体和基体材料的组合,生产者可以生产出完全符合用于特定目的的特定结构所需的性能。该合适的复合材料同样可以承受热和腐蚀。上述优点使得他们理想地用于暴露于极端环境,如船舶、化学操作设备和交替性能量机构如风力涡轮机的产品中。这种复合材料同时具有高水平的化学稳定性和热稳定性。
人们通常需要将复合部件连接起来,优选采用粘合剂将复合部件连接起来,以产生最高强度的接头。然而,困难之一在于将这些复合材料结合在一起形成各种形状的结构。特别地,风力涡轮机制造应用要求粘合剂能够承受施加于每个叶片上的离心力。这些粘合剂应当能够同时粘接非常大的部件,如叶片套的两半(the two halves of a blade envelope)和梁,同时又能填补对于接头结构而言不可避免的长达60米的大量间隙。然后它们必须在叶片使用期内持续的热循环和环境侵袭的条件下保持粘结强度。粘接必须能够承受每天循环操作的外部环境条件,保持直至25年不屈服(yielding)。
将复合部件结合在一起所使用的一个方法就是施加膏状粘合剂(pasteadhesive)。膏状粘合剂能够提供高强度接头,但由于其高粘度而难于加工。环氧粘合剂也能提供高强度接头,但环氧粘合剂可能难于加工。通过将环氧树脂与催化剂合并并使其在混合时开始反应而制得环氧粘合剂。该反应改变了粘度, 使得加工困难。固化时间也能够随温度有显著的变化。某些环氧体系在高于90°F的温度下迅速地固化,以致其变得几乎不能用。而在例如低于60°F的较冷温度下,某些体系可需要数天甚至更长的时间才能固化。其它可能的粘合剂材料如聚酯类或乙烯基酯类却不能提供足够的粘接强度。
粘合剂不仅必须提供持久的结合,还必须易于加工,从而能够在现场在各种条件下使用。商业可得的粘合剂不能满足例如粘接风力涡轮机复合部件所需的粘接强度、使用时间和可加工性的需求。
因此,需要将复合部件持久地相互连接在一起。
发明内容
本发明涉及粘合制剂(adhesive formulation)及用该制剂制备的复合材料(composite)。
在一个实施方案中,本发明提供粘合制剂,其包含丙烯酸酯和/或甲基丙烯酸酯单体、重均分子量为约450至约3000的乙烯基酯树脂和催化剂。
在另一个实施方案中,本发明提供将第一复合材料粘合性连接到第二复合材料的方法,该方法包含:在第一和第二复合材料之间设置粘合制剂;其中该粘合制剂包含丙烯酸酯和/或甲基丙烯酸酯单体、重均分子量为约450至约3000的乙烯基酯树脂和催化剂;和将该粘合制剂固化,以提供搭接剪切强度(lapshear strength)与在第一和第二复合材料之间使用不含单体的粘合制剂的强度相比提高20%。
在又一个实施方案中,形成复合材料的方法包含制备浸渍树脂(infusionresin);将许多干燥的纤维层(fiber ply)叠层以得到干燥的层压材料;将所述树脂浸渍于所述干燥层压材料中,得到纤维增强的树脂复合材料,其中该浸渍树脂包含丙烯酸酯和/或甲基丙烯酸酯单体、重均分子量为约450至约3000的乙烯基酯树脂和催化剂;然后将该浸渍树脂固化。
通过参考下列的本发明各个特征的详细说明和其中包括的实施例,本发明将更易于理解。
附图说明
下图仅用于示例说明的目的,其中相似的要素用附图标记类似地编排。
图1证实本发明搭接剪切强度测试的结果,具体公开了DION 9800和10%甲基丙烯酸酯单体的混合物的搭接剪切强度(SLS)测试结果,其中SLS基于4层式UD玻璃-Dion 9800IR。
图2为用于将两个复合部件结合到一起的本发明粘合材料的示例性实施方案。
具体实施方式
本发明涉及粘合剂和树脂制剂(adhesive and resin formulation)及其制备的复合材料。更具体地,本发明涉及甲基丙烯酸酯单体和乙烯基酯树脂的新型混合物、由其制备的固化的聚合物、及采用上述制剂持久粘接在一起的复合制品。在此公开的粘合制剂具有有利的物理性能,包括但不限于:结合复合部件(composite part)所需的增加的结合强度、使用寿命和加工性。所述粘合制剂尤其适用于将风力涡轮机的复合部件结合在一起。
所述粘合剂和树脂制剂包括在催化剂存在下发生反应的甲基丙烯酸酯和/或丙烯酸酯单体和乙烯基酯树脂。在一个实施方案中,加入一种或多种催化剂,得到的混合物发生固化,或者将得到的混合物施加于复合材料并随后固化。
式(I)的所述丙烯酸酯和/或甲基丙烯酸酯单体如下所示:
其中R1为氢或C1-C10脂族基团;R2选自C1-C10脂族基团、C3-C30芳族基团和C3-C20环脂族基团,且n为1至4的整数。在各种实施方案中,R2可包含基团比如亚烷基、羟基亚烷基、烷氧基取代的芳族化物。R2也可包含尿烷、醚、酯或硅氧烷键。
根据本发明的合适的丙烯酸酯和/或甲基丙烯酸酯单体包括但不局限于:新戊二醇二甲基丙烯酸酯、乙氧基化的2-双酚A二甲基丙烯酸酯、甲基丙烯酸苯氧基乙基酯、脂族尿烷丙烯酸酯低聚物、丙烯酸酯化的尿烷、三羟甲基丙烷三丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、低粘度脂族单丙烯酸酯低聚物、三官能甲基丙烯酸酯、尿烷甲基丙烯酸酯和二乙二醇二甲基丙烯酸酯。
合适的乙烯基酯树脂具有低分子量。术语“低分子量”是指优选重均分子 量为约450至约3000的乙烯基酯树脂。最优选所述分子量为约500至约1500。对于本发明而言,合适的乙烯基酯树脂可通过使不饱和的单羧酸或酸酐与环氧树脂反应制得。在一个实施方案中,反应物的用量使得酸基/环氧基团的比例为约0.95∶1至约1.05∶1,优选该比例为约1∶1。不饱和单羧酸或酸酐与环氧树脂之间的反应可在下述温度条件下进行足够的时间以完成该反应:在某些实施方案中为约90℃至130℃,在另外实施方案中为约100℃至120℃,和在另外实施方案中为约105℃-110℃。当剩余的酸百分量达到1或更小时,通常认为反应结束。反应时间通常为约3至6小时。
可以用于形成乙烯基酯树脂的酸和酸酐的例子包括(甲基)丙烯酸或酸酐、α-苯基丙烯酸、α-氯代丙烯酸、巴豆酸、马来酸或富马酸的单甲基酯和单乙基酯、乙烯基乙酸、山梨酸和肉桂酸等。
可使用的环氧树脂是已知的且实际上包括多官能化卤代醇如表氯醇与酚或多羟基酚的任意反应产物。合适的酚或多羟基酚包括例如间苯二酚、四酚乙烷和各种双酚类,如双酚A、4,4’-二羟基二苯基砜、4,4’-二羟基联苯、4,4’-二羟基-二苯基甲烷、2,2’-二羟基二苯基氧等。根据本发明,双酚A的量限于适量使用。
任意合适的环氧树脂均可用于形成乙烯基酯树脂。环氧树脂典型地每分子具有平均多于一个的连位环氧基团,和不饱和多元羧酸(The epoxy resinstypically have an average of more than one vicinal epoxy group permolecule with an unsaturated polycarboxylic acid)。也可使用酚醛清漆环氧树脂。特定的环氧化合物包括间苯二酚、邻苯二酚、对苯二酚、双酚A的多种缩水甘油醚;氟,苯酚-醛树脂或甲酚-醛树脂及其卤代(如溴代)衍生物。也可使用上述环氧树脂的任意混合物。
为了促进不饱和多元羧酸或酸酐与环氧树脂的反应,可以使用催化剂。适用的催化剂包括例如三(二甲基氨基甲基)苯酚、四乙基溴化铵、四甲基氯化铵、己酸锆、三苯基膦等。也可使用上述任意组合。特别合适的催化剂包括,例如己酸锆或三苯基膦,或其任意组合等。催化剂的用量通常为约0.03至约0.15份,优选约0.05至0.1份,最优选约0.06份,以多元羧酸或酸酐与环氧树脂形成的每100份最终混合物计。乙烯基酯树脂组合物还可进一步包含由烯属不饱和单体组成的反应性稀释剂,所述单体在乙烯基酯树脂的随后固化过程中参与该乙烯基酯树脂的交联。可以使用的合适的反应性稀释剂的例子包括苯乙烯、 乙烯基甲苯、α-甲基苯乙烯、叔丁基苯乙烯、和2-乙烯基吡咯烷酮、二乙烯基苯、及丙烯酸或甲基丙烯酸的甲基、乙基、异丙基、和辛基酯。优选苯乙烯。在本发明的树脂组合物中的反应性稀释剂存在量通常占组合物总重量的约40-约60重量%。
在例举实施方案中,采用的乙烯基酯树脂是DION-9800-05A乙烯基酯,购于Reichhold Chemicals,Inc.,Research Triangle Park,N.C.
如上所述,该粘合制剂包括丙烯酸酯和/或甲基丙烯酸酯单体,乙烯基酯树脂和催化剂。合适的粘合制剂催化剂包括例如环烷酸钴,乙酰丙酮,甲基乙基酮过氧化物,辛酸钴,N,N-二甲基苯胺,N,N-二甲基乙酰胺和N,N-二甲基对甲苯胺。可以使用上述物质的混合物。在一个实施方案中,催化剂的用量为约0.05-1.5重量%。催化剂用量可以改变,从而达到所需的粘合制剂可使用寿命,尤其是其中商业用途所需的较长可使用寿命。
粘合制剂固化时将具有玻璃化转变温度,其将根据确切的甲基丙烯酸酯单体和固化过程来改变。代表性组合物的玻璃化转变温度(Tg)已通过DynamicMechanical Analysis(DMA)测定。制备Sartomer SR 240甲基丙烯酸苯氧基乙基酯与DION 9800-05A的各种混合物,然后用0.2%环烷酸钴与1.2%MEKP-9H过氧化物进行催化。当在60℃下固化90分钟后,混合物的玻璃化转变温度(Tg)通过DMA测定。以下表1表示玻璃化转变测定结果,其中改变粘合剂组合物的配方中甲基丙烯酸苯氧基乙基酯的百分比。在优选的用于结合复合部件的实施方案中,玻璃化转变温度不低于70℃适宜。因而,根据取样结果,甲基丙烯酸酯单体为20%或更低的混合物适宜。
表1.
甲基丙烯酸苯氧基乙基酯(%) | 玻璃化转变温度(℃) |
10 | 92 |
20 | 80 |
30 | 45 |
40 | 50 |
50 | 12 |
粘合剂工作时间可通过使用的催化剂来控制并改变。在一个实施方案中,工作时间(至固化的时间)通常大于1小时。例如,通过将10%的Sartomer SR340 甲基丙烯酸苯氧基乙基酯、90%的DION 9800-05A、0.22pbw的6%的环烷酸钴和1.21%的MEKP-9H过氧化物组合来制备粘合制剂。不含其它组分的等分试样保持可使用状态为50分钟。包含0.09%乙酰丙酮的第二等分试样的可使用寿命为65分钟,含有0.19%乙酰丙酮的第三等分试样的可使用寿命为180分钟。使用寿命因此可以得到控制。粘合制剂的可使用寿命优选大于1小时。可使用寿命的结果概括在下面表2中。
表2
乙酰丙酮(%) | 使用寿命(分钟) |
0 | 50 |
0.09 | 65 |
0.19 | 180 |
这种新型混合物的低粘度适于持久地粘接复合部件的过程。该制剂可具有低于500厘泊的粘度从而使其较易加工。同样,两种复合基体之间的结合层(bondline)可以从约5至约10微米,至多至大约1厘米。由于所属制剂基本无粘性并且易流动,可以用材料垫置于所述结合层中芯吸粘合剂并在固化前将其保持就位。
可以用该粘合制剂结合的合适材料包括例如由固化树脂如环氧树脂、聚酯或乙烯基酯与织造玻璃纤维或碳布制备的复合部件。在例举的实施方案中,本发明提供了结合风力涡轮机的复合部件的方法。在此公开的粘合剂材料与现有的粘合剂相比,更易于加工。因而,它们提供在现有粘合剂所不能工作的环境中将复合部件结合起来的机会。例如,为了提高效率,需要具有较长的风力涡轮机叶片的较大的风力涡轮机。然而,涡轮机叶片由于太长而不能以经济合算的方式运输到风力农场所在地。当在工厂里将叶片制成两部分然后运输时,能经济可行地将风力涡轮机叶片运输到风力农场所在地。适用于风力涡轮机叶片复合材料的粘合剂必须具备以下性能:高于70℃的玻璃化转变温度,使用寿命大于1小时,能够填补20mm的结合层中的所有空隙(预计要求粘度为小于500厘泊),足够的粘接强度,即在单次搭接剪切强度测试大于1400psi。本发明提供将两部分叶片固定在一起的简易方法,其通过采用本发明的粘合制剂粘接复合部件。
为了从各个的复合部件形成结构,可通过任意合适的方法来实现粘接,该 方法在粘合制剂和待粘接的复合材料之间提供有效且紧密的接触。任选,可以将粘合促进剂与粘合制剂和/或与复合材料本身一起使用。图2为用粘合剂10将两种复合部件(12,14)结合在一起的示意实施方案。在另一个例举的实施方案中,上述粘合剂施加在待结合的复合部件的至少一个表面上。强行将复合部件置于一起从而将任何多余的粘合剂推出,该多余的粘合剂被除去,随后将组件固化并烧制。在固化过程中,或者如果该组件过大或复杂而不能用夹具或其它常用工具使得各个复合部件接触在一起直至固化和烧制完成,可以将该组件置于真空袋中。在另一个实施方案中,固化可以在惰性气体如氮气的存在下进行。固化可以采用任意适当的固化方法完成,该方法包括但不局限于加热固化,热固化或电子束固化。
在本发明的另一个实施方案中,还发现在此公开的制剂作为浸渍树脂具有改善的性能。树脂浸渍作为先进层压方法,其用于提高玻璃纤维部件的质量和强度。通过非限制性实例,例如,本发明的制剂可以采用真空包装方法应用于树脂浸渍过程中。在一个实施方案中,该制剂作为浸渍树脂用于形成复合风力涡轮机叶片。
在一个实施方案中,将大量干燥纤维层叠层在一起形成干燥层压材料。各种纤维层的取向取决于最终一体式结构所需的方向强度。将由本发明制剂所制备的至少一层浸渍树脂,注入到干燥层压材料中,然后可在多于一个位置将树脂注入。例如,除了注入到层压材料上面的层之外,还可以在层压材料下面的层中注入树脂。接着,在层压材料中加入剥离层。例如该剥离层可以是紧密织造的织物,如尼龙或聚酯,并且经脱模剂浸渍过。此外,可以施加流动介质层以使树脂在整个层压材料中易于流动且不留下任何干燥碎片。流动介质可以是使树脂容易流动的任何合适的材料;在一个实施方案中,它是蜂窝状、交叉图案或任意漩涡状图案结构化的塑料网。接着,将干燥层压材料与树脂层的结合,或叠层体(layerup),与排空导管接触,该排空导管如一层或多层的通气带(breather tape)。然后,将该叠层体与排空导管装入树脂含量控制袋内,排空导管穿过该控制袋。然后将该树脂含量控制袋装入真空袋内。接着将真空袋内的气体排空。由于排空导管,树脂含量控制袋及干燥层压材料内的气体随着真空袋的排空而被排空。最终,真空袋及其内含物排空气体。在气体被排空之后,引向树脂源的注入管线被打开,排空的袋和树脂源之间的压力差致使树脂注入 干燥层压材料内从而得到纤维增强型树脂复合材料。在某些应用中,真空袋包住整个材料,或者在其它应用中,采用模具形成层压材料的一个表面,将真空袋用于单面从而将层压材料的外表面密封在该模具上来。开口端密封,气体由真空泵抽出。因此,接近一个大气压的均一压力施加到袋内物体的表面,在树脂固化时将部件保持在一起。整个袋子可以置于温度可控的烘箱、油浴或水浴中并将其缓慢加热以加速固化。平板状物体的层压在加热的层压机下可更有效地进行,然而如果该物体呈卷曲或不规则的形状,则通常采用真空袋。
在另一个实例中,将干燥层压材料和采用本发明制剂制备的树脂,置于可以形成一部分真空袋的工具上。该工具可以通过隔离膜从干燥层压材料和树脂分离,所述隔离膜然后形成树脂含量控制袋的一部分。该工具在纤维增强树脂复合材料形成时使得该纤维增强树脂复合材料的相邻表面成型。在另一个实施方案中,第二工具位于干燥预成型体的另一面上,来自第一工具的树脂用于在纤维增强复合材料形成时使其相对表面成型。该工具可以通过脱模层和该上面的树脂分离。或者,可将该工具穿孔,并置于树脂和干燥预成型体之间,位于穿孔工具中的孔洞能够使树脂在固化时流入干燥预成型体内。最后将真空袋、进料软管、流动介质和剥离层除去,完成浸渍。
下面实施例用于解释本发明,但本发明并不局限于此。
为了测定本发明的有效性,在实验室内进行实验。采用不同的甲基丙烯酸酯单体制备数个试样,然后测定其粘接强度、玻璃化转变温度和可使用寿命。以下实施例仅用于解释本发明,但并不意欲限制本发明的范围。
实施例1
在本实施例中,采用4层玻璃和购于Reichhold的DION 9800-05A乙烯基酯树脂制备复合基体。从该复合基体裁下测试条,并将其彼此粘接在一起,使用的是10%的甲基丙烯酸酯单体与90%的DION 9800-05A的混合物,并用0.2%的环烷酸钴(6%)、0.2%的乙酰丙酮和1.2%的MEKP-9H过氧化物进行催化。MEKP-9H是甲基乙基酮过氧化物。将该混合物置于环境温度下整夜固化,然后在60℃固化8小时。采用不同的甲基丙烯酸酯单体样品制备连续混合物并对其进行测试。根据上述实施例测试的单体包括可商购于Sartomer公司的商品名为SR231的二乙二醇二甲基丙烯酸酯,可商购于Sartomer公司的商品名为SR9009 的三官能甲基丙烯酸酯,可商购于Sartomer公司的商品名为SR248的新戊二醇二甲基丙烯酸酯,可商购于Sartomer公司的商品名为SR214的丁二醇二甲基丙烯酸酯,可商购于Sartomer公司的商品名为CN2920的脂族尿烷丙烯酸酯低聚物,可商购于Sartomer公司的商品名为SR348的乙氧基化BPA二甲基丙烯酸酯,可商购于Sartomer公司的商品名为CN152的脂族单丙烯酸酯低聚物,可商购于Rahn AG的商品名为Genomer 4302的脂族聚酯三尿烷丙烯酸酯,可商购于Sartomer公司的商品名为CN1963的基于脂族聚酯的尿烷二甲基丙烯酸酯低聚物,可商购于Sartomer公司的商品名为SR9011的三官能甲基丙烯酸酯单体。
图1显示了搭接剪切强度测试结果。搭接剪切决定用于结合材料的粘合剂的剪切强度。测试方法主要是比较性的。用本发明粘合剂将两种试样结合起来并按规定固化。将该测试试样置于Instron通用实验机的夹钳上并拉伸直至失效。如图所示,含有SR214单体的粘合制剂的粘接强度为1560psi;SR248提供的粘接强度为1553psi,SR348提供的粘接强度为1493psi,SR340提供的粘接强度为1487psi,CN2920提供的粘接强度为1586psi,和Rahn’s Genomer4302提供的粘接强度为1613psi。
所有甲基丙烯酸酯单体表现出某种改善的粘接强度,然而,本发明的某些单体较其它单体表现出更加改善的粘接强度。例如,将10%SR231二乙二醇二甲基丙烯酸酯加入到DION 9800-05A乙烯基酯产生的粘接强度为1160psi,并不明显好于单独使用DION 9800-05A得到的粘接强度。不欲受任何理论的束缚,据推测这是由于二乙二醇的加入产生更脆的制剂变体,这在搭接剪切测试中过早破裂。
实施例2
在本实施例中,通过将5层的15英寸×15英寸的单向玻璃板和剥离层层叠起来形成第一复合层压材料。采用标准真空袋技术浸渍树脂。使浸渍的复合材料于环境温度下凝胶,其后将其放于65℃后固化3.5小时。将剥离层从该固化的复合材料中除去并将特氟隆商标胶带沿该固化的复合材料的一边放置。第二复合层压材料在第一复合层压材料的顶部上制备,其通过将12英寸×13英寸的单向玻璃板层叠到固化的剥离层表面上来进行。使用于制备第一复合层压材料的相同树脂在环境温度下凝胶,然后将其放于65℃后固化3.5小时。修剪所述板边缘并将该板剪裁成用于测试粘接强度的1英寸×10英寸的试样条。采用 Instron商标测试仪进行测定,从而测量迫使第一和第二复合层压材料分离所需的力。测定磅力并计算置信区间(confidence interval,CI)。表3对使用DION 9800-05A乙烯基酯,及DION 9800-05A与可商购于Sartomer公司的商品名为SR340的甲基丙烯酸苯氧基乙基酯的制剂进行测试的粘接强度结果进行了比较。如表3所示,与单独使用乙烯基二酯相比,本发明的制剂呈现显著改善的粘合。
表3
测试的复合材料 | 载荷(Ibf) | 95%CI |
DION 9800-05A | 3.6392 | 0.181 |
DION 9800-05A与15%SR340 | 12.26251 | 1.22387 |
对比实施例1
在本对比实施例中,用4层玻璃和未加入甲基丙烯酸酯单体的仅仅DION9800-05A乙烯基酯树脂制备复合基体。从该复合基体裁下测试条并用DION9800-05A乙烯基酯树脂将其彼此粘接在一起。固化后,搭接剪切强度测试证明粘接强度为1133psi。因此,结果表明,使用包含乙烯基酯树脂与甲基丙烯酸酯单体的本发明的混合物在粘接复合材料时表现出显著的优势。
该写成的说明书采用实施例用来公开本发明,包括最佳形式,还用来使本领域任意技术人员制造并使用本发明。本发明可专利的范围由权利要求进行限定,并且可包含本领域技术人员可想到的其它实例。如果这种其它实例具有与权利要求的字面意思并非不同的结构要素,或者如果它们包括与权利要求的字面意思无实质性差异的等价结构元素,则均在权利要求的范围内。
部件列表
10粘合剂
12复合部件
14复合部件
Claims (10)
1.粘合制剂,所述粘合制剂由以下成分组成:
丙烯酸酯和/或甲基丙烯酸酯单体;
重均分子量为450至3000的乙烯基酯树脂;和
催化剂;
其中所述催化剂的量为0.05-1.5%重量,所述丙烯酸酯和/或甲基丙烯酸酯的量为20%重量以下。
2.如权利要求1所述的粘合制剂,其中所述丙烯酸酯单体和/或甲基丙烯酸酯单体具有以下式:
其中R1为氢或甲基;R2选自C1-C10脂族基团、C3-C30芳族基团和C3-C20环脂族基团,n为1至4的整数。
3.如权利要求1所述的粘合制剂,其中所述丙烯酸酯单体和/或甲基丙烯酸酯单体选自新戊二醇二甲基丙烯酸酯、乙氧基化的2-双酚A二甲基丙烯酸酯、甲基丙烯酸苯氧基乙基酯、脂族尿烷丙烯酸酯低聚物、丙烯酸酯化的尿烷、三官能甲基丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、低粘度脂族单丙烯酸酯低聚物、尿烷甲基丙烯酸酯和二乙二醇二甲基丙烯酸酯。
4.如权利要求1所述的粘合制剂,其中当固化时,所述制剂与不含单体的制剂相比,搭接剪切强度提高20%。
5.如权利要求1所述的粘合制剂,其中所述制剂在固化前的粘度低于500厘泊。
6.将第一复合材料(12)粘合性连接到第二复合材料(14)的方法,包含:
在第一和第二复合材料之间设置粘合制剂(10),其中所述粘合制剂由以下成分组成:丙烯酸酯单体和/或甲基丙烯酸酯单体,
重均分子量为450至3000的乙烯基酯树脂,和
催化剂;
其中所述催化剂的量为0.05-1.5%重量,所述丙烯酸酯和/或甲基丙烯酸酯的量为20%重量以下;和
将所述粘合制剂固化,以使得搭接剪切强度与在第一和第二复合材料之间使用不含单体的粘合制剂的搭接剪切强度相比提高20%。
7.如权利要求6所述的方法,其中所述粘合制剂(10)的粘度低于500厘泊。
8.如权利要求6所述的方法,其中粘合制剂(10)在固化后的玻璃化转变温度高于70℃。
9.如权利要求6所述的方法,其中所述丙烯酸酯单体和/或甲基丙烯酸酯单体选自新戊二醇二甲基丙烯酸酯、乙氧基化的2-双酚A二甲基丙烯酸酯、甲基丙烯酸苯氧基乙基酯、脂族尿烷丙烯酸酯低聚物、丙烯酸酯化的尿烷、三官能甲基丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、低粘度脂族单丙烯酸酯低聚物、尿烷甲基丙烯酸酯和二乙二醇二甲基丙烯酸酯。
10.如权利要求6所述的方法,其中该方法为树脂浸渍层压法。
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DE102009003567A1 (de) | 2009-11-12 |
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BRPI0901398A2 (pt) | 2010-11-16 |
DK200900326A (en) | 2009-09-13 |
BRPI0901398B8 (pt) | 2019-03-06 |
BRPI0901398B1 (pt) | 2019-02-12 |
US20090229747A1 (en) | 2009-09-17 |
DK178355B1 (en) | 2016-01-11 |
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