CN109679282B - 一种具有特定纳米结构的高强高韧环氧复合材料 - Google Patents
一种具有特定纳米结构的高强高韧环氧复合材料 Download PDFInfo
- Publication number
- CN109679282B CN109679282B CN201811427649.6A CN201811427649A CN109679282B CN 109679282 B CN109679282 B CN 109679282B CN 201811427649 A CN201811427649 A CN 201811427649A CN 109679282 B CN109679282 B CN 109679282B
- Authority
- CN
- China
- Prior art keywords
- bxls
- block copolymer
- epoxy resin
- parts
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 16
- 239000004593 Epoxy Substances 0.000 title claims abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 57
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 57
- 229920001400 block copolymer Polymers 0.000 claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 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
- -1 polydimethylsiloxane Polymers 0.000 claims description 6
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical group C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 5
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Chemical group 0.000 claims 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 12
- 239000004793 Polystyrene Substances 0.000 description 11
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 11
- 238000000235 small-angle X-ray scattering Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 8
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 210000003495 flagella Anatomy 0.000 description 2
- 238000007656 fracture toughness test Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- GGXRSUUOWQBVFB-UHFFFAOYSA-N 2,3-dibromo-2-methylpropanoyl bromide Chemical compound BrCC(Br)(C)C(Br)=O GGXRSUUOWQBVFB-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 241000223785 Paramecium Species 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000013466 adhesive and sealant Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
- C08G59/40—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 curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
- C08G59/40—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 curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6952—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明提供了一种具有特定纳米结构的高强高韧环氧复合材料,它是由下述重量配比的原料制备而成的:环氧树脂50份、固化剂20份、BXLS嵌段共聚物1.25~20份。实验结果表明,BXLS嵌段共聚物在环氧树脂中形成了类“草履虫”状的新型纳米结构,使得本发明制备得到的BXLS/环氧树脂复合材料在BXLS嵌段共聚物添加量极低的情况下实现了材料韧性的显著增加并且还具有更优异的力学强度,极大的拓宽了环氧树脂的应用领域。
Description
技术领域
本发明属于高分子复合材料领域,具体涉及一种具有特定纳米结构的高强高韧环氧复合材料。
背景技术
环氧树脂(EP)是一种优良的高强度热固性树脂,是应用非常广泛的基体材料。EP分子上带有两个或两个以上环氧基团,能与胺类、酸酐类、聚酰胺类物质交联固化,形成高度交联的空间三维网状结构,其固化物具有耐磨性好、耐热性优异、化学稳定性良好、电绝缘性优良、强度高、收缩率低、易加工成型、耐化学试剂、对基材具有良好的黏附性能和价格低廉等优点,作为电子涂装、涂料、电气材料、浇注封装材料、胶黏剂、密封胶的基体树脂,被广泛应用在航空航天、汽车、造船、建筑、铁路交通等国民经济的各个领域。但是EP固化后形成的固化物交联密度高,呈空间三维网状结构,分子链间不易滑动,内应力大,从而导致固化物硬脆、易开裂、耐冲击性和抗剥离性差,在实际应用中难以满足使用要求,使其应用受到一定限制,这些缺点都是EP固化物韧性不足造成的。
当前,对环氧树脂的增韧改性途径主要有橡胶弹性体增韧、树脂合金化增韧、热致液晶聚合物增韧、树枝形分子增韧、纳米粒子增韧以及在交联网络中引入柔性链段增韧等方法。随着纳米技术研究的不断深入,通过引入少量纳米结构单元(如纳米粒子、纳米线、纳米管、纳米片层等)而制备出的环氧树脂基纳米复合材料可大大提高树脂固化物的抗冲击性能,而其他物理性能很少受到影响,因而纳米增韧改性环氧树脂非常具有应用前景。
发明内容
本发明的目的在于提供了一种具有特定纳米结构的高强高韧环氧复合材料,它是由下述重量配比的原料制备而成的:
环氧树脂50份、固化剂20份、BXLS嵌段共聚物1.25~20份。
进一步地,它是由下述重量配比的原料制备而成的:
环氧树脂50份、固化剂20份、BXLS嵌段共聚物1.25~5份。
进一步地,它是由下述重量配比的原料制备而成的:
环氧树脂50份、固化剂20份、BXLS嵌段共聚物1.25~2.5份。
进一步地,它是由下述重量配比的原料制备而成的:
环氧树脂50份、固化剂20份、BXLS嵌段共聚物2.5份。
进一步地,所述BXLS嵌段共聚物中BX-OH与PCL、PS的分子量之比为1:1.16:1.43。
进一步地,所述BX-OH为单羟基封端的聚二甲基硅氧烷。
进一步地,所述环氧树脂为双酚A型环氧树脂。
进一步地,所述双酚A型环氧树脂选自E-51、E-44。
进一步地,所述固化剂选自3,3′-二氯-4,4′-二氨基二苯基甲烷、4,4′-二氨基二苯基砜、二氨基二苯甲烷。
进一步地,它是由下述方法制备而成:
(1)BXLS嵌段共聚物的制备:由BX-OH引发ε-己内酯开环聚合后,用原子转移自由基聚合方法合成BXLS嵌段共聚物即可;
(2)按重量配比称取环氧树脂以及BXLS嵌段共聚物,混匀后加入固化剂后再次混匀,真空除泡、固化即可。
实验结果表明,BXLS嵌段共聚物在环氧树脂中形成了类“草履虫”状的新型纳米结构,使得本发明制备得到的具有特定纳米结构的高强高韧环氧复合材料(BXLS/环氧树脂复合材料)在BXLS嵌段共聚物添加量极低的情况下实现了材料韧性的显著增加,并且还具有更优异的力学强度,极大的拓宽了环氧树脂的应用领域。
显然,根据本发明的上述内容,按照本领域的普通技术知识和惯用手段,在不脱离本发明上述基本技术思想前提下,还可以做出其它多种形式的修改、替换或变更。
以下通过实施例形式的具体实施方式,对本发明的上述内容再作进一步的详细说明。但不应将此理解为本发明上述主题的范围仅限于以下的实例。凡基于本发明上述内容所实现的技术均属于本发明的范围。
附图说明
图1为力学性能测试试样尺寸图,(a)为拉伸性能测试试样,(b)为断裂韧性测试试样,S为测试跨距,P为载荷,B为试样厚度,W为试样宽度,A为裂纹深度。
图2为原料BX-OH、中间产物BXL以及嵌段共聚物BXLS的GPC曲线。
图3为嵌段共聚物BXLS的1HNMR谱图。
图4为含不同嵌段共聚物添加量的环氧树脂的TEM照片,a和a’中嵌段共聚物的添加量为1.75wt%;b和b’中嵌段共聚物的添加量为6.67wt%;c和c’中嵌段共聚物的添加量为22.22wt%。
图5为含不同嵌段共聚物添加量的环氧树脂SAXS曲线。
图6为含6.67wt%BXLS嵌段共聚物的环氧树脂固化前后的SAXS曲线。
图7为含6.67wt%BXL嵌段共聚物环氧树脂的FESEM照片。
图8为含不同嵌段共聚物添加量的环氧树脂的拉伸性能的表征图。
图9为含不同嵌段共聚物添加量的环氧树脂的断裂韧性的表征图。
具体实施方式
实施例1、本发明复合材料的制备与性能检测
一、本发明复合材料的制备
1实验原料与试剂
BX-OH:聚二甲基硅氧烷,日本信越化学工业株式会社,货号X-22-107BX(结构式中的R以及R'为短烃链封端单元,例如:丁基(R-:CH3-CH2-CH2-CH2-)、乙基(-R'-:-CH2-CH2-),然而厂商并没有给出具体的结构式)。己内酯、聚苯乙烯、二溴异丁酰溴、辛酸亚锡等均为化学纯,购于上海阿拉丁生化科技股份有限公司。EP:双酚A型环氧树脂(E51),凤凰牌环氧树脂,型号WSR618(E51),南通星成材料有限公司。色度:≤40Pt-Co,环氧当量:184~195g/mol,水解氯:≤0.2%,50mg/kg,挥发物:0.5%,粘度(25℃):10000~16000mPa.s。4,4'-二氨基-3,3'-二氯二苯甲烷(MOCA):工业级,常山贝尔化学有限公司。
2实验部分
2.1嵌段共聚物BX-b-PCL(BXL-OH)的合成
嵌段共聚物PDMS-PCL的合成是以辛酸亚锡[Sn(Oct)2]为催化剂,端羟基聚二甲基硅氧烷(BX-OH)引发己内酯(ε-CL)开环聚合得到。具体过程如下:首先,BX-OH(15g,3.83mmol)和干燥的甲苯(20ml)在250ml无水无氧瓶中共沸除水,蒸出多余的甲苯,然后将ε-CL(19.15g,167.98mmol)和Sn(Oct)2(添加量为1wt‰的ε-CL)加入到上述纯化后的BX中。经过三次液氮冷冻-真空脱气-解冻循环后,将负压状态下烧瓶置入120℃的恒温油浴中搅拌反应36h。待反应结束后,将粗产物溶解于适量的二氯甲烷溶液中,然后加入大量的冷冻甲醇沉淀,过滤。重复此溶解-沉淀-过滤过程三次以除去体系中可能存在的副产物和残余单体。将纯化后的产物在30℃的真空烘箱中干燥至恒重。
2.2大分子引发剂BX-b-PCL-Br(BXL-Br)的合成
在三乙胺(TEA)和催化剂4-二甲氨基吡啶(DMAP)存在的条件下,上述方法制备得到的BXL-OH与2-溴异丁基酰溴(2-BiB)在纯化干燥的二氯甲烷(DCM)中反应,合成大分子引发剂BXL-Br。具体过程如下:将溶有TEA(480mg,4.74mmol)、BXL-OH(20g,2.37mmol)和DMAP(869mg,7.11mmol)的DCM(200ml)溶液加入到三口圆底烧瓶中,在氩气及冰浴的状态下,搅拌混合均匀。将2-BiB(2.49g,11.85mmol)溶于50ml的DCM中,冰浴状态下通过恒压漏斗加入到上述混合液中,加入完成后在室温继续搅拌反应24h。反应结束后将溶液旋蒸除去一半溶剂,将剩余产物逐滴滴入冷冻甲醇中沉淀,过滤。重复此溶解-沉淀-过滤过程三次,将纯化后的产物在30℃的真空烘箱中干燥至恒重。
2.3嵌段共聚物聚二甲基硅氧烷-聚己内酯-聚苯乙烯BX-b-PCL-b-PS(BXLS)的合成
BXLS嵌段共聚物是以溴化亚铜(CuBr)为催化剂,N,N,N',N”,N”-五甲基二乙烯三胺(PMDETA)为配位剂,上述产物为大分子引发剂进行原子转移自由基聚合得到。合成步骤表述如下:向250ml的无水无氧瓶中依次加入大分子引发剂(BXL-Br,17.2g,2mmol)、苯乙烯单体(9.47g,91.06mmol)、CuBr(340mg)和PMDETA(990μL),搅拌均匀,经过三次液氮冷冻-真空脱气-解冻循环后,将负压状态下烧瓶置入110℃的油浴中磁力搅拌24小时。待反应结束后,将产物暴漏在空气中冷却至室温使反应停止。将产物溶于二氯甲烷并通过中性氧化铝柱子以除去催化剂。旋蒸浓缩溶液并逐滴滴入大量冷冻甲醇中沉淀,过滤。经三次溶解-沉淀-过滤过程后,将最终产物在30℃的真空烘箱中干燥至恒重。
2.4 BXLS/环氧树脂复合材料的制备
将上述合成的嵌段共聚物加入到环氧预聚体(DGEBA)中,在120℃下剧烈搅拌直至形成均匀溶液,再将固化剂MOCA加入体系中,混合均匀。将所得共混溶液放入110℃真空烘箱以除去体系内气泡,然后将其倒入聚四氟乙烯模具,150℃固化2小时,然后升温至180℃固化2小时。固化反应结束后,脱模得到含嵌段共聚物的环氧热固性树脂。各样品编号及组成如表1所示。
表1.BXLS/环氧树脂复合材料的配方
二、本发明复合材料的性能检测
1测试与表征
1.1凝胶渗透色谱(GPC)
采用美国Waters公司的Waters1515型凝胶渗透色谱仪,以流速0.5μL/min的四氢呋喃为流动相,聚苯乙烯作为标准样,30℃下对原料及合成产物进行分子量测试。
1.2核磁共振氢谱(NMR)
采用德国Bruker公司的DRX-400核磁共振光谱仪,以氘代氯仿作为溶剂,在25℃获得了400MHz的核磁波谱图。
1.3透射电镜(TEM)
利用徕卡UC7低温超薄切片机在-120℃下对样品进行切片,所得式样厚度100~150nm。经过15min四氧化钌常温熏染后,在Tecnai G2F20型透射电镜上进行观察,低电子束流小于10mA,加速电压为120keV。
1.4小角X射线散射(SAXS)
采用法国Xenocs公司配备PILATUS 3R 300K检测器及热台的Xeuss 2.0SAXS/WAXS对样品进行小角X射线散射测试,X射线波长为50kV,0.6mA,曝光时间为10min。
1.5场发射扫描电镜(FESEM)
样品首先在液氮中进行脆断,在真空中对其脆断面进行喷金处理,采用美国FEI公司Nova NanoSEM 450型场发射扫描电镜对样品进行微观结构表征,加速电压为5kV。
1.6拉伸及裂韧性测试
采用Instron 5567万能材料试验机,对样条进行拉伸及断裂韧性测试,样条尺寸如图1所示。拉伸性能测试速度为2mm/min。根据ASTM D5045标准测试试样的断裂韧性,由下式计算试样的断裂韧性,测试速率为2mm/min。
2结果与讨论
2.1嵌段共聚物的合成表征
从图2可以看出,BX-OH、BXL和BXLS的分子量分别为3915(Mw/Mn=1.06),8449(Mw/Mn=1.24)和14034(Mw/Mn=1.06)。经计算得出BXLS中BX-OH、PCL与PS的分子量之比为3915:4534:5585。
从图3可以看出,合成的嵌段共聚物同时具有BX-OH、PCL以及PS的结构特征。
2.2微观结构表征
根据染色原理可知,TEM照片颜色由深到浅分别为PS、环氧树脂基体和富BX-OH相。由图4的TEM照片可知,嵌段共聚物以类“草履虫”的形态分布在环氧树脂基体内部,内部球状结构为富PDMS聚集相,周围形成“PS为壳,PDMS为核”的管状“鞭毛”结构。同时类“草履虫”状结构均是以PDMS为核、PS为壳、PCL为“晕”的“核-壳-晕”(C-S-C)结构。随着嵌段共聚物含量的增加,纳米结构的形态不发生变化,但纳米结构的尺寸有所增加。当添加量为1.75wt%时,球状富PDMS相及整个微观结构的直径分别为~120nm和~280nm。添加量为6.67wt%,球状富PDMS相及整个微观结构的直径分别为~250nm和~550nm。图5的SAXS测试进一步证明了TEM结果,当嵌段共聚物引入环氧树脂中后,SAXS曲线在处观察到明显的散射峰,表明嵌段共聚物在环氧树脂中有纳米结构出现。根据布拉格公式(L=2π/Q),可计算出散射峰对应纳米结构间平均距离为16.11nm。结合TEM照片,SAXS曲线中散射峰应归属于“鞭毛”结构。
2.3微观结构形成过程研究
图6为含6.67wt%BXLS嵌段共聚物的环氧树脂固化前后的SAXS曲线。为进一步研究该阶段纳米结构的形态,我们利用相同的BX-OH合成制备了分子量与BXLS相同的BXL两嵌段共聚物并将其引入环氧树脂中固化,微观形态如图7所示,PDMS在环氧树脂中形成球状分散相。因此,对于BXLS/EP体系,在环氧树脂固化前,BXLS首先自组装形成球状PDMS相。随环氧树脂的固化,PS段开始发生反应诱致微相分离,导致前期形成的球状PDMS相不能稳定存在,纳米结构发生局部重排,同时PCL段被固定在环氧树脂的交联网络中形成“晕”,其固化后SAXS曲线如图6所示。
2.4拉伸性能测试
从图8可以看出,纯环氧树脂的拉伸强度和断裂伸长率分别为71.3MPa和4.4%。当嵌段共聚物添加量仅为1.75wt%时,拉伸强度达到最大值93.6MPa,为环氧树脂的1.31倍。材料断裂伸长率在添加量为3.45wt%时达到最大值,为环氧树脂的1.84倍,进一步增加嵌段共聚物的添加量断裂伸长率略微降低后不变。
2.5断裂韧性测试
从图9可以看出,随嵌段共聚物添加量的增多,材料的断裂韧性与断裂伸长率具有相同的变化趋势。纯环氧树脂的断裂韧性为47N/mm3/2。当嵌段共聚物含量仅为1.75wt%时,材料断裂韧性即有明显的提升,137.4N/mm3/2(为纯环氧树脂的2.92倍)。当添加量为3.45wt%时,材料的断裂韧性达到最大值,为纯环氧树脂的3.2倍。相比于现有技术,本发明可以在嵌段共聚物极低添加量下实现材料韧性的显著增加,具有明显的优势。
综上,BXLS嵌段共聚物在环氧树脂中形成了类“草履虫”状的新型纳米结构,使得本发明制备得到的BXLS/环氧树脂复合材料在BXLS嵌段共聚物添加量极低的情况下实现了材料韧性的显著增加并且还具有更优异的力学强度,极大的拓宽了环氧树脂的应用领域。
Claims (5)
1.一种具有特定纳米结构的高强高韧环氧复合材料:它是由下述重量配比的原料制备而成的:
环氧树脂50份、固化剂20份、BXLS嵌段共聚物1.25~2.5份;
所述BXLS嵌段共聚物由BX-OH引发ε-己内酯开环聚合后,用原子转移自由基聚合方法合成;
所述BXLS嵌段共聚物的结构式为;
其中R选自丁基或乙基;R’选自亚丁基或亚乙基;
所述BXLS嵌段共聚物中BX-OH与PCL、PS的分子量之比为1:1.16:1.43;
所述BX-OH为单羟基封端的聚二甲基硅氧烷;
所述复合材料是由下述方法制备而成:
(1)BXLS嵌段共聚物的制备:由BX-OH引发ε-己内酯开环聚合后,用原子转移自由基聚合方法合成BXLS嵌段共聚物即可;
(2)按重量配比称取环氧树脂以及BXLS嵌段共聚物,混匀后加入固化剂后再次混匀,真空除泡、固化即可。
2.根据权利要求1所述的复合材料,其特征在于:它是由下述重量配比的原料制备而成的:
环氧树脂50份、固化剂20份、BXLS嵌段共聚物2.5份。
3.根据权利要求1或2所述的复合材料,其特征在于:所述环氧树脂为双酚A型环氧树脂。
4.根据权利要求3所述的复合材料,其特征在于:所述双酚A型环氧树脂选自E-51、E-44。
5.根据权利要求1或2所述的复合材料,其特征在于:所述固化剂选自3,3´-二氯-4,4´-二氨基二苯基甲烷、4,4´-二氨基二苯基砜、二氨基二苯甲烷。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811427649.6A CN109679282B (zh) | 2018-11-27 | 2018-11-27 | 一种具有特定纳米结构的高强高韧环氧复合材料 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811427649.6A CN109679282B (zh) | 2018-11-27 | 2018-11-27 | 一种具有特定纳米结构的高强高韧环氧复合材料 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109679282A CN109679282A (zh) | 2019-04-26 |
CN109679282B true CN109679282B (zh) | 2024-05-17 |
Family
ID=66184971
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811427649.6A Active CN109679282B (zh) | 2018-11-27 | 2018-11-27 | 一种具有特定纳米结构的高强高韧环氧复合材料 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109679282B (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110128789A (zh) * | 2019-05-27 | 2019-08-16 | 四川大学 | 一种高强高韧环氧树脂复合材料 |
CN110093015B (zh) * | 2019-05-27 | 2024-01-19 | 四川大学 | 一种囊泡型高性能环氧树脂复合材料 |
CN110128790A (zh) * | 2019-05-27 | 2019-08-16 | 四川大学 | 一种高强高韧环氧树脂复合材料及其制备方法 |
CN110079053A (zh) * | 2019-05-27 | 2019-08-02 | 四川大学 | 一种纳米改性环氧树脂复合材料及其制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101111560A (zh) * | 2004-11-10 | 2008-01-23 | 陶氏环球技术公司 | 两性嵌段共聚物-增韧的环氧树脂 |
CN101935436A (zh) * | 2010-07-09 | 2011-01-05 | 浙江大学 | 一种纳米结构环氧树脂固化物的制备方法和用途 |
CN102675826A (zh) * | 2012-04-25 | 2012-09-19 | 北京化工大学常州先进材料研究院 | 一种耐温型高强高韧复合环氧树脂组成及其制造方法 |
JP2012197413A (ja) * | 2010-09-28 | 2012-10-18 | Toray Ind Inc | エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料 |
CN107057282A (zh) * | 2017-01-05 | 2017-08-18 | 四川大学 | 一种梯度复合材料及其制备方法 |
CN107163204A (zh) * | 2017-07-11 | 2017-09-15 | 四川大学 | 一种高强高韧热固性树脂基复合材料的制备方法及应用 |
CN107459612A (zh) * | 2017-09-11 | 2017-12-12 | 四川大学 | 一种增强增韧剂、增韧环氧树脂复合材料及其制备方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2809741B1 (fr) * | 2000-05-31 | 2002-08-16 | Atofina | Materiaux thermodurs a tenue au choc amelioree |
US20070005130A1 (en) * | 2005-06-29 | 2007-01-04 | Thierry Glauser | Biodegradable polymer for coating |
-
2018
- 2018-11-27 CN CN201811427649.6A patent/CN109679282B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101111560A (zh) * | 2004-11-10 | 2008-01-23 | 陶氏环球技术公司 | 两性嵌段共聚物-增韧的环氧树脂 |
CN101935436A (zh) * | 2010-07-09 | 2011-01-05 | 浙江大学 | 一种纳米结构环氧树脂固化物的制备方法和用途 |
JP2012197413A (ja) * | 2010-09-28 | 2012-10-18 | Toray Ind Inc | エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料 |
CN102675826A (zh) * | 2012-04-25 | 2012-09-19 | 北京化工大学常州先进材料研究院 | 一种耐温型高强高韧复合环氧树脂组成及其制造方法 |
CN107057282A (zh) * | 2017-01-05 | 2017-08-18 | 四川大学 | 一种梯度复合材料及其制备方法 |
CN107163204A (zh) * | 2017-07-11 | 2017-09-15 | 四川大学 | 一种高强高韧热固性树脂基复合材料的制备方法及应用 |
CN107459612A (zh) * | 2017-09-11 | 2017-12-12 | 四川大学 | 一种增强增韧剂、增韧环氧树脂复合材料及其制备方法 |
Non-Patent Citations (3)
Title |
---|
Controllable design of nanostructure in block copolymer reinforced epoxy composites;Heng Z G, et al.;《Journal of Applied Polymer Science》;20180223;第135卷(第23期);46362 * |
Fan W C, et al.Nanostructures in Thermosetting Blends of Epoxy Resin with Polydimethylsiloxane-block-poly(ε-caprolactone)- block-polystyrene ABC Triblock Copolymer.《Macromolecules》.2008,第42卷第327-336页. * |
Nanostructures in Thermosetting Blends of Epoxy Resin with Polydimethylsiloxane-block-poly(ε-caprolactone)- block-polystyrene ABC Triblock Copolymer;Fan W C, et al;《Macromolecules》;20081204;第42卷;第327-336页 * |
Also Published As
Publication number | Publication date |
---|---|
CN109679282A (zh) | 2019-04-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109679282B (zh) | 一种具有特定纳米结构的高强高韧环氧复合材料 | |
CN109694551B (zh) | 一种具有特定纳米结构的高性能环氧复合材料的制备方法 | |
EP1866369A2 (en) | Thermoset materials with improved impact resistance | |
Xu et al. | Morphology and thermal properties of organic–inorganic hybrid material involving monofunctional-anhydride POSS and epoxy resin | |
CN113861421B (zh) | 一种聚酰亚胺型环氧树脂增韧剂及其制备方法 | |
WO2019011244A1 (zh) | 一种高强高韧热固性树脂基复合材料的制备方法及应用 | |
US20110294963A1 (en) | Method of toughening epoxy resin and toughened epoxy resin composite | |
Li et al. | Preparation and properties of room temperature vulcanized silicone rubber based on rosin-grafted polydimethylsiloxane | |
Jia et al. | Toxic phthalate-free and highly plasticized polyvinyl chloride materials from non-timber forest resources in plantation | |
CN115403764B (zh) | 一种含有环氧基团的聚芳醚酮化合物及其制备方法 | |
Liu et al. | Simultaneous reinforcement and toughness improvement of an epoxy–phenolic network with a hyperbranched polysiloxane modifier | |
Lee et al. | Toughening of semi‐IPN structured epoxy using a new PEEK‐type polymer via in situ azide–alkyne click polymerization | |
Zhao et al. | Morphology and properties of nanostructured epoxy blends toughened with epoxidized carboxyl-terminated liquid rubber | |
AU2016266802B2 (en) | Silicone elastomers and their preparation and use | |
Heng et al. | Enhancing mechanical performance of epoxy thermosets via designing a block copolymer to self-organize into “core–shell” nanostructure | |
Yang et al. | Low dielectric constant and high thermal stability of liquid crystal epoxy polymers based on functionalized poly (phenylene oxide) | |
Naguib et al. | Non-reactive and reactive block copolymers for toughening of UV-cured epoxy coating | |
Zhang et al. | Thermomechanical, surface and shape memory properties of thermosetting blends of epoxy with Poly (ethylene oxide): An impact of POSS microdomain formation | |
CN110093015B (zh) | 一种囊泡型高性能环氧树脂复合材料 | |
CN110577629B (zh) | 一种可降解的环氧树脂及其制备方法 | |
CN110437624B (zh) | 一种透明双官能环氧树脂-硅橡胶嵌段网络材料 | |
CN109734854B (zh) | 一种可在环氧树脂中自发构筑特定纳米结构的嵌段共聚物及其在环氧树脂高性能化中的应用 | |
Morell et al. | Multiarm star poly (glycidol)-block-poly (styrene) as modifier of anionically cured diglycidylether of bisphenol A thermosetting coatings | |
Jothibasu et al. | Synthesis and characterization of a POSS-maleimide precursor for hybrid nanocomposites | |
Wu et al. | Graphene oxide as a covalent-crosslinking agent for EVM-g-PA6 thermoplastic elastomeric nanocomposites |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |