CN116215046A - 一种耐冲击型及环境适应性纤维增强树脂基复合材料及其预浸料制造方法 - Google Patents
一种耐冲击型及环境适应性纤维增强树脂基复合材料及其预浸料制造方法 Download PDFInfo
- Publication number
- CN116215046A CN116215046A CN202211738451.6A CN202211738451A CN116215046A CN 116215046 A CN116215046 A CN 116215046A CN 202211738451 A CN202211738451 A CN 202211738451A CN 116215046 A CN116215046 A CN 116215046A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- thermoplastic
- constituent
- resin
- fiber
- 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.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 229920005989 resin Polymers 0.000 title claims abstract description 18
- 239000011347 resin Substances 0.000 title claims abstract description 18
- 239000011159 matrix material Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000000835 fiber Substances 0.000 title claims abstract description 14
- 239000003822 epoxy resin Substances 0.000 claims abstract description 123
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 123
- 239000002245 particle Substances 0.000 claims abstract description 87
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 239000000470 constituent Substances 0.000 claims abstract description 37
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 36
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 36
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 10
- 239000002344 surface layer Substances 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229920002292 Nylon 6 Polymers 0.000 claims description 9
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 8
- 239000004814 polyurethane Substances 0.000 claims description 8
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 239000004695 Polyether sulfone Substances 0.000 claims description 7
- 229920006393 polyether sulfone Polymers 0.000 claims description 7
- 239000000805 composite resin Substances 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 150000001412 amines Chemical group 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004677 Nylon Substances 0.000 claims description 4
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- -1 ether amine Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/105—Coating or impregnating independently of the moulding or shaping step of reinforcement of definite length with a matrix in solid form, e.g. powder, fibre or sheet form
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- 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
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
- B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
本发明提供一种耐冲击型及环境适应性纤维增强树脂基复合材料及其预浸料制造方法。其包含以下构成要素[A]~[E]:构成要素[A]为一种粒径在10~20μm不溶于环氧树脂的热塑性粒子;构成要素[B]为一种粒径在10~20μm不溶于环氧树脂的晶体粒子。其预浸料构成由构成要素[C]强化纤维基材和在构成要素[C]内浸入的至少含有环氧树脂和可溶解于环氧树脂的热塑性树脂及构成要素[B]的环氧树脂组合物[D]构成的一次预浸料;由在一次预浸料的单面或者两面形成的至少含有环氧树脂和可溶解于环氧树脂的热塑性树脂及构成要素[A]的环氧树脂组合物[E]构成表面层。所制备的材料具有优良的耐冲击性和环境适应性。
Description
技术领域
本发明涉及适用于汽车船舶、工程基建、体育休闲或其他领域具备高强、高韧性及环境适应性的纤维增强树脂基复合材料及预浸料制造方法。
背景技术
随着轻量化的发展,聚合物基复合材料因为其高比强度、高比模量及密度低等特点已被广泛的应用在航空航天、风电叶片、汽车船舶等领域。其中间体预浸料的出现及广泛应用大大缩短了产品制造周期,扩展了应用领域,其中以热固性环氧树脂预浸料的应用最为广泛,但其往往因为高交联密度在预浸料制备的复合材料表现出低的耐冲击性。现有的改善复合材料耐冲击性方法主要以热塑性树脂、薄膜为主,但其用量高等特点导致树脂粘度大成型后复合材料空隙率高等原因,导致最终的力学性能发挥率低,环境适应性低。本发明主要从提高树脂韧性、及复合材料层间韧性角度出发。提供一种高韧性耐冲击性及环境适应性的预浸料,并合适的获得该纤维增强树脂基复合材料及其预浸料的方法。
发明内容
针对现有环氧树脂基复合材料普遍存在面外性能差缺点,本发明的目的在于提供一种高强高韧性,耐冲击性及环境适应性的预浸料,并合适的获得该纤维增强树脂基复合材料及其预浸料的方法。以提高所制备的高性能复合材料纵向抵御外在载荷的能力,拓宽树脂基复合材料的应用领域。
本发明采取了以下技术方案:
一种耐冲击型及环境适应性纤维增强树脂基复合材料,包含构成要素[A]~[E]组成,其预浸料构成由构成要素[C]强化纤维基材和在构成要素[C]内浸入的至少含有环氧树脂和可溶解于环氧树脂的热塑性树脂及构成要素[B]的环氧树脂组合物[D]构成的一次预浸料;由在一次预浸料的单面或者两面形成的至少含有环氧树脂和可溶解于环氧树脂的热塑性树脂及构成要素[A]的环氧树脂组合物[E]构成表面层。
[A]粒径在10~20μm不溶于环氧树脂的热塑性粒子
[B]粒径在10~20μm不溶于环氧树脂的晶体粒子
[C]强化纤维基材
[D]环氧树脂组合物,至少含有环氧树脂和可溶解于环氧树脂的热塑性树脂及构成要素[B]
[E]环氧树脂组合物,至少含有环氧树脂和可溶解于环氧树脂的热塑性树脂及构成要素[A]。
在上述一种耐冲击型及环境适应性纤维增强树脂基复合材料及其预浸料制造方法中构成要素[A]为不溶于环氧树脂的热塑性粒子。
具体的构成要素[A]占构成要素[E]中重量比为5wt%~15wt%。所述热塑性粒子选自非晶型尼龙、尼龙6、尼龙66、聚酰亚胺、聚氨酯中的至少一种。热塑性粒子可以是具备三维改性结构的热塑性粒子。其中热塑性粒子粒径分布在10~20μm,球形度高于95%。
在上述一种耐冲击型及环境适应性纤维增强树脂基复合材料及其预浸料制造方法中构成要素[B]为不溶于环氧树脂的热塑性粒子。
具体的构成要素[B]占构成要素[D]中重量比为5wt%~15wt%。所述不溶于环氧树脂的热塑性粒子选自晶型尼龙、尼龙6、尼龙66、晶型聚酰亚胺中的至少一种,热塑性粒子粒径分布在10~20μm。其中晶型热塑性粒子的熔点不高于所制备的预浸料固化温度。
在上述一种耐冲击型及环境适应性纤维增强树脂基复合材料及其预浸料制造方法中构成要素[C]强化纤维为碳纤维、玻璃纤维、芳纶纤维、玄武岩纤维、超高分子量聚乙烯纤维中的一种。构成要素[C]的强化纤维可以是纤维、织物或毡形式。
在上述一种耐冲击型及环境适应性纤维增强树脂基复合材料及其预浸料制造方法中构成要素[D]和[E]至少含热塑性树脂、固化剂,构成要素[D]中含有构成要素[A],构成要素[E]中含有构成要素[B]。
具体的所述环氧树脂选自缩水甘油醚性环氧树脂、脂环族环氧树脂、缩水甘油胺类环氧树脂、环氧化烯烃类、聚氨酯改性环氧树脂或异氰酸酯改性环氧树脂中的一种以上。所述热塑性树脂为可溶于环氧树脂中的热塑性树脂。可溶性热塑性树脂可以为聚砜、聚醚砜、聚芳醚砜、聚醚醚酮、聚碳酸酯中的一种。所述固化剂为胺型固化剂,固化剂可为二氨基二苯砜、二氨基二苯甲烷或双氰胺等中的一种或多种混合物或其衍生物和异构体。
在上述一种耐冲击型及环境适应性纤维增强树脂基复合材料及其预浸料制造方法中,其特征在于由构成要素[C]强化纤维基材和在构成要素[C]内浸入的至少含有环氧树脂和可溶解于环氧树脂的热塑性树脂及构成要素[B]的环氧树脂组合物[D]构成的一次预浸料;由在一次预浸料的单面或者两面形成的至少含有环氧树脂和可溶解于环氧树脂的热塑性树脂及构成要素[A]的环氧树脂组合物[E]构成表面层。
在上述一种耐冲击型及环境适应性纤维增强树脂基复合材料及其预浸料制造方法中,其特征在于所制备的预浸料在成型制备时,熔融构成要素[B]存在连接构成要素[A]作用。
在上述一种耐冲击型及环境适应性纤维增强树脂基复合材料及其预浸料制造方法中其特征在于所制备的纤维增强复合材料具有优良的耐冲击性和环境适应性。
与现有技术相比,本发明的优点是:
本发明采用热塑性粒子和晶型粒子层间增韧环氧树脂基复合材料,在所制备的预浸料固化时熔融的晶体粒子可与高活性三维交联结构热塑性粒子紧密结合。同时本发明相比现有预浸料成型技术采用2次含浸技术,在预浸料成型过程分别制备含热塑性粒子和晶型粒子的环氧树脂,先含浸的含晶型粒子环氧树脂膜存在增强材料表面,可抵御后含浸的含热塑性粒子环氧树脂膜因含浸工艺将热塑性粒子进入层间,含浸后热塑性粒子和晶体粒子可均匀分布于表面,通过晶体粒子紧密结合的热塑性粒子在受到纵向载荷作用时可抵御更大的外在作用力,从而提高其复合材料层压板的抗冲击性能。
附图说明:
图1是本发明材料示意图。
图中A为不溶于环氧树脂的热塑性粒子,B为不溶于环氧树脂的晶体粒子,C为强化纤维,D为环氧树脂组合物,由环氧树脂和可溶解于环氧树脂的热塑性树脂及构成要素[B]组成,E为环氧树脂组合物,由环氧树脂和可溶解于环氧树脂的热塑性树脂及构成要素[A]组成。
其中一次预浸料是由D在C的单面或者双面形成的。本发明所述预浸料是由E在一次预浸料的单面或双面形成。
具体实施方式
以下举出实施例更详细的说明本发明,但本发明不限定于这些实施例。
实施实例中2官能团环氧树脂选择双酚F型环氧树脂,四官能团环氧树脂选择四缩水甘油醚胺型环氧树脂,3官能团树脂选用三缩水甘油醚型胺型环氧树脂。
热塑性树脂选择聚醚砜;热塑性粒子选择聚氨酯粒子;晶体粒子选择尼龙6粒子和尼龙12粒子。
固化剂为4,4二氨基二苯砜。
强化纤维为T800级碳纤维。
实施例1:
使用含搅拌与分散功能与一体的搅拌机,将热塑性树脂聚醚砜在120℃溶解于环氧树脂中,聚醚砜是环氧树脂重量的12%,环氧树脂是由2官能团缩水甘油醚性环氧树脂、3官能团缩水甘油醚性环氧树脂和4官能团胺型环氧树脂组成。2官能团缩水甘油醚性环氧树脂、3官能团缩水甘油醚性环氧树脂和4官能团胺型环氧树脂的质量比例为2:1:7。2官能团缩水甘油醚性环氧树脂的环氧值0.51~0.54。3官能团缩水甘油醚性环氧树脂的环氧值0.7~0.9。4官能团胺型环氧树脂的环氧值0.7~0.9,聚醚砜粒径为20μm。聚醚砜溶解完成后,降温至70~80℃,添加晶体粒子混合搅拌40分钟,晶体粒子为平均粒径为20μm的尼龙6粒子,球形度高于95%,尼龙6粒子在环氧树脂组合物配方中占比为10wt%。最后加入固化剂混合40分钟,配制环氧树脂组合物[D]。固化剂为4,4二氨基二苯砜。
以相同的方法配制环氧树脂组合物[E],环氧树脂组合物[E]配制过程中热塑性粒子为3维交联结构聚氨酯粒子,平均粒径15μm,玻璃化转变温度90℃,聚氨酯粒子在环氧树脂组合物配方中占比为10wt%。
使用涂膜机分别将环氧树脂组合物[D]和环氧树脂组合物[E]涂膜至离型纸上,得到单位面积质量的环氧树脂组合物膜[D]和环氧树脂组合物膜[E],环氧树脂组合物膜[D]和环氧树脂组合物膜[E]单位面积质量为25g/m2,所制备的预浸料树脂膜单位面积质量100g/m2。
在预浸料含浸机上,采用4膜含浸工艺。通过含浸机放卷装置将T800碳纤维引至含浸机压辊间隙内,所制备的预浸料纤维单位面积质量为194g/m2,通过放卷装置在T800碳纤维表面先引入环氧树脂组合物膜[D],环氧树脂组合物膜[D]在120℃加压和加热,压力为4kg,得到1次预浸料。通过放卷装置在上述1次预浸料上引入环氧树脂组合物膜[E],环氧树脂组合物膜[E]在100℃加压和加热,压力为4kg,得到预浸料,树脂质量份数为34%。所获预浸料热塑性粒子在预浸料表面固化后具备优良的抵御外在载荷能力。
实施例2、比较例1~比较例2,所采用的热塑性粒子和晶体粒子不同,其制备工艺与实施例1相同。
实施例2中环氧树脂组合物[D]所采用的晶体粒子为平均粒径20μm的尼龙6粒子,环氧树脂组合物[E]所采用的热塑性粒子为平均粒径20μm的尼龙12粒子。
比较例1中环氧树脂组合物[D]所采用的晶体粒子为平均粒径20μm的尼龙6粒子,环氧树脂组合物[E]未使用热塑性粒子。
比较例2中环氧树脂组合物[D]未使用晶体粒子,环氧树脂组合物[E]所采用热塑性粒子为3维交联结构聚氨酯粒子
本发明所制备的预浸料均是经过真空辅助热压罐成型工艺获得测试样板。实施例1和比较例1比较发现仅使用晶体粒子进行层间增韧制备的复合材料韧性提高有限,实施例和比较例2比较发现仅使用交联结构的热塑性粒子进行层间增韧制备的复合材料韧性有一定的提高,但均低于热塑性粒子和晶体粒子组合使用。实施例1~实施例2均使用热塑性粒子和晶体粒子,实施例1和实施例2均具有较高的冲击后压缩强度、Ⅰ型断裂韧性和Ⅱ型断裂韧性。实施例1和实施例2所制备的预浸料先含浸的含晶型粒子环氧树脂膜存在增强材料表面,可抵御后含浸的含热塑性粒子环氧树脂膜因含浸工艺将热塑性粒子进入层间,含浸后热塑性粒子和晶体粒子可均匀分布于表面,预浸料固化时熔融的晶体粒子可与高活性三维交联结构热塑性粒子紧密结合,当制件受到纵向载荷作用时可抵御更大的外在作用力,从而提高其复合材料层压板的抗冲击性能。
Claims (6)
1.一种耐冲击型及环境适应性纤维增强树脂基复合材料,其特征在于:
包含构成要素[A]~[E];构成要素[C]强化纤维基材、和构成要素[C]内浸入的至少含有环氧树脂和可溶解于环氧树脂的热塑性树脂及构成要素[B]的环氧树脂组合物[D]构成一次预浸料;
由在一次预浸料的单面或者两面形成的环氧树脂组合物[E]构成表面层,环氧树脂组合物[E]至少含有环氧树脂和可溶解于环氧树脂的热塑性树脂及构成要素[A];
[A]粒径在10~20μm不溶于环氧树脂的热塑性粒子
[B]粒径在10~20μm不溶于环氧树脂的晶体粒子
[C]强化纤维基材
环氧树脂组合物[D],至少含有环氧树脂和可溶解于环氧树脂的热塑性树脂及构成要素[B]
环氧树脂组合物[E],至少含有环氧树脂和可溶解于环氧树脂的热塑性树脂及构成要素[A]。
2.如权利要求1所述的一种耐冲击型及环境适应性纤维增强树脂基复合材料,其中构成要素[A]为不溶于环氧树脂的热塑性粒子;具体的构成要素[A]占环氧树脂组合物[E]中重量比为5wt%~15wt%;所述热塑性粒子选自非晶型尼龙、尼龙6、尼龙66、聚酰亚胺、聚氨酯中的至少一种;其中热塑性粒子粒径分布在10~20μm,球形度高于95%。
3.如权利要求1所述所述的一种耐冲击型及环境适应性纤维增强树脂基复合材料,其中构成要素[B]为不溶于环氧树脂的晶体粒子;构成要素[B]占环氧树脂组合物[D]中重量比为5wt%~15wt%;所述不溶于环氧树脂的晶体粒子选自晶型尼龙、尼龙6、尼龙66、晶型聚酰亚胺中的至少一种,晶型粒子粒径分布在10~20μm。
4.如权利要求1所述所述的一种耐冲击型及环境适应性纤维增强树脂基复合材料,其中构成要素[C]强化纤维为碳纤维、玻璃纤维、芳纶纤维、玄武岩纤维、超高分子量聚乙烯纤维中的一种。
5.如权利要求1所述的一种耐冲击型及环境适应性纤维增强树脂基复合材料,其中环氧树脂组合物[D]和[E]至少含热塑性树脂、固化剂;
所述环氧树脂选自缩水甘油醚性环氧树脂、脂环族环氧树脂、缩水甘油胺类环氧树脂、环氧化烯烃类、聚氨酯改性环氧树脂或异氰酸酯改性环氧树脂中的一种以上;所述热塑性树脂为可溶于环氧树脂中的热塑性树脂;可溶性热塑性树脂为聚砜、聚醚砜、聚芳醚砜、聚醚醚酮、聚碳酸酯中的一种;所述固化剂为胺型固化剂。
6.制备如权利要求1所述的复合材料的方法,其特征在于由构成要素[C]强化纤维基材和在构成要素[C]内浸入的至少含有环氧树脂和可溶解于环氧树脂的热塑性树脂及构成要素[B]的环氧树脂组合物[D]构成的一次预浸料;由在一次预浸料的单面或者两面形成的至少含有环氧树脂和可溶解于环氧树脂的热塑性树脂及构成要素[A]中一种的环氧树脂组合物[E]构成表面层。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211738451.6A CN116215046A (zh) | 2022-12-31 | 2022-12-31 | 一种耐冲击型及环境适应性纤维增强树脂基复合材料及其预浸料制造方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211738451.6A CN116215046A (zh) | 2022-12-31 | 2022-12-31 | 一种耐冲击型及环境适应性纤维增强树脂基复合材料及其预浸料制造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN116215046A true CN116215046A (zh) | 2023-06-06 |
Family
ID=86570694
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211738451.6A Pending CN116215046A (zh) | 2022-12-31 | 2022-12-31 | 一种耐冲击型及环境适应性纤维增强树脂基复合材料及其预浸料制造方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116215046A (zh) |
-
2022
- 2022-12-31 CN CN202211738451.6A patent/CN116215046A/zh active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101511186B1 (ko) | 열가소성 입자들의 블렌드를 갖는 복합 재료 | |
Campbell Jr | Manufacturing processes for advanced composites | |
CA2769557C (en) | Improvements in composite materials | |
US11167502B2 (en) | Composites with interlaminar toughening particles and method of making the same | |
US20170158829A1 (en) | Two-pack type epoxy resin composition for fiber-reinforced composite material, and fiber-reinforced composite material | |
JP2010126702A (ja) | エポキシ樹脂組成物、繊維強化複合材料およびそれらの製造方法 | |
EP3129428B1 (en) | Composite materials | |
KR101767699B1 (ko) | 엔지니어링 열가소성 물질 중의 다작용기성 첨가제 | |
KR20160052638A (ko) | 섬유 강화 수지 및 그의 제조 방법, 및 성형품 | |
JP4475880B2 (ja) | エポキシ樹脂組成物 | |
CN116694030A (zh) | 一种超轻质高强复合材料及其制备方法和应用 | |
EP0351028A2 (en) | Resin particle-filled, fiber-reinforced composites | |
CN106062051B (zh) | 具有聚酰胺颗粒混合物的复合材料 | |
CN110202905B (zh) | 原位三维树脂复合材料及其应用 | |
JP2012193322A (ja) | プリプレグ、および炭素繊維強化複合材料 | |
JPH05239317A (ja) | エポキシ樹脂組成物、プリプレグおよびプリプレグの製造法 | |
CN116215046A (zh) | 一种耐冲击型及环境适应性纤维增强树脂基复合材料及其预浸料制造方法 | |
CN110337461B (zh) | 热塑性增韧的环氧复合材料在热和湿条件下保持压缩强度 | |
JP5034176B2 (ja) | プリフォーム用バインダー組成物、プリフォーム用強化繊維基材、プリフォームの製造方法および繊維強化複合材料の製造方法 | |
CN115210318B (zh) | 环氧树脂组合物、预浸料及纤维增强复合材料 | |
CA2044787A1 (en) | Fiber-reinforced composites toughened with porous resin particles | |
KR101884606B1 (ko) | 고내충격성고강도 특성을 갖는 복합재료용 에폭시 수지 조성물 | |
KR20180029805A (ko) | 스키 제조용 저온 경화형 에폭시 수지 조성물과 이에 의해 제조된 스키 제조용 프리프레그 및 이를 이용한 섬유 강화 고분자 복합재료 | |
JP2010059300A (ja) | 炭素繊維強化複合材料およびその製造方法 | |
CN114044922B (zh) | 纳米合金热塑粒子、纳米合金膜及其制备方法和应用 |
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 |