CN109971138A - A kind of selfreparing PCBT composite material and preparation method - Google Patents
A kind of selfreparing PCBT composite material and preparation method Download PDFInfo
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- 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
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08K7/14—Glass
Abstract
The invention discloses a kind of selfreparing PCBT composite material and preparation methods, the present invention is crosslinked with environmental-friendly furyl polyester and bismaleimide, prepare the unsaturated polyester (UP) with Diels-Alder key, then by the unsaturated polyester (UP) of the key containing Diels-Alder and CBT resin alloy, make to generate graft copolymerization on PCBT chain.The block of the unsaturated polyester (UP) enters, and on the one hand reduces the crystallinity of PCBT, improves its brittleness, improves its comprehensive performance, on the other hand makes to assign its self-healing properties containing Diels-Alder key on the strand of PCBT.
Description
Technical field
The present invention relates to technical field of composite materials more particularly to a kind of selfreparing PCBT composite material and its preparation sides
Method.
Background technique
Since 20th century, on the basis of scientific and technological stable development, society are constantly progressive, demand of the people to engineering material
It further increases, the requirement such as lightweight, high-strength, structure-function combining design technology especially shows Aeronautics and Astronautics, electronics etc.
High-end technology field.Traditional simple function material has been far from satisfying the multiple requirements of engineer application.With new material
With the continuous development of new technology, composite material relies on the advantage of its designability, deserving as the new of engineering material
Favorite.And thermoplastic composite has preferable toughness and shock resistance, molding cycle compared with same with thermosetting compound material
Short, the advantages that manufacturing cost is low, waste material recoverable and product can be with secondary operation, many industry have been widely used in it
Field.
Polycyclic shape mutual-phenenyl two acid bromide two alcohol ester (PCBT) is being catalyzed by cyclic butylene terephthalate (CBT)
Under the action of agent, thermoplastic engineering plastic obtained from ring-opening polymerisation.PCBT possesses higher intensity, preferable tough
With recoverable, make it that there is fabulous development potentiality in thermoplastic composite field.CBT prepares the polymerization of PCBT
In reaction, reactionless heat release crystallizes and polymerize while occurring, being not required to cooling can demould, and entire molding cycle is shorter.But this
The PCBT crystallization that kind molding mode is produced is more perfect, causes its brittleness big, poor toughness.And at present to PCBT toughening modifying
Research it is very limited, and the effect of toughening modifying is generally bad.
In addition, material will receive the destruction on macroscopical or microcosmic unavoidably in use, and it is typically exactly impact failure, it is microcosmic
On be micro-crack occur.Micro-crack influences the various mechanical properties of material, such as intensity, rigidity, dimensional stability.Meanwhile it is micro-
Crackle also provides place for environmental aging material, leads to the decline of material degradation and performance, influences material normal use and contracting
Short service life.The Complicated primary of crackle, especially selfreparing are a reality and important problem.With to polymer material
Self-healing properties research deepens continuously, and selfreparing is developed to from foreign aid's type selfreparing not to be needed additionally to add the intrinsic of renovation agent
Type selfreparing.Intrinsical selfreparing mainly realizes selfreparing using the reversible covalent bonds of material internal or reversible non-covalent key,
Since the active force between covalent bond is much larger than the active force between non-covalent bond, researchers to reversible covalent bonds from
Reparation system conducts extensive research.Thermal reversion Diels-Alder reaction is the ring carried out between diene body and dienophile
Addition reaction does not need catalyst, and have good thermal reversibility, therefore become since its reaction condition is milder
One of the hot spot of self-repair material research.Currently, yet there are no the correlative study report for carrying out selfreparing to PCBT material.
Summary of the invention
It is an object of the invention to solve above-mentioned shortcoming and defect existing in the prior art, a kind of selfreparing PCBT is provided
Composite material and preparation method.The present invention is crosslinked with environmental-friendly furyl polyester and bismaleimide, and preparation has
The unsaturated polyester (UP) of Diels-Alder key makes then by the unsaturated polyester (UP) of the key containing Diels-Alder and CBT resin alloy
Graft copolymerization is generated on PCBT chain.The block of the unsaturated polyester (UP) enters, and on the one hand reduces the crystallinity of PCBT, improves it
Brittleness, improves its comprehensive performance, on the other hand makes to assign its self-repairability containing Diels-Alder key on the strand of PCBT
Energy.
To realize its purpose, the technical scheme adopted by the invention is as follows:
A kind of selfreparing PCBT composite material comprising the component of following parts by weight: 90~100 parts of CBT resin contains
10~20 parts of unsaturated polyester (UP), 50~100 parts of unidirectional continuous fiber cloth, 0.2~0.6 part of the catalyst, nothing of Diels-Alder key
0.5~2.5 part and 0.5~1.5 part of mill base of machine fire retardant.
Preferably, the selfreparing PCBT composite material includes the component of following parts by weight: 100 parts of CBT resin contains
20 parts of the unsaturated polyester (UP) of Diels-Alder key, 80 parts of unidirectional continuous fiber cloth, 0.4 part of catalyst, 1.5 parts of inorganic fire retardants
With 1 part of mill base.
Preferably, the unsaturated polyester (UP) of the key containing Diels-Alder the preparation method comprises the following steps: by furyl polyester and span
Carry out acid imide in excessive N, N '-dimethyl formamide (DMF), 24~30h is reacted under 62~68 DEG C of mechanical stirrings, then
Reaction solution is cooled to room temperature, places reaction liquid into and is settled in anhydrous ether 2~4 times, it is finally that sediment is true in 40~50 DEG C
Dry 18 in empty baking oven~for 24 hours, obtain the unsaturated polyester (UP) of the key containing Diels-Alder.
Preferably, in the preparation method of the unsaturated polyester (UP) of the key containing Diels-Alder, furyl polyester and span come
Imido molar ratio is (8:1)~(10:1).The present invention has found that furyl polyester and span come by a large amount of creative experiments
Imido dosage is affected to the yield of product, when with the above-mentioned molar ratio complex reaction of the present invention, the yield of product
It is higher.And the molar ratio of furyl polyester and bismaleimide be 9:1 when, the yield highest of product.
Preferably, the furyl polyester is poly- 2,5-furandicarboxylic acid glycol ester (PEF), poly- 2,5-furandicarboxylic acid
At least one of butanediol ester (PBF).PEF and PBF belongs to biology base polyester, is with renewable resource 2,5-furandicarboxylic acid
It is product made from raw material with dihydric alcohol, there is preferable mechanics and hot property.
Preferably, the unidirectional continuous fiber cloth is made by least one of glass fibre, carbon fiber, basalt fibre
It forms.CBT resin has fabulous dipping effect to glass fibre, carbon fiber and basalt fibre, CBT resin and glass fibre,
Carbon fiber and basalt fibre carry out compound, can prepare surface smoothness height, good mechanical property, environmentally friendly reusable
PCBT composite material.
Preferably, the catalyst is made of organotin catalysts and organo aluminum catalyst.Preferably, it counts in mass ratio,
In the catalyst, organotin catalysts: organo aluminum catalyst=5:(1~3).Most preferably, it counts in mass ratio, the catalysis
In agent, organotin catalysts: organo aluminum catalyst=5:2.Preferably, the organotin catalysts are Mono-n-butyltin, two
At least one of hydroxybutyl stannic chloride, tin oxygen alkane.Preferably, the organo aluminum catalyst is three aluminium ethylates, three isopropanols
At least one of aluminium, ethylene glycol aluminium.The activity for the organo aluminum catalyst that the present invention uses preferably, is free of heavy metal, to people and animals
It is harmless, it is a kind of novel catalyst for meeting environmental requirement.The organo aluminum catalyst is compounded with organotin catalysts, can be reduced
The dosage of organotin catalysts, and catalyzing cooperation effect can be generated, catalytic activity is higher, increases the quantity in activated centre, produces
The molecule chain growth of object, molecular weight increase, and the mechanical property of PCBT composite material obtained is more excellent.
Preferably, the inorganic fire retardants be nano-aluminum hydroxide, nanometer grade antimony trioxide, in nano-zinc borate extremely
Few one kind.It is highly preferred that the inorganic fire retardants is made of nano-aluminum hydroxide, nanmeter antimong trioxide and nano-zinc borate.
The granularity for the inorganic fire retardants that the present invention uses is nanometer scale, has biggish specific surface area, activity is high, and dosage is few, right
The permeability of fabric is big, and adhesive force is high, will not influence the surface smoothness of composite material, has fire-retardant, smoke elimination, three big function of filling
Can, flame retardant effect is obvious, without secondary pollution, the good dispersion in burning, moreover it is possible to improve the mechanical property of material.Meanwhile nanometer
Aluminium hydroxide, nanmeter antimong trioxide and nano-zinc borate compounding, can generate flame retardant synergistic effect, make the anti-flammability of composite material
It can be more preferable.
Preferably, it counts in mass ratio, in the inorganic fire retardants, nano-aluminum hydroxide: nanmeter antimong trioxide: nanometer boron
Sour zinc=(1~3): 1:1.Most preferably, it counts in mass ratio, in the inorganic fire retardants, nano-aluminum hydroxide: nanometer three is aoxidized
Two antimony: nano-zinc borate=2:1:1.Nano-aluminum hydroxide, nanmeter antimong trioxide and nano-zinc borate are compounded with said ratio,
Flame retardant synergistic effect becomes apparent from.
Preferably, the preparation method of the selfreparing PCBT composite material, includes the following steps:
(1) CBT resin, the unsaturated polyester (UP) of the key containing Diels-Alder and catalyst are prefabricated into powdered, mixing respectively
Uniformly, heated under vacuum is to 160~180 DEG C, after melting, inorganic fire retardants is added, stirs evenly, adds mill base, stir
It mixes uniformly, is then filled into unidirectional continuous fiber cloth, cooling sufficiently after infiltration, prepreg is made in winding；
(2) prepreg is put into mold, mold is placed on hot press, very by the prepreg of single layer by 45 ° of cross-level pavings
Empty condition, hot-forming at 190~220 DEG C, cooling after keeping 1~4h, the selfreparing PCBT composite material is made in demoulding.
After CBT toner, unsaturated polyester (UP) powder and catalyst fines are sufficiently mixed by the present invention, it is heated to 160~
180 DEG C, mixed-powder is made to melt to very low viscosity, fiber cloth is sufficiently infiltrated before CBT does not occur to polymerize completely, so
After cool down, winding prepreg is made, it is finally in a manner of 45 ° of intersection layings that prepreg is hot-forming at 190~220 DEG C,
Make CBT ring-opening polymerisation at PCBT, and is embedded in the unsaturated polyester (UP) of the key containing Diels-Alder on the strand of PCBT simultaneously.
The unidirectional continuous fiber cloth that the present invention uses is to only use the bundled loop bonding of roving in 0 ° or 90 ° direction to form
, there is good corrosion resistance, be easy to by resin infiltration, ply adhesion is good, can be suitble to various curved surfaces, and construction efficiency is high.Through
It is combined into composite material with thermoplastic material, there is good damping effect, the coefficient of expansion is small, and skeleton is light, deforms the advantages that small.Separately
Outside, unidirectional continuous fiber cloth has high rigidity and high intensity, can effectively increase the intensity of composite material, but the toughness of fibrous material
It is lower, and the addition of unsaturated polyester (UP) can effectively solve this technical problem.Meanwhile the tensile strength of unidirectional fibre transversely
It is low, it is more easily damaged when absorbing impact load, therefore, present invention hot pressing in such a way that prepreg is by 45 ° of cross-level pavings
Standby PCBT composite material, effectively increases the tensile strength of material transversely.
Compared with prior art, the beneficial effects of the present invention are:
1, CBT resin is blended the present invention with unsaturated-resin, unsaturated polyester (UP) is embedded on the strand of PCBT, effectively
The brittleness for reducing PCBT composite material improves its comprehensive performance.Simultaneously as the unsaturated polyester (UP) contains Diels-
Alder key be automatically repaired PCBT composite material can to crackle at 100~110 DEG C.
2, for the present invention by optimizing to formula, PCBT composite material obtained has excellent intensity, toughness and resistance
Performance is fired, is suitable for the moulding process such as the molding of automatic stone, compression molding and vacuum forming, can be used for automobile, exercise etc.
Multiple fields have a wide range of application, and market prospects are good.
Detailed description of the invention
Fig. 1 is the schematic diagram of prepreg cross-level of the present invention paving.
Specific embodiment
To better illustrate the object, technical solutions and advantages of the present invention, the present invention passes through the following example furtherly
It is bright.It should be understood that the embodiment of the present invention is merely to illustrate technical effect of the invention, protection model and is not intended to limit the present invention
It encloses.In embodiment, method therefor is conventional method unless otherwise instructed.
Part material source:
CBT resin (CBT100), Cyclics company, the U.S. (are dried using preceding drying and processing in 105 DEG C of vacuum ovens
12h)；
Unidirectional continuous fiber cloth, Chinese Yixing Hua Heng fiber Manufacturing Co., Ltd use preceding drying and processing (110 DEG C of vacuum
6h is dried in drying box).
Embodiment 1
A kind of preparation method of the unsaturated polyester (UP) of the key containing Diels-Alder comprising following steps: by furyl polyester
It,, then will reaction with 1000 revs/min of mechanic whirl-nett reaction 28h at 65 DEG C with bismaleimide in excessive DMF
Liquid is cooled to room temperature, and is placed reaction liquid into and is settled in anhydrous ether 2~4 times, finally does sediment in 45 DEG C of vacuum drying ovens
Dry 20h obtains the unsaturated polyester (UP) of the key containing Diels-Alder.The molar ratio of the furyl polyester and bismaleimide is
9:1, the furyl polyester are made of PEF and PBF, and the molar ratio of PEF and PBF is 13:1.
Embodiment 2
A kind of preparation method of the unsaturated polyester (UP) of the key containing Diels-Alder comprising following steps: by furyl polyester
It, for 24 hours with 1000 revs/min of mechanic whirl-nett reactions, then will reaction at 68 DEG C with bismaleimide in excessive DMF
Liquid is cooled to room temperature, and is placed reaction liquid into and is settled in anhydrous ether 2~4 times, finally does sediment in 40 DEG C of vacuum drying ovens
It is dry for 24 hours, obtain the unsaturated polyester (UP) of the key containing Diels-Alder.The molar ratio of the furyl polyester and bismaleimide is
9:1, the furyl polyester are made of PEF and PBF, and the molar ratio of PEF and PBF is 13:1.
Embodiment 3
A kind of preparation method of the unsaturated polyester (UP) of the key containing Diels-Alder comprising following steps: by furyl polyester
It,, then will reaction with 1000 revs/min of mechanic whirl-nett reaction 30h at 62 DEG C with bismaleimide in excessive DMF
Liquid is cooled to room temperature, and is placed reaction liquid into and is settled in anhydrous ether 2~4 times, finally does sediment in 50 DEG C of vacuum drying ovens
Dry 18h obtains the unsaturated polyester (UP) of the key containing Diels-Alder.The molar ratio of the furyl polyester and bismaleimide is
9:1, the furyl polyester are made of PEF and PBF, and the molar ratio of PEF and PBF is 13:1.
The yield of the unsaturated polyester (UP) of the key containing Diels-Alder of Examples 1 to 3 is as shown in table 1.
Table 1
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Yield/% | 89.3 | 86.7 | 83.1 |
As can be seen from Table 1, the yield of Examples 1 to 3 is higher, wherein best with the yield of embodiment 1.
The present invention, in the case where other conditions are constant, has probed into furyl polyester and span also according to embodiment 1
Carry out influence of the imido molar ratio to product (unsaturated polyester (UP) of the key containing Diels-Alder) yield, the results are shown in Table 2.
Table 2
It can be seen that from the result of table 2, with the increase of furyl polyester amount, yield works as furans in trend is obviously increased
When the molar ratio of base polyester and bismaleimide is 9:1, reaction yield reaches highest.
Embodiment 4
A kind of selfreparing PCBT composite material comprising the component of following parts by weight: 100 parts of CBT resin, embodiment 1 are made
20 parts of the unsaturated polyester (UP) of the key containing Diels-Alder, 80 parts of unidirectional continuous carbon fibre cloth, 0.4 part of catalyst, inorganic fire-retarded
1.5 parts and 1 part of mill base of agent.The catalyst is made of Mono-n-butyltin and ethylene glycol aluminium, is counted in mass ratio, monobutyl oxidation
Tin: ethylene glycol aluminium=5:2.The inorganic fire retardants is made of nano-aluminum hydroxide, nanmeter antimong trioxide and nano-zinc borate,
It counts in mass ratio, nano-aluminum hydroxide: nanmeter antimong trioxide: nano-zinc borate=2:1:1.
The preparation method of the selfreparing PCBT composite material, includes the following steps:
(1) CBT resin, the unsaturated polyester (UP) of the key containing Diels-Alder and catalyst are prefabricated into powdered, mixing respectively
Uniformly, it is added in resin container, resin container is vacuumized, nitrogen protection is reinjected, is heated to 180 DEG C, after melting, inorganic resistance is added
Agent is fired, stirs evenly, adds mill base, stir evenly, be then filled into unidirectional continuous carbon fibre cloth, it is cold sufficiently after infiltration
But, it winds, prepreg is made；
(2) prepreg is put into mold, the prepreg of single layer spreads (as shown in Figure 1) by 45 ° of cross-levels, and mold is placed on
On hot press, mold is vacuumized, then hot-forming at 210 DEG C, cooling after keeping 4h, the selfreparing is made in demoulding
PCBT composite material.
Embodiment 5
A kind of selfreparing PCBT composite material comprising the component of following parts by weight: 90 parts of CBT resin, embodiment 1 are made
10 parts of the unsaturated polyester (UP) of the key containing Diels-Alder, 50 parts of unidirectional continuous glass fibre cloth, 0.2 part of catalyst, inorganic fire-retarded
0.5 part and 0.5 part of mill base of agent.The catalyst is made of Mono-n-butyltin and ethylene glycol aluminium, is counted in mass ratio, monobutyl oxygen
Change tin: ethylene glycol aluminium=5:2.The inorganic fire retardants is by nano-aluminum hydroxide, nanmeter antimong trioxide and nano-zinc borate group
At counting in mass ratio, nano-aluminum hydroxide: nanmeter antimong trioxide: nano-zinc borate=2:1:1.
The preparation method of the selfreparing PCBT composite material, includes the following steps:
(1) CBT resin, the unsaturated polyester (UP) of the key containing Diels-Alder and catalyst are prefabricated into powdered, mixing respectively
Uniformly, it is added in resin container, resin container is vacuumized, nitrogen protection is reinjected, is heated to 160 DEG C, after melting, inorganic resistance is added
Agent is fired, stirs evenly, adds mill base, stir evenly, be then filled into unidirectional continuous glass fibre cloth, sufficiently after infiltration,
Cooling, prepreg is made in winding；
(2) prepreg is put into mold, mold is placed on hot press by the prepreg of single layer by 45 ° of cross-level pavings, right
Mold vacuumizes, then hot-forming at 220 DEG C, cooling after keeping 1h, and the selfreparing PCBT composite wood is made in demoulding
Material.
Embodiment 6
A kind of selfreparing PCBT composite material comprising the component of following parts by weight: 100 parts of CBT resin, embodiment 1 are made
15 parts of unsaturated polyester (UP), 100 parts of unidirectional continuous basalt fiber cloth, 0.6 part of the catalyst, nothing of the key containing Diels-Alder obtained
2.5 parts and 1.5 parts of mill base of machine fire retardant.The catalyst is made of Mono-n-butyltin and ethylene glycol aluminium, is counted in mass ratio, single
Butyl tin oxide: ethylene glycol aluminium=5:2.The inorganic fire retardants is by nano-aluminum hydroxide, nanmeter antimong trioxide and nanometer boron
Sour zinc composition, is counted, nano-aluminum hydroxide: nanmeter antimong trioxide: nano-zinc borate=2:1:1 in mass ratio.
The preparation method of the selfreparing PCBT composite material, includes the following steps:
(1) CBT resin, the unsaturated polyester (UP) of the key containing Diels-Alder and catalyst are prefabricated into powdered, mixing respectively
Uniformly, it is added in resin container, resin container is vacuumized, nitrogen protection is reinjected, is heated to 180 DEG C, after melting, inorganic resistance is added
Agent is fired, stirs evenly, adds mill base, stir evenly, be then filled into unidirectional continuous basalt fiber cloth, is sufficiently infiltrated
Afterwards, cooling, prepreg is made in winding；
(2) prepreg is put into mold, mold is placed on hot press by the prepreg of single layer by 45 ° of cross-level pavings, right
Mold vacuumizes, then hot-forming at 190 DEG C, cooling after keeping 4h, and the selfreparing PCBT composite wood is made in demoulding
Material.
Comparative example 1: the difference with embodiment 4 is only that the insatiable hunger for not adding the key containing Diels-Alder made from embodiment 1
And polyester, and preparation method is the same as embodiment 4.
One, performance test
The selfreparing PCBT composite material of embodiment 4~6 and comparative example 1 is fabricated to same size (long 300mm × wide
200mm × thickness 3mm) testing bar tested, test sample number be 3, take mean value.
Testing standard:
1, tensile strength test is according to GB/T 1040.4-2006 standard, on SANS microcomputer controlled electronic universal tester
It is tested, tensile speed 2mm/min；
2, bending strength test is enterprising in SANS microcomputer controlled electronic universal tester according to GB/T 9341-2008 standard
Row test is 16:1, loading velocity 2mm/min across thickness rate；
3, using X-ray diffractometer (XRD-6000) test PCBT composite material crystal property, test scope be 5~
60 °, scanning speed is 5 °/min, and the crystallinity of PCBT composite material is calculated using jade software；
4, self-repair efficiency is characterized by measuring the impact strength of sample, and impact strength is to measure one kind of toughness of material
Intensity index, characterization material resist the ability that shock loading is destroyed；
Shock-testing is tested on TH-6050 type Charpy impact machine tester according to 1043 standard of GB/T, is used
The impact of freely-supported beam type, non-notch sample, impact velocity 5m/s, impact energy 10J.Sample after impact fracture is pressed from both sides with G type
Tool is gently clamped in fracture position, is placed in 110 DEG C of vacuum drying oven and is placed 4h, then repeats the above test process.
The calculation formula of self-repair efficiency (η) are as follows:
η=Ib/Ⅰa× 100%
In formula, IaFor sample initial impact intensity (KJ/m2), IbFor sample impact strength (KJ/m after reparation2)
5, vertical combustion performance is provided to test by UL 94.
Test result is as shown in table 3.
Table 3
As can be seen from Table 3, selfreparing PCBT composite material of the invention has preferable mechanical property and anti-flammability, contains
The crystallinity of PCBT composite material can be effectively reduced in the addition of the unsaturated polyester (UP) of Diels-Alder key, improve its toughness, make material
The comprehensive performance of material is more preferable, while also imparting the performance that material is automatically repaired.
Two, influence of the catalyst to the mechanical property of PCBT composite material is probed into, 7 groups of design experiment group, every group of catalysis
The group of agent be grouped as and component between mass ratio be shown in Table 4.
Table 4
Test group 1~7 is prepared into the PCBT composite material (parts by weight of catalyst by the formula and preparation method of embodiment 4
It is 0.4 part), the tensile property and bending property of PCBT composite material are tested, test result is shown in Table 5.
Table 5
As can be seen from Table 5, organo aluminum catalyst is compounded with organotin catalysts, and the mechanical property of PCBT composite material is more excellent
Different, the catalytic activity for illustrating that organo aluminum catalyst is compounded with organotin catalysts is higher, increases the quantity in activated centre, product
Molecule chain growth, molecular weight increase.Meanwhile the mechanical property of test group 3 is optimal, illustrates that organotin catalysts are urged with organo-aluminium
Agent is compounded with the mass ratio of 5:2, and catalyzing cooperation effect is most obvious.
Three, influence of the inorganic fire retardants to the flame retardant property of PCBT composite material is probed into, 8 groups of design experiment group, every group
The group of inorganic fire retardants be grouped as and component between mass ratio be shown in Table 6.
Table 6
Test group 1~8 is prepared into the PCBT composite material (weight of inorganic fire retardants by the formula and preparation method of embodiment 4
Measuring part is 1.5 parts), the flame retardant property of PCBT composite material is tested, test result is shown in Table 7.
Table 7
| Sample | Fire-retardant rank |
| 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, nano-aluminum hydroxide, nanmeter antimong trioxide and nano-zinc borate compounding, PCBT composite material
Flame retardant property it is more excellent, illustrate nano-aluminum hydroxide, nanmeter antimong trioxide and nano-zinc borate compounding, fire-retardant association can be generated
Same effect.Meanwhile the flame retardant property of test group 2~4 is better than test group 1 and test group 5, illustrates nano-aluminum hydroxide: nanometer three
Aoxidize two antimony: nano-zinc borate=(1~3): when 1:1, flame retardant synergistic effect is become apparent from.Although in addition, test group 2, test group 3
94V-0 grades of UL are attained by with the fire-retardant rank of test group 4, but the mechanical property of test group 3 is than test group 2 and test group 4
More preferably, therefore, the present invention is using nano-aluminum hydroxide: nanmeter antimong trioxide: nano-zinc borate=2:1:1 is as inorganic fire retardants
Optimal proportion.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (10)
1. a kind of selfreparing PCBT composite material, which is characterized in that the component including following parts by weight: CBT resin 90~100
Part, 10~20 parts of the unsaturated polyester (UP) of the key containing Diels-Alder, 50~100 parts of unidirectional continuous fiber cloth, catalyst 0.2~0.6
Part, 0.5~2.5 part of inorganic fire retardants and 0.5~1.5 part of mill base.
2. selfreparing PCBT composite material as described in claim 1, which is characterized in that the component including following parts by weight: CBT
It is 100 parts of resin, 20 parts of the unsaturated polyester (UP) of the key containing Diels-Alder, 80 parts of unidirectional continuous fiber cloth, 0.4 part of catalyst, inorganic
1.5 parts and 1 part of mill base of fire retardant.
3. selfreparing PCBT composite material as claimed in claim 1 or 2, which is characterized in that the key containing Diels-Alder
Unsaturated polyester (UP) the preparation method comprises the following steps: by furyl polyester and bismaleimide in excessive N, N '-dimethyl formamide,
24~30h is reacted under 62~68 DEG C of mechanical stirrings, and then reaction solution is cooled to room temperature, is placed reaction liquid into anhydrous ether
Sedimentation 2~4 times, finally by sediment dry 18 in 40~50 DEG C of vacuum drying ovens~for 24 hours, obtain the key containing Diels-Alder
Unsaturated polyester (UP).
4. selfreparing PCBT composite material as claimed in claim 3, which is characterized in that the key containing Diels-Alder is not
In the preparation method of saturated polyester, the molar ratio of furyl polyester and bismaleimide is (8:1)~(10:1).
5. selfreparing PCBT composite material as claimed in claim 3, which is characterized in that the furyl polyester is poly- 2,5- furan
It mutters at least one of naphthalate (PEF), poly- 2,5- furandicarboxylic acid butanediol ester (PBF).
6. selfreparing PCBT composite material as described in claim 1, which is characterized in that the unidirectional continuous fiber cloth is by glass
At least one of fiber, carbon fiber, basalt fibre are made.
7. selfreparing PCBT composite material as described in claim 1, which is characterized in that the catalyst is by organotin catalysts
It is formed with organo aluminum catalyst；Preferably, it counts in mass ratio, in the catalyst, organotin catalysts: organo aluminum catalyst=
5:(1~3)；Most preferably, it counts in mass ratio, in the catalyst, organotin catalysts: organo aluminum catalyst=5:2.
8. selfreparing PCBT composite material as claimed in claim 7, which is characterized in that the organotin catalysts are monobutyl
At least one of tin oxide, dihydroxy dibutyl tin oxide, tin oxygen alkane；The organo aluminum catalyst is three aluminium ethylates, three isopropyls
At least one of aluminium alcoholates, ethylene glycol aluminium.
9. selfreparing PCBT composite material as described in claim 1, which is characterized in that the inorganic fire retardants is nanometer hydrogen-oxygen
Change at least one of aluminium, nanometer grade antimony trioxide, nano-zinc borate；Preferably, the inorganic fire retardants is by nanometer hydrogen-oxygen
Change aluminium, nanmeter antimong trioxide and nano-zinc borate composition；Preferably, it counts in mass ratio, in the inorganic fire retardants, nanometer hydrogen
Aluminium oxide: nanmeter antimong trioxide: nano-zinc borate=(1~3): 1:1；Most preferably, it counts in mass ratio, it is described inorganic fire-retarded
In agent, nano-aluminum hydroxide: nanmeter antimong trioxide: nano-zinc borate=2:1:1.
10. the preparation method of selfreparing PCBT composite material according to any one of claims 1 to 9, which is characterized in that including such as
Lower step:
(1) CBT resin, the unsaturated polyester (UP) of the key containing Diels-Alder and catalyst are prefabricated into respectively powdered, mixing is equal
Even, heated under vacuum is to 160~180 DEG C, after melting, inorganic fire retardants is added, stirs evenly, adds mill base, stir
Uniformly, it is then filled into unidirectional continuous fiber cloth, cooling sufficiently after infiltration, prepreg is made in winding；
(2) prepreg is put into mold, mold is placed on hot press, vacuum item by the prepreg of single layer by 45 ° of cross-level pavings
Part, hot-forming at 190~220 DEG C, cooling after keeping 1~4h, the selfreparing PCBT composite material is made in demoulding.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111719311A (en) * | 2020-06-23 | 2020-09-29 | 上海交通大学 | Modified carbon fiber, modified carbon fiber reinforced epoxy resin composite material and preparation method thereof |
| CN113527646A (en) * | 2021-08-25 | 2021-10-22 | 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 (6)
| 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 |
| 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 |
-
2019
- 2019-03-22 CN CN201910225371.2A patent/CN109971138B/en active Active
Patent Citations (6)
| 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 |
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111719311A (en) * | 2020-06-23 | 2020-09-29 | 上海交通大学 | Modified carbon fiber, modified carbon fiber reinforced epoxy resin composite material and preparation method thereof |
| 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 |
| CN113527646A (en) * | 2021-08-25 | 2021-10-22 | 四川大学 | Self-repairable furan group-containing bio-based unsaturated polyester resin and preparation method and application 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 |
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