CN109971138B - Self-repairing PCBT composite material and preparation method thereof - Google Patents
Self-repairing PCBT composite material and preparation method thereof Download PDFInfo
- Publication number
- CN109971138B CN109971138B CN201910225371.2A CN201910225371A CN109971138B CN 109971138 B CN109971138 B CN 109971138B CN 201910225371 A CN201910225371 A CN 201910225371A CN 109971138 B CN109971138 B CN 109971138B
- Authority
- CN
- China
- Prior art keywords
- pcbt
- self
- composite material
- catalyst
- parts
- 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
Images
Classifications
-
- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- 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
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/06—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The invention discloses a self-repairing PCBT composite material and a preparation method thereof. The unsaturated polyester block enters, so that on one hand, the crystallinity of the PCBT is reduced, the brittleness of the PCBT is improved, the comprehensive performance of the PCBT is improved, and on the other hand, the molecular chain of the PCBT contains Diels-Alder bonds, and the PCBT is endowed with the self-repairing performance.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a self-repairing PCBT composite material and a preparation method thereof.
Background
Since the 20 th century, on the basis of steady development of science and technology and continuous social progress, the requirements of people on engineering materials, such as light weight, high strength, structural and functional integrated design and the like, are further improved, and the requirements are particularly reflected in high-end technical fields of aviation, aerospace, electronics and the like. Traditional single functional materials have been far from meeting the multifaceted requirements of engineering applications. With the continuous development of new materials and new technologies, composite materials are creditably a new pet for engineering materials by virtue of their designability. Compared with thermosetting composite materials, thermoplastic composite materials have the advantages of better toughness and impact resistance, short molding period, low manufacturing cost, recyclable waste materials, secondary processing of products and the like, and are widely applied to various industrial fields.
Poly Cyclic Butylene Terephthalate (PCBT) is thermoplastic engineering plastic obtained by ring-opening polymerization of Cyclic Butylene Terephthalate (CBT) under the action of catalyst. PCBT has higher strength, better impact toughness and recyclability, so that the PCBT has excellent development potential in the field of thermoplastic composite materials. In the polymerization reaction for preparing PCBT from CBT, no reaction heat is released, crystallization and polymerization occur simultaneously, demoulding can be carried out without cooling, and the whole forming period is short. However, the PCBT crystal produced by the forming mode is perfect, so that the PCBT crystal has high brittleness and poor toughness. However, the research on the toughening modification of PCBT is very limited at present, and the toughening modification effect is generally poor.
In addition, the material is not protected from macroscopic or microscopic damage, typically impact damage, and microscopic microcracking. The microcracks affect various mechanical properties of the material, such as strength, stiffness, dimensional stability, and the like. Meanwhile, the microcracks also provide places for environmental aging of the material, which leads to degradation of the material and performance reduction, influences normal use of the material and shortens the service life. Early repair, and in particular self-repair, of cracks is a real and important problem. With the continuous and deep research on the self-repairing performance of polymer materials, the self-repairing is developed from external self-repairing to intrinsic self-repairing without adding a repairing agent additionally. Intrinsic self-repairing is realized mainly by utilizing reversible covalent bonds or reversible non-covalent bonds in materials, and researchers have conducted extensive research on reversible covalent bond self-repairing systems because the acting force between covalent bonds is far greater than that between non-covalent bonds. The thermally reversible Diels-Alder reaction is a cycloaddition reaction between a diene and a dienophile, and is one of hot spots for research on self-repairing materials because the reaction conditions are mild, a catalyst is not needed, and the thermally reversible Diels-Alder reaction has good thermal reversibility. At present, no relevant research report on self-repairing of PCBT materials is found.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provide a self-repairing PCBT composite material and a preparation method thereof. According to the invention, environment-friendly furyl polyester and bismaleimide are crosslinked to prepare unsaturated polyester with Diels-Alder bonds, and then the unsaturated polyester containing the Diels-Alder bonds is blended with CBT resin to generate graft copolymerization on a PCBT chain. The unsaturated polyester block enters, so that on one hand, the crystallinity of the PCBT is reduced, the brittleness of the PCBT is improved, the comprehensive performance of the PCBT is improved, and on the other hand, the molecular chain of the PCBT contains Diels-Alder bonds, and the PCBT is endowed with the self-repairing performance.
In order to realize the purpose, the invention adopts the technical scheme that:
a self-repairing PCBT composite material comprises the following components in parts by weight: 90-100 parts of CBT resin, 10-20 parts of unsaturated polyester containing Diels-Alder bonds, 50-100 parts of unidirectional continuous fiber cloth, 0.2-0.6 part of catalyst, 0.5-2.5 parts of inorganic flame retardant and 0.5-1.5 parts of color paste.
Preferably, the self-repairing PCBT composite material comprises the following components in parts by weight: 100 parts of CBT resin, 20 parts of unsaturated polyester containing Diels-Alder bonds, 80 parts of unidirectional continuous fiber cloth, 0.4 part of catalyst, 1.5 parts of inorganic flame retardant and 1 part of color paste.
Preferably, the preparation method of the unsaturated polyester containing the Diels-Alder bond comprises the following steps: reacting furyl polyester and bismaleimide in excessive N, N' -Dimethylformamide (DMF) for 24-30 h under mechanical stirring at 62-68 ℃, cooling the reaction liquid to room temperature, placing the reaction liquid in anhydrous ether for settling for 2-4 times, and finally drying the precipitate in a vacuum oven at 40-50 ℃ for 18-24 h to obtain the unsaturated polyester containing Diels-Alder bonds.
Preferably, in the preparation method of the Diels-Alder bond-containing unsaturated polyester, the molar ratio of the furyl polyester to the bismaleimide is (8:1) - (10: 1). According to the invention, a great deal of creative experiments show that the yield of the product is greatly influenced by the dosage of the furyl polyester and the bismaleimide, and the yield of the product is higher when the furyl polyester and the bismaleimide are matched and reacted at the molar ratio of the invention. And when the molar ratio of the furyl polyester to the bismaleimide is 9:1, the yield of the product is highest.
Preferably, the furyl polyester is at least one of polyethylene 2, 5-furandicarboxylate (PEF), and polybutylene 2, 5-furandicarboxylate (PBF). PEF and PBF belong to bio-based polyester, are products prepared by using renewable resources 2, 5-furandicarboxylic acid and dihydric alcohol as raw materials, and have better mechanical and thermal properties.
Preferably, the unidirectional continuous fiber cloth is made of at least one of glass fiber, carbon fiber and basalt fiber. The CBT resin has excellent impregnation effect on the glass fiber, the carbon fiber and the basalt fiber, and the PCBT composite material with high surface finish, good mechanical property, environmental protection and reutilization can be prepared by compounding the CBT resin, the glass fiber, the carbon fiber and the basalt fiber.
Preferably, the catalyst consists of an organotin catalyst and an organoaluminum catalyst. Preferably, in the catalyst, the ratio of organic tin catalyst: (1-3) an organoaluminum catalyst. Most preferably, in the catalyst, the ratio by mass of the organotin catalyst: organoaluminum catalyst 5: 2. Preferably, the organic tin catalyst is at least one of monobutyl tin oxide, dihydroxy butyl tin chloride and stannoxane. Preferably, the organic aluminum catalyst is at least one of aluminum triethoxide, aluminum triisopropoxide and aluminum ethylene glycol. The organic aluminum catalyst adopted by the invention has better activity, does not contain heavy metal, is harmless to people and livestock, and is a novel catalyst meeting the requirement of environmental protection. The organic aluminum catalyst and the organic tin catalyst are compounded, so that the using amount of the organic tin catalyst can be reduced, a catalytic synergistic effect can be generated, the catalytic activity is higher, the number of active centers is increased, the molecular chain of a product is increased, the molecular weight is increased, and the prepared PCBT composite material has more excellent mechanical properties.
Preferably, the inorganic flame retardant is at least one of nano aluminum hydroxide, nano antimony trioxide and nano zinc borate. More preferably, the inorganic flame retardant consists of nano aluminum hydroxide, nano antimony trioxide and nano zinc borate. The inorganic flame retardant adopted by the invention has the advantages of nano-level granularity, large specific surface area, high activity, small dosage, large permeability to fabrics, high adhesion, no influence on the surface smoothness of the composite material, three functions of flame retardance, smoke abatement and filling, obvious flame retardance effect, no secondary pollution during combustion, good dispersibility and capability of improving the mechanical property of the material. Meanwhile, the compounding of the nano aluminum hydroxide, the nano antimony trioxide and the nano zinc borate can generate a flame-retardant synergistic effect, so that the flame-retardant property of the composite material is better.
Preferably, in the inorganic flame retardant, the ratio of nano aluminum hydroxide: nano antimony trioxide: and (1-3) the ratio of nano zinc borate to nano zinc borate is 1: 1. Most preferably, in the inorganic flame retardant, the ratio of nano aluminum hydroxide: nano antimony trioxide: nano zinc borate is 2:1: 1. The nanometer aluminum hydroxide, the nanometer antimony trioxide and the nanometer zinc borate are compounded according to the proportion, so that the flame retardant synergistic effect is more obvious.
Preferably, the preparation method of the self-repairing PCBT composite material comprises the following steps:
(1) respectively prefabricating CBT resin, unsaturated polyester containing Diels-Alder bonds and a catalyst into powder, uniformly mixing, heating to 160-180 ℃ under a vacuum condition, melting, adding an inorganic flame retardant, uniformly stirring, adding color paste, uniformly stirring, pouring into unidirectional continuous fiber cloth, fully soaking, cooling, and winding to obtain a prepreg;
(2) and (2) placing the prepreg into a mould, paving the single-layer prepreg in a 45-degree crossed layer, placing the mould on a hot press, carrying out hot press molding under a vacuum condition at 190-220 ℃, keeping for 1-4 h, cooling, and demoulding to obtain the self-repairing PCBT composite material.
The preparation method comprises the steps of fully mixing CBT resin powder, unsaturated polyester powder and catalyst powder, heating to 160-180 ℃ to enable the mixed powder to be molten to be very low in viscosity, fully infiltrating fiber cloth before CBT is completely polymerized, cooling, winding to prepare a prepreg, and finally hot-pressing and molding the prepreg at 190-220 ℃ in a 45-degree cross-ply mode to enable CBT to be subjected to ring-opening polymerization to form PCBT, and embedding unsaturated polyester containing Diels-Alder bonds into a molecular chain of the PCBT.
The unidirectional continuous fiber cloth adopted by the invention is formed by binding, stitching and only using the zero-twist roving in the direction of 0 degree or 90 degrees, has good corrosion resistance, is easy to be soaked by resin, has good interlayer bonding, can be suitable for various curved surfaces, and has high construction efficiency. The composite material compounded with thermoplastic material has the advantages of high damping effect, small expansion coefficient, light skeleton, less deformation, etc. In addition, the unidirectional continuous fiber cloth has high rigidity and high strength, can effectively increase the strength of the composite material, but the toughness of the fiber material is lower, and the addition of the unsaturated polyester can effectively solve the technical problem. Meanwhile, the unidirectional fibers have low tensile strength along the transverse direction and are easy to damage when bearing impact load, so that the PCBT composite material is prepared by hot pressing the prepreg in a 45-degree crossed layered mode, and the tensile strength of the material along the transverse direction is effectively improved.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the CBT resin and the unsaturated resin are blended, and the unsaturated polyester is embedded in the molecular chain of the PCBT, so that the brittleness of the PCBT composite material is effectively reduced, and the comprehensive performance of the PCBT composite material is improved. Meanwhile, the unsaturated polyester contains Diels-Alder bonds, so that the PCBT composite material can automatically repair cracks at 100-110 ℃.
2. According to the invention, by optimizing the formula, the prepared PCBT composite material has excellent strength, toughness and flame retardant property, is suitable for forming processes such as automatic material paving forming, compression molding forming and vacuum forming, can be used in multiple fields such as automobiles and sports equipment, and has wide application range and good market prospect.
Drawings
FIG. 1 is a schematic view of the cross lay up of prepregs according to the present invention.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention is further illustrated by the following examples. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention. In the examples, the methods used were all conventional methods unless otherwise specified.
Part of raw material sources are as follows:
CBT resin (CBT100), available from Cyclics, USA, using a pre-drying treatment (drying in a vacuum oven at 105 ℃ for 12 h);
unidirectional continuous fiber cloth, China Yixing Hengbo fiber manufacturing Co., Ltd, is dried before use (drying in a vacuum drying oven at 110 ℃ for 6 h).
Example 1
A preparation method of unsaturated polyester containing Diels-Alder bonds comprises the following steps: mechanically stirring and reacting furyl polyester and bismaleimide in excess DMF at 65 ℃ at 1000 revolutions per minute for 28 hours, then cooling the reaction liquid to room temperature, placing the reaction liquid in anhydrous ether for settling for 2-4 times, and finally drying the precipitate in a vacuum oven at 45 ℃ for 20 hours to obtain the unsaturated polyester containing Diels-Alder bonds. The molar ratio of the furyl polyester to the bismaleimide is 9:1, the furyl polyester consists of PEF and PBF, and the molar ratio of the PEF to the PBF is 13: 1.
Example 2
A preparation method of unsaturated polyester containing Diels-Alder bonds comprises the following steps: mechanically stirring and reacting furyl polyester and bismaleimide in excess DMF at 68 ℃ at 1000 revolutions per minute for 24 hours, then cooling the reaction liquid to room temperature, placing the reaction liquid in anhydrous ether for settling for 2-4 times, and finally drying the precipitate in a vacuum oven at 40 ℃ for 24 hours to obtain the unsaturated polyester containing Diels-Alder bonds. The molar ratio of the furyl polyester to the bismaleimide is 9:1, the furyl polyester consists of PEF and PBF, and the molar ratio of the PEF to the PBF is 13: 1.
Example 3
A preparation method of unsaturated polyester containing Diels-Alder bonds comprises the following steps: mechanically stirring and reacting furyl polyester and bismaleimide in excess DMF at 62 ℃ at 1000 rpm for 30h, cooling the reaction liquid to room temperature, placing the reaction liquid in anhydrous ether for settling for 2-4 times, and finally drying the precipitate in a vacuum oven at 50 ℃ for 18h to obtain the unsaturated polyester containing the Diels-Alder bond. The molar ratio of the furyl polyester to the bismaleimide is 9:1, the furyl polyester consists of PEF and PBF, and the molar ratio of the PEF to the PBF is 13: 1.
The yields of the Diels-Alder bond-containing unsaturated polyesters of examples 1 to 3 are shown in Table 1.
TABLE 1
| Examples | Example 1 | Example 2 | Example 3 |
| Yield/% | 89.3 | 86.7 | 83.1 |
As can be seen from Table 1, the yields in examples 1 to 3 were all high, with the yield in example 1 being the best.
The invention is also based on example 1 and the results are shown in Table 2, which explores the effect of the molar ratio of furan-based polyester to bismaleimide on the yield of the product (unsaturated polyester containing Diels-Alder bond) without changing other conditions.
TABLE 2
As can be seen from the results in Table 2, the yield showed a significant increase with the amount of the furanyl polyester, and the reaction yield was the highest when the molar ratio of the furanyl polyester to the bismaleimide was 9: 1.
Example 4
A self-repairing PCBT composite material comprises the following components in parts by weight: 100 parts of CBT resin, 20 parts of unsaturated polyester containing Diels-Alder bonds prepared in example 1, 80 parts of unidirectional continuous carbon fiber cloth, 0.4 part of catalyst, 1.5 parts of inorganic flame retardant and 1 part of color paste. The catalyst consists of monobutyl tin oxide and ethylene glycol aluminum, wherein the mass ratio of the monobutyl tin oxide: ethylene glycol aluminum ═ 5: 2. The inorganic flame retardant consists of nano aluminum hydroxide, nano antimony trioxide and nano zinc borate, wherein the mass ratio of the nano aluminum hydroxide: nano antimony trioxide: nano zinc borate is 2:1: 1.
The preparation method of the self-repairing PCBT composite material comprises the following steps:
(1) respectively prefabricating CBT resin, unsaturated polyester containing Diels-Alder bonds and a catalyst into powder, uniformly mixing, adding into a resin tank, vacuumizing the resin tank, injecting nitrogen for protection, heating to 180 ℃, melting, adding an inorganic flame retardant, uniformly stirring, adding color paste, uniformly stirring, injecting into unidirectional continuous carbon fiber cloth, fully soaking, cooling, and winding to obtain a prepreg;
(2) and (2) putting the prepreg into a mould, paving the single-layer prepreg in a 45-degree crossed layer mode (as shown in figure 1), putting the mould on a hot press, vacuumizing the mould, then carrying out hot press molding at 210 ℃, keeping for 4 hours, cooling, and demoulding to obtain the self-repairing PCBT composite material.
Example 5
A self-repairing PCBT composite material comprises the following components in parts by weight: 90 parts of CBT resin, 10 parts of unsaturated polyester containing Diels-Alder bonds prepared in example 1, 50 parts of unidirectional continuous glass fiber cloth, 0.2 part of catalyst, 0.5 part of inorganic flame retardant and 0.5 part of color paste. The catalyst consists of monobutyl tin oxide and ethylene glycol aluminum, wherein the mass ratio of the monobutyl tin oxide: ethylene glycol aluminum ═ 5: 2. The inorganic flame retardant consists of nano aluminum hydroxide, nano antimony trioxide and nano zinc borate, wherein the mass ratio of the nano aluminum hydroxide: nano antimony trioxide: nano zinc borate is 2:1: 1.
The preparation method of the self-repairing PCBT composite material comprises the following steps:
(1) respectively prefabricating CBT resin, unsaturated polyester containing Diels-Alder bonds and a catalyst into powder, uniformly mixing, adding into a resin tank, vacuumizing the resin tank, injecting nitrogen for protection, heating to 160 ℃, melting, adding an inorganic flame retardant, uniformly stirring, adding color paste, uniformly stirring, injecting into unidirectional continuous glass fiber cloth, fully soaking, cooling, and winding to obtain a prepreg;
(2) and (2) putting the prepreg into a mould, paving the single-layer prepreg in a 45-degree crossed layer, putting the mould on a hot press, vacuumizing the mould, then carrying out hot press molding at 220 ℃, keeping for 1h, cooling and demoulding to obtain the self-repairing PCBT composite material.
Example 6
A self-repairing PCBT composite material comprises the following components in parts by weight: 100 parts of CBT resin, 15 parts of Diels-Alder bond-containing unsaturated polyester prepared in example 1, 100 parts of unidirectional continuous basalt fiber cloth, 0.6 part of catalyst, 2.5 parts of inorganic flame retardant and 1.5 parts of color paste. The catalyst consists of monobutyl tin oxide and ethylene glycol aluminum, wherein the mass ratio of the monobutyl tin oxide: ethylene glycol aluminum ═ 5: 2. The inorganic flame retardant consists of nano aluminum hydroxide, nano antimony trioxide and nano zinc borate, wherein the mass ratio of the nano aluminum hydroxide: nano antimony trioxide: nano zinc borate is 2:1: 1.
The preparation method of the self-repairing PCBT composite material comprises the following steps:
(1) respectively prefabricating CBT resin, unsaturated polyester containing Diels-Alder bonds and a catalyst into powder, uniformly mixing, adding into a resin tank, vacuumizing the resin tank, injecting nitrogen for protection, heating to 180 ℃, melting, adding an inorganic flame retardant, uniformly stirring, adding color paste, uniformly stirring, injecting into unidirectional continuous basalt fiber cloth, fully infiltrating, cooling, and winding to obtain a prepreg;
(2) and (2) placing the prepreg into a mould, paving the single-layer prepreg in a 45-degree crossed layer, placing the mould on a hot press, vacuumizing the mould, then carrying out hot press molding at 190 ℃, keeping for 4 hours, cooling, and demoulding to obtain the self-repairing PCBT composite material.
Comparative example 1: the only difference from example 4 is that the Diels-Alder bond-containing unsaturated polyester obtained in example 1 was not added, and the preparation method was the same as in example 4.
First, performance test
The self-repairing PCBT composite materials of the embodiments 4-6 and the comparative example 1 are manufactured into sample strips with the same specification (length is 300mm, width is 200mm, thickness is 3mm) for testing, and the average value is taken.
And (4) testing standard:
1. the tensile strength test is carried out on an SANS microcomputer control electronic universal tester according to the GB/T1040.4-2006 standard, and the tensile speed is 2 mm/min;
2. the bending strength test is carried out on an SANS microcomputer controlled electronic universal tester according to the GB/T9341-2008 standard, the span-thickness ratio is 16:1, and the loading speed is 2 mm/min;
3. testing the crystallization performance of the PCBT composite material by using an X-ray diffractometer (XRD-6000), wherein the testing range is 5-60 degrees, the scanning speed is 5 degrees/min, and calculating the crystallinity of the PCBT composite material by using jade software;
4. the self-repairing efficiency is characterized by measuring the impact strength of a sample, wherein the impact strength is a strength index for measuring the toughness of the material and represents the capability of the material for resisting the damage of impact load;
the impact test is carried out on a TH-6050 type pendulum impact tester according to the GB/T1043 standard, and a simple beam type impact and unnotched test sample is used, the impact speed is 5m/s, and the impact energy is 10J. The samples after the impact fracture were lightly clamped at the fracture site with a G-type jig, placed in a vacuum oven at 110 ℃ for 4h, and then the above test procedure was repeated.
The self-repair efficiency (eta) is calculated by the following formula:
η＝Ⅰb/Ⅰa×100％
in the formula IaAs the initial impact strength (KJ/m) of the test specimen2)，ⅠbFor the impact strength (KJ/m) of the repaired sample2)
5. The vertical burning performance was tested according to the UL 94 regulations.
The test results are shown in table 3.
TABLE 3
As can be seen from Table 3, the self-repairing PCBT composite material has good mechanical property and flame retardance, and the crystallinity of the PCBT composite material can be effectively reduced, the toughness of the PCBT composite material is improved, the comprehensive performance of the PCBT composite material is better, and meanwhile, the PCBT composite material is endowed with automatic repairing performance.
Secondly, researching the influence of the catalyst on the mechanical property of the PCBT composite material, and designing 7 groups of test groups, wherein the component composition and the mass ratio of the components of the catalyst of each group are shown in a table 4.
TABLE 4
PCBT composite materials (0.4 part of catalyst in parts by weight) are prepared from the test groups 1-7 according to the formula and the preparation method of the embodiment 4, the tensile property and the bending property of the PCBT composite materials are tested, and the test results are shown in Table 5.
TABLE 5
As can be seen from Table 5, the combination of the organoaluminum catalyst and the organotin catalyst results in a more excellent mechanical property of the PCBT composite material, which indicates that the combination of the organoaluminum catalyst and the organotin catalyst has higher catalytic activity, so that the number of active centers is increased, the molecular chain of the product is increased, and the molecular weight is increased. Meanwhile, the mechanical property of the test group 3 is optimal, which shows that the organic tin catalyst and the organic aluminum catalyst are compounded in a mass ratio of 5:2, and the catalytic synergistic effect is most obvious.
Thirdly, researching the influence of the inorganic flame retardant on the flame retardant property of the PCBT composite material, designing 8 groups of test groups, wherein the component composition and the mass ratio of the components of the inorganic flame retardant of each group are shown in Table 6.
TABLE 6
The PCBT composite material (1.5 parts of inorganic flame retardant) is prepared by the test groups 1-8 according to the formula and the preparation method of the embodiment 4, the flame retardant performance of the PCBT composite material is tested, and the test results are shown in Table 7.
TABLE 7
| Test specimen | Flame retardant rating |
| Test group 1 | UL 94V-1 |
| Test group 2 | UL 94V-0 |
| Test group 3 | UL 94V-0 |
| Test group 4 | UL 94V-0 |
| Test group 5 | UL 94V-1 |
| Test group 6 | UL 94V-2 |
| Test group 7 | UL 94V-2 |
| Test group 8 | UL 94V-2 |
As can be seen from Table 7, the flame retardant performance of the PCBT composite material is more excellent due to the compounding of the nano aluminum hydroxide, the nano antimony trioxide and the nano zinc borate, which indicates that the flame retardant synergistic effect can be generated due to the compounding of the nano aluminum hydroxide, the nano antimony trioxide and the nano zinc borate. Meanwhile, the flame retardant property of the test groups 2-4 is superior to that of the test group 1 and the test group 5, which shows that the nano aluminum hydroxide: nano antimony trioxide: when the ratio of the nano zinc borate to the nano zinc borate is (1-3) to 1:1, the flame-retardant synergistic effect is more obvious. In addition, although the flame retardant grades of the test group 2, the test group 3 and the test group 4 can reach the UL 94V-0 grade, the mechanical property of the test group 3 is better than that of the test group 2 and the test group 4, so that the flame retardant coating is prepared by mixing the nano aluminum hydroxide: nano antimony trioxide: the optimal proportion of the nano zinc borate as the inorganic flame retardant is 2:1: 1.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (11)
1. The self-repairing PCBT composite material is characterized by comprising the following components in parts by weight: 90-100 parts of CBT resin, 10-20 parts of unsaturated polyester containing Diels-Alder bonds, 50-100 parts of unidirectional continuous fiber cloth, 0.2-0.6 part of catalyst, 0.5-2.5 parts of inorganic flame retardant and 0.5-1.5 parts of color paste; the preparation method of the unsaturated polyester containing the Diels-Alder bond comprises the following steps: reacting furyl polyester and bismaleimide in excessive N, N-dimethylformamide for 24-30 hours under mechanical stirring at 62-68 ℃, then cooling the reaction liquid to room temperature, placing the reaction liquid in anhydrous ether for settling for 2-4 times, and finally drying the precipitate in a vacuum oven at 40-50 ℃ for 18-24 hours to obtain unsaturated polyester containing Diels-Alder bonds; in the preparation method of the unsaturated polyester containing Diels-Alder bonds, the molar ratio of the furyl polyester to the bismaleimide is (8:1) - (10: 1).
2. The self-healing PCBT composite material of claim 1, consisting of, in parts by weight: 100 parts of CBT resin, 20 parts of unsaturated polyester containing Diels-Alder bonds, 80 parts of unidirectional continuous fiber cloth, 0.4 part of catalyst, 1.5 parts of inorganic flame retardant and 1 part of color paste.
3. The self-healing PCBT composite material of claim 1, in which the furan-based polyester is at least one of polyethylene 2, 5-furandicarboxylate (PEF), polybutylene 2, 5-furandicarboxylate (PBF).
4. The self-healing PCBT composite material of claim 1, in which the unidirectional, continuous fiber cloth is fabricated from at least one of glass fibers, carbon fibers, basalt fibers.
5. The self-healing PCBT composite of claim 1, wherein the catalyst consists of an organotin catalyst and an organoaluminum catalyst; in the catalyst, the mass ratio of the organic tin catalyst: (1-3) an organoaluminum catalyst.
6. The self-healing PCBT composite material of claim 5, in which the ratio of organotin catalysts: organoaluminum catalyst 5: 2.
7. The self-healing PCBT composite material of claim 6, in which the organotin catalyst is at least one of monobutyl tin oxide, dihydroxy butyl tin chloride, stannoxane; the organic aluminum catalyst is at least one of aluminum triethoxide, aluminum triisopropoxide and aluminum ethylene glycol.
8. The self-healing PCBT composite material of claim 1, in which the inorganic flame retardant is at least one of nano aluminum hydroxide, nano antimony trioxide, and nano zinc borate.
9. The self-healing PCBT composite material of claim 1, in which the inorganic flame retardant consists of nano aluminum hydroxide, nano antimony trioxide, and nano zinc borate; in the inorganic flame retardant, the mass ratio of nano aluminum hydroxide: nano antimony trioxide: and (1-3) the ratio of nano zinc borate to nano zinc borate is 1: 1.
10. The self-healing PCBT composite material of claim 9, in which the inorganic flame retardant is a mixture of nano aluminum hydroxide: nano antimony trioxide: nano zinc borate is 2:1: 1.
11. The preparation method of the self-repairing PCBT composite material as recited in any one of claims 1-10, comprising the steps of:
(1) respectively prefabricating CBT resin, unsaturated polyester containing Diels-Alder bonds and a catalyst into powder, uniformly mixing, heating to 160-180 ℃ under a vacuum condition, melting, adding an inorganic flame retardant, uniformly stirring, adding color paste, uniformly stirring, pouring into unidirectional continuous fiber cloth, fully soaking, cooling, and winding to obtain a prepreg;
(2) and (2) placing the prepreg into a mould, paving the single-layer prepreg in a 45-degree crossed layer, placing the mould on a hot press, carrying out hot press molding under a vacuum condition at 190-220 ℃, keeping for 1-4 h, cooling, and demoulding to obtain the self-repairing PCBT composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910225371.2A CN109971138B (en) | 2019-03-22 | 2019-03-22 | Self-repairing PCBT composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910225371.2A CN109971138B (en) | 2019-03-22 | 2019-03-22 | Self-repairing PCBT composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109971138A CN109971138A (en) | 2019-07-05 |
| CN109971138B true CN109971138B (en) | 2021-08-17 |
Family
ID=67080318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910225371.2A Active CN109971138B (en) | 2019-03-22 | 2019-03-22 | Self-repairing PCBT composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109971138B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111719311B (en) * | 2020-06-23 | 2021-05-11 | 上海交通大学 | Modified carbon fiber, modified carbon fiber reinforced epoxy resin composite material and preparation method thereof |
| CN113527646B (en) * | 2021-08-25 | 2022-04-01 | 四川大学 | Self-repairable furan group-containing bio-based unsaturated polyester resin and preparation method and application thereof |
| CN116278194A (en) * | 2023-02-16 | 2023-06-23 | 联塑科技发展(贵阳)有限公司 | Low-resistance PVC wire tube and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321347A (en) * | 2010-10-15 | 2012-01-18 | 深圳市科聚新材料有限公司 | High creepage trace index polyester composite and preparation method thereof |
| CN104098875A (en) * | 2013-04-09 | 2014-10-15 | 上海杰事杰新材料(集团)股份有限公司 | Continuous fiber-enhanced CBT prepreg, and preparation method and application thereof |
| CN104109355A (en) * | 2013-04-22 | 2014-10-22 | 上海杰事杰新材料(集团)股份有限公司 | High-strength high-impact resistance polybutylece terephthalate (PBT) composite material and preparation method thereof |
| CN105153409A (en) * | 2015-10-16 | 2015-12-16 | 浙江大学 | Thermoplastic copolyester composition with thermally reversible chemical crosslinking properties and preparation method and application thereof |
| CN106883544A (en) * | 2017-01-18 | 2017-06-23 | 福建省支点三维科技有限公司 | A kind of polyester 3D printing material with cross-linked structure and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110152457A1 (en) * | 2009-12-17 | 2011-06-23 | E. I. Du Pont De Nemours And Company | Polyester Compositions with Good Melt Rheological Properties |
-
2019
- 2019-03-22 CN CN201910225371.2A patent/CN109971138B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321347A (en) * | 2010-10-15 | 2012-01-18 | 深圳市科聚新材料有限公司 | High creepage trace index polyester composite and preparation method thereof |
| CN104098875A (en) * | 2013-04-09 | 2014-10-15 | 上海杰事杰新材料(集团)股份有限公司 | Continuous fiber-enhanced CBT prepreg, and preparation method and application thereof |
| CN104109355A (en) * | 2013-04-22 | 2014-10-22 | 上海杰事杰新材料(集团)股份有限公司 | High-strength high-impact resistance polybutylece terephthalate (PBT) composite material and preparation method thereof |
| CN105153409A (en) * | 2015-10-16 | 2015-12-16 | 浙江大学 | Thermoplastic copolyester composition with thermally reversible chemical crosslinking properties and preparation method and application thereof |
| CN106883544A (en) * | 2017-01-18 | 2017-06-23 | 福建省支点三维科技有限公司 | A kind of polyester 3D printing material with cross-linked structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109971138A (en) | 2019-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109971138B (en) | Self-repairing PCBT composite material and preparation method thereof | |
| Fink | Reactive polymers: fundamentals and applications: a concise guide to industrial polymers | |
| CN106433537B (en) | Modified epoxy adhesive and preparation method thereof | |
| US7972685B2 (en) | Glass mat laminate comprised of polymerizable cyclic polyester oligomers suitable for composites with a class-A surface | |
| CN110804282B (en) | Modified flat glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof | |
| KR910007593B1 (en) | Thermoplastic composition for the interial of ship or car and its manufacturing method | |
| CN101328309A (en) | Toughening sheet moulding compound for cable stand | |
| KR102293828B1 (en) | Thermoplastic resin composition having excellent hydrolysis resistance and laser transmittance and molded article comprising the same | |
| CN1872913A (en) | Method for preparing polycondensation reaction type reinforced thermoplastic resin in long fibres | |
| KR20150024824A (en) | Molding material, molded body of same, and method for producing molded body | |
| WO2021200793A1 (en) | Fiber-reinforced plastic molding material | |
| CN109912749B (en) | Self-repairing unsaturated polyester composite material for 3D printing and preparation method thereof | |
| CN111040358A (en) | Functional master batch for improving surface polarity of PP (polypropylene) material as well as preparation method and application thereof | |
| CN114015403B (en) | Polyurethane adhesive, hot-pressing insulating film prepared from polyurethane adhesive and application of hot-pressing insulating film | |
| CN104470969A (en) | High-toughness materials based on unsaturated polyesters | |
| CN114231013A (en) | Environment-friendly plastic building template material and preparation method thereof | |
| EP0549827B1 (en) | Unsaturated polyester resin compostions, molding compounds and molded products therefrom | |
| KR101959029B1 (en) | Automotive Underbody With High Rigidity And Sound Absorption | |
| CN111909493B (en) | Novel environment-friendly base material, preparation method thereof and novel environment-friendly base material composite board | |
| CN111171525A (en) | PBT reclaimed material and preparation method thereof | |
| CN115286899B (en) | Toughening-flame-retardant bisphenol type epoxy resin composite material and application thereof | |
| CN114805883B (en) | Bismaleimide modified basalt fiber cloth and polyaryl ether nitrile composite material and preparation method thereof | |
| CN109762306B (en) | High-strength, high-toughness and low-shrinkage PBT (polybutylene terephthalate) composite material and preparation method thereof | |
| CN116444839A (en) | PBT (polybutylene terephthalate) modified recycled polycarbonate composite plastic and preparation method thereof | |
| JP2021080379A (en) | Fiber-reinforced resin and method for producing fiber-reinforced resin |
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 | ||
| CB02 | Change of applicant information |
Address after: 529000 1-210, building 1, 12 Hongda Road, Pengjiang district, Jiangmen City, Guangdong Province Applicant after: JIANGMEN DESHAN COMPOSITES TECHNOLOGY Co.,Ltd. Address before: 529000 1-210, building 8, No. 10, Huangzhuang Avenue West, Pengjiang district, Jiangmen City, Guangdong Province Applicant before: JIANGMEN DESHAN COMPOSITES TECHNOLOGY Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |