CN114874541B - Flame-retardant smoke-suppressing polymer composite material and preparation method thereof - Google Patents
Flame-retardant smoke-suppressing polymer composite material and preparation method thereof Download PDFInfo
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- CN114874541B CN114874541B CN202210392561.5A CN202210392561A CN114874541B CN 114874541 B CN114874541 B CN 114874541B CN 202210392561 A CN202210392561 A CN 202210392561A CN 114874541 B CN114874541 B CN 114874541B
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- 239000002131 composite material Substances 0.000 title claims abstract description 103
- 239000003063 flame retardant Substances 0.000 title claims abstract description 81
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 141
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 141
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229920005989 resin Polymers 0.000 claims abstract description 61
- 239000011347 resin Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000011159 matrix material Substances 0.000 claims abstract description 40
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 32
- 238000011065 in-situ storage Methods 0.000 claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 19
- 239000000779 smoke Substances 0.000 claims abstract description 15
- 238000009755 vacuum infusion Methods 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 230000008020 evaporation Effects 0.000 claims abstract description 6
- 238000001338 self-assembly Methods 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 23
- 239000004917 carbon fiber Substances 0.000 claims description 23
- BHTBHKFULNTCHQ-UHFFFAOYSA-H zinc;tin(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Sn+4] BHTBHKFULNTCHQ-UHFFFAOYSA-H 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 238000000975 co-precipitation Methods 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 239000012763 reinforcing filler Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000297 Rayon Polymers 0.000 claims description 4
- 239000010426 asphalt Substances 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001947 vapour-phase growth Methods 0.000 claims description 2
- 230000001629 suppression Effects 0.000 abstract description 7
- 238000003618 dip coating Methods 0.000 abstract description 2
- 239000004743 Polypropylene Substances 0.000 description 36
- 229920001155 polypropylene Polymers 0.000 description 36
- 238000012360 testing method Methods 0.000 description 17
- 239000004793 Polystyrene Substances 0.000 description 16
- 239000002861 polymer material Substances 0.000 description 15
- 239000004800 polyvinyl chloride Substances 0.000 description 15
- 229920002223 polystyrene Polymers 0.000 description 14
- 229920000915 polyvinyl chloride Polymers 0.000 description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000012796 inorganic flame retardant Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052599 brucite Inorganic materials 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08K3/24—Acids; Salts thereof
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame-retardant smoke-suppressing polymer composite material and a preparation method thereof, wherein the method comprises the following steps: s1: the preparation method comprises the following steps of: 10-15% of three-dimensional carbon felt, 5-10% of zinc stannate and 75-85% of matrix resin; s2: loading zinc stannate on the three-dimensional carbon felt to prepare a three-dimensional zinc stannate loaded carbon felt preform; s3: and (3) carrying out vacuum infusion or in-situ polymerization on the three-dimensional zinc stannate-loaded carbon felt preform to obtain the flame-retardant smoke-suppressing polymer composite material with the zinc stannate loaded by the three-dimensional carbon felt. The invention utilizes the structural characteristics that fibers in the three-dimensional carbon felt preform are mutually overlapped to form the carbon felt, utilizes dip coating evaporation self-assembly to introduce zinc stannate, constructs a three-dimensional flame-retardant smoke-suppressing network framework and prepares the composite material through in-situ vacuum infusion or in-situ polymerization of matrix resin. The composite material prepared by the invention has excellent flame retardance, smoke suppression and mechanical properties, and can be widely applied to the flame retardance field.
Description
Technical Field
The invention belongs to the technical field of high polymer flame-retardant materials, and particularly relates to a flame-retardant smoke-suppressing high polymer composite material and a preparation method thereof.
Background
The polymer material is a long-chain molecule composed of repeating units, and is considered as a novel material for promoting social development together with steel, wood and cement. The polymer material has the characteristics of easy processing, flexibility, fatigue resistance, light weight, low production cost, high dielectric constant, high mechanical strength and the like, is widely applied to the industries of aerospace, electronic industry, biomedicine, automobiles and the like, but most of the polymer materials have inflammability and fire hazard. The flame retardant can endow the synthetic material with self-extinguishing property, flame retardance and smoke abatement property, so that the flame retardant becomes one of important auxiliary agents for developing and applying high polymer synthetic materials
Due to the high flame retardant efficiency of halogen containing flame retardants, they can function by suppressing ignition and slowing down flame propagation. However, halogen-containing flame retardants are prone to emission of toxic gases and fumes during combustion, releasing acidic fumes. Therefore, there is a need to develop halogen-free flame retardants to replace the current halogen-containing flame retardants. Zinc Hydroxystannate (ZHS) and Zinc Stannate (ZS) are novel inorganic flame-retardant smoke-suppressing agents, have the advantages of environmental protection, no toxicity and the like, are widely applied to the field of high polymer materials, and are considered to be one of novel, stable, efficient and green flame retardants. However, the inorganic flame retardants Zinc Hydroxystannate (ZHS) and Zinc Stannate (ZS) have problems of poor dispersibility (difficult to disperse uniformly) in polymer composite materials, and the like, so that the flame retardant performance is greatly limited and the complete release is difficult to obtain. Meanwhile, because Zinc Hydroxystannate (ZHS) and Zinc Stannate (ZS) have poor interfacial compatibility with organic high polymer materials, the problems of difficult dispersion and uneven dispersion exist in the high polymer materials, and the two problems can influence the performances of the high polymer materials, such as the mechanical properties, tensile strength and toughness of the high polymer materials, are obviously reduced.
In addition, the existing flame-retardant smoke-suppressing polymer composite material has the defects of complex preparation process, large addition amount of flame-retardant smoke-suppressing agent, low flame-retardant smoke-suppressing efficiency, obvious deterioration of mechanical properties and decorative effects of the material and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the flame-retardant smoke-suppressing polymer composite material and the preparation method thereof, and by introducing the three-dimensional carbon felt and synchronously improving the preparation method and the adopted components and the proportion, the addition amount of the flame-retardant smoke-suppressing agent can be greatly reduced, the preparation process is simplified, and the prepared composite material can continuously maintain the excellent mechanical property and the decorative effect of the polymer material on the basis of excellent flame-retardant smoke-suppressing performance.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the flame-retardant smoke-suppressing polymer composite material is characterized by comprising the following steps of:
s1: the preparation method comprises the following steps of: 10-15% of three-dimensional carbon felt, 5-10% of zinc stannate and 75-85% of matrix resin;
s2: loading zinc stannate on the three-dimensional carbon felt by a coprecipitation method, a hydrothermal synthesis method or a homogeneous precipitation method to prepare a three-dimensional zinc stannate loaded carbon felt preform, wherein the zinc stannate loaded carbon felt preform accounts for 15-25% of the total weight of the final composite material;
s3: vacuum pouring or in-situ polymerizing matrix resin to the three-dimensional zinc stannate-loaded carbon felt preform to prepare the flame-retardant smoke-suppressing polymer composite material with zinc stannate loaded by the three-dimensional carbon felt;
s4: and further cutting or hot-pressing the prepared flame-retardant smoke-suppression polymer composite material to finally prepare the flame-retardant smoke-suppression polymer composite material.
S2, which specifically comprises the following steps:
s21: ultrasonic soaking the three-dimensional carbon felt in a mixed solution of ethanol and acetone for 40min, taking out and drying to obtain a three-dimensional carbon felt A with a clean surface and active groups;
s22: and adding the three-dimensional carbon felt A into a solution system of zinc stannate prepared in advance, preparing a three-dimensional zinc stannate-loaded carbon felt preform by adopting a coprecipitation method or a hydrothermal synthesis method or a homogeneous precipitation method, taking out, drying and reserving.
The matrix resin is PP, PVC, PS resin or one of monomers thereof.
The matrix resin is one of polypropylene (PP), polyvinyl chloride (PVC) and Polystyrene (PS).
S3, the matrix resin is PP resin, and specifically comprises the following steps:
s31: firstly, adding dimethylbenzene with the volume three times that of PP resin into a beaker, then gradually adding the PP resin, heating and stirring, controlling the heating temperature to be between 120 and 140 ℃, and adding the three-dimensional zinc stannate-loaded carbon felt into the dissolved PP resin after the PP resin is dissolved; and then drying the xylene solvent to obtain the three-dimensional zinc stannate-loaded carbon felt PP system composite material, namely the flame-retardant smoke-suppressing polymer composite material.
S3, the matrix resin is PVC, and specifically comprises the following steps:
s32: adding an appropriate amount of deionized water, an appropriate amount of dispersing agent, an initiator and other auxiliary agents, a PVC monomer and a three-dimensional zinc stannate carbon felt loaded in a polymerization reaction kettle, controlling the reaction temperature to be 60 ℃, adding a terminator when the reaction pressure is reduced to a specified pressure, discharging, cleaning and drying to obtain the three-dimensional zinc stannate carbon felt loaded PVC system composite material, namely the flame-retardant smoke-suppressing polymer composite material.
S3, wherein the matrix resin is PS, and the method specifically comprises the following steps:
s33: mixing a three-dimensional zinc stannate-loaded carbon felt with a styrene PS monomer, magnetically stirring at room temperature for a period of time, adding a certain amount of dibenzoyl peroxide as an initiator into the mixed solution, pouring the mixed solution into a three-neck flask after the initiator is stirred and dissolved, and stirring at 90 ℃ for condensation reflux to initiate polymerization; when the polymerization is to be sticky, the condensing tube is taken down and stirred slowly for a period of time to discharge styrene monomer which is not polymerized; and then taking down the three-mouth bottle, rapidly pouring out the initial polymerization product, placing the initial polymerization product into a container, and placing the container into a 90 ℃ drying oven for continuous polymerization until the reaction is complete, thus obtaining the three-dimensional zinc stannate-loaded carbon felt PS composite material, namely the flame-retardant smoke-suppressing polymer composite material. .
The three-dimensional carbon felt is one or more of polyacrylonitrile carbon fiber, petroleum asphalt-based carbon fiber, viscose-based carbon fiber, vapor grown carbon fiber, polyimide-based carbon fiber and various carbonized fibers, wherein the surface of the polyacrylonitrile carbon fiber is provided with carboxyl or hydroxyl active groups; the fibers are mutually overlapped in the three-dimensional space to form a carbon felt, and the diameter of the fibers is 5-20 mu m.
The zinc stannate is one of zinc stannate or zinc hydroxystannate or a compound of the zinc stannate and the zinc hydroxystannate, and is prepared by adopting a coprecipitation method, a hydrothermal synthesis method or a homogeneous precipitation method.
The flame-retardant smoke-suppressing polymer composite material prepared by the method is characterized in that a three-dimensional carbon felt is used as a dispersion template, dipping coating evaporation is utilized for self-assembly, zinc stannate is uniformly dispersed and loaded in a three-dimensional structure of the three-dimensional carbon felt, a three-dimensional carbon felt prefabricated body with flame-retardant smoke-suppressing network frameworks which are mutually overlapped to form the carbon felt is constructed, and then a resin matrix is poured into the three-dimensional network frameworks in an in-situ vacuum manner, so that a composite material system which takes the three-dimensional carbon felt prefabricated body as a framework and takes matrix resin as reinforcing filler is obtained.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the flame-retardant smoke-suppressing polymer composite material and the preparation method, the three-dimensional carbon felt is introduced, the preparation method and the adopted components and the proportion are synchronously improved, the addition amount of the flame-retardant smoke-suppressing agent can be greatly reduced, the preparation process is simplified, and the prepared composite material continuously maintains the excellent mechanical property and the decorative effect of the polymer material on the basis of excellent flame-retardant smoke-suppressing performance.
2. According to the flame-retardant smoke-suppressing polymer composite material and the preparation method thereof, the introduced three-dimensional carbon felt has a good three-dimensional network, can contain a large number of groups on fibers, provides enough active sites, and can form good interface combination with an inorganic flame retardant, so that the three-dimensional structure of the three-dimensional carbon felt is used as a template for impregnating the polymer resin, the inorganic flame retardant can be well dispersed in the composite material, and the flame retardant performance of the three-dimensional carbon felt can be fully exerted; the three-dimensional carbon felt has good flame retardant effect as an inorganic carbon material, and the composite material with the three-dimensional structure has excellent mechanical property, flame retardance and smoke suppression performance, and is a polymer flame retardant composite material with a very good prospect and a preparation method thereof.
3. According to the invention, through the mutual synergistic effect between the three-dimensional carbon felt and the zinc stannate, the compatibility of the matrix resin and the zinc stannate interface is improved; the preparation method provided by the invention can skillfully disperse zinc stannate/zinc hydroxystannate in a three-dimensional carbon felt structure, and further enables the zinc stannate/zinc hydroxystannate to enhance the original performance in matrix resin, so that the mechanical, flame retardant and smoke suppression performances of the composite material system are obviously and synchronously improved.
4. The flame-retardant smoke-suppressing polymer composite material prepared by the invention has excellent flame-retardant and smoke-suppressing performances, and simultaneously better maintains the excellent mechanical and solvent-resistant performances of the polymer material. Meanwhile, the preparation method provided by the invention has the advantages of short time, easy control of technological process and lower manufacturing cost, can be used for producing composite material systems based on different resins, and is easy for industrialization.
Drawings
Fig. 1: SEM structure diagram of raw materials and intermediate materials adopted in embodiment 1 of the present invention;
fig. 2: SEM structure of the raw material and intermediate material used in example 3 of the present invention.
Detailed Description
The present invention will now be further described with reference to the drawings and examples, which are intended to be illustrative only of the principles and practice of the present invention.
The invention provides a preparation method of a flame-retardant smoke-suppressing polymer composite material, which comprises the following steps:
s1: the preparation method comprises the following steps of: 10-15% of three-dimensional carbon felt, 5-10% of zinc stannate and 75-85% of matrix resin;
s2: loading zinc stannate on the three-dimensional carbon felt by a coprecipitation method, a hydrothermal synthesis method or a homogeneous precipitation method to prepare a three-dimensional zinc stannate loaded carbon felt preform, wherein the zinc stannate loaded carbon felt preform accounts for 15-25% of the total weight of the final composite material; the method comprises the following steps:
s21: ultrasonic soaking the three-dimensional carbon felt in a solution of ethanol and acetone for 40min, taking out and drying to obtain a three-dimensional carbon felt A with a clean surface and active groups;
s22: adding the three-dimensional carbon felt A into a solution system of zinc stannate prepared in advance, preparing a three-dimensional zinc stannate-loaded carbon felt preform by adopting a coprecipitation method or a hydrothermal synthesis method or a homogeneous precipitation method, taking out, drying and reserving;
s3: vacuum pouring or in-situ polymerizing matrix resin to the three-dimensional zinc stannate-loaded carbon felt preform to prepare the flame-retardant smoke-suppressing polymer composite material with zinc stannate loaded by the three-dimensional carbon felt;
the matrix resin is one of polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS) resin or monomer thereof; the PP/PVC/PS can be a modified resin matrix with good flame retardant property and properly filled with aluminum hydroxide and magnesium hydroxide (brucite powder).
When the matrix resins are PP, PVC, PS, steps S31, S32, S33 are selectively performed: one of:
when the matrix resin is PP resin, the step S3 specifically includes the following steps:
s31: firstly, adding dimethylbenzene with the volume three times that of PP resin into a beaker, then gradually adding the PP resin, heating and stirring, controlling the heating temperature to be between 120 and 140 ℃, and adding the three-dimensional zinc stannate-loaded carbon felt into the dissolved PP resin after the PP resin is dissolved; and then drying the xylene solvent to obtain the three-dimensional zinc stannate-loaded carbon felt PP system composite material, namely the flame-retardant smoke-suppressing polymer composite material.
When the matrix resin is PVC, the step S3 specifically includes the following steps:
s32: adding an appropriate amount of deionized water, an appropriate amount of dispersing agent, an initiator and other auxiliary agents, a PVC monomer and a three-dimensional zinc stannate carbon felt loaded in a polymerization reaction kettle, controlling the reaction temperature to be 60 ℃, adding a terminator when the reaction pressure is reduced to a specified pressure, discharging, cleaning and drying to obtain the three-dimensional zinc stannate carbon felt loaded PVC system composite material, namely the flame-retardant smoke-suppressing polymer composite material.
When the matrix resin is PS, the step S3 specifically includes the following steps:
s33: mixing a three-dimensional zinc stannate-loaded carbon felt with a styrene PS monomer, magnetically stirring at room temperature for a period of time, adding a certain amount of dibenzoyl peroxide as an initiator into the mixed solution, pouring the mixed solution into a three-neck flask after the initiator is stirred and dissolved, and stirring at 90 ℃ for condensation reflux to initiate polymerization; when the polymerization is to be sticky, the condensing tube is taken down and stirred slowly for a period of time to discharge styrene monomer which is not polymerized; then taking down the three-mouth bottle, pouring out the initial polymerization product rapidly, placing the initial polymerization product in a container, putting the container into a 90 ℃ drying oven, and continuing to polymerize until the reaction is complete, thus obtaining the three-dimensional zinc stannate-loaded carbon felt PS composite material, namely the flame-retardant smoke-suppressing polymer composite material;
s4: and further cutting or hot-pressing the prepared flame-retardant smoke-suppression polymer composite material to finally prepare the flame-retardant smoke-suppression polymer composite material.
The three-dimensional carbon felt is one or more of polyacrylonitrile carbon fiber, petroleum asphalt-based carbon fiber, viscose-based carbon fiber, vapor grown carbon fiber, polyimide-based carbon fiber and various carbonized fibers, wherein the surface of the polyacrylonitrile carbon fiber is provided with carboxyl or hydroxyl active groups; the fibers are mutually overlapped in the three-dimensional space to form a carbon felt, and the diameter of the fibers is 5-20 mu m.
The zinc stannate is one of zinc stannate or zinc hydroxystannate or a compound of the zinc stannate and the zinc hydroxystannate, and is prepared by adopting a coprecipitation method, a hydrothermal synthesis method or a homogeneous precipitation method.
The flame-retardant smoke-suppressing polymer composite material prepared by the method is characterized in that a three-dimensional carbon felt is used as a dispersion template, dipping coating evaporation self-assembly is utilized, zinc stannate is uniformly dispersed and loaded in a three-dimensional structure of the three-dimensional carbon felt, a three-dimensional carbon felt prefabricated body with flame-retardant smoke-suppressing network frameworks which are mutually overlapped to form the carbon felt is constructed, and then matrix resin is subjected to in-situ vacuum infusion or in-situ polymerization to the three-dimensional network frameworks, so that a composite material system taking the three-dimensional carbon felt prefabricated body as a framework and the matrix resin as a reinforcing filler is obtained.
Example 1
Referring to fig. 1, the flame-retardant smoke-suppressing polymer composite material provided in the embodiment is prepared from a three-dimensional carbon felt, zinc stannate and PP, and the preparation method specifically comprises the following steps:
s1: the preparation method comprises the following steps:
preparing a three-dimensional carbon felt, zinc stannate and matrix resin PP respectively, wherein the three components are sequentially in percentage by weight: 10%, 5%, 85%; wherein, the three-dimensional zinc stannate carbon felt preform is 15%, the zinc stannate load is 5%, and the PP resin or monomer is 85%;
the three-dimensional carbon felt in the embodiment is polyimide-based carbon fiber, and the fibers are mutually overlapped in a three-dimensional space to form the carbon felt, wherein the diameter of the fibers is 10-20 mu m.
The PP in the embodiment is a modified resin matrix with good flame retardant property and modified by filling proper amount of aluminum hydroxide and magnesium hydroxide (brucite powder), which is beneficial to the finally prepared polymer composite material to achieve the triple effects of structural reinforcement, flame retardance and smoke abatement;
s2: loading zinc stannate on the three-dimensional carbon felt through a coprecipitation method, a hydrothermal synthesis method or a homogeneous precipitation method to prepare a three-dimensional zinc stannate loaded carbon felt preform, wherein the zinc stannate loaded carbon felt preform accounts for 15% of the total weight of the final composite material; the method comprises the following steps:
s21: ultrasonic soaking the three-dimensional carbon felt in a mixed solution of ethanol and acetone for 40min, taking out and drying to obtain a three-dimensional carbon felt A with a clean surface and active groups;
s22: adding the three-dimensional carbon felt A into a solution system of zinc stannate prepared in advance, preparing a three-dimensional zinc stannate-loaded carbon felt preform by adopting a coprecipitation method or a hydrothermal synthesis method or a homogeneous precipitation method, taking out, drying and reserving;
s3: vacuum pouring matrix resin PP into the three-dimensional zinc stannate-loaded carbon felt preform to prepare a flame-retardant smoke-suppressing polymer composite material with zinc stannate loaded by the three-dimensional carbon felt; when in-situ vacuum infusion is adopted, interfacial interaction between the three-dimensional carbon felt and resin is generated in the in-situ vacuum infusion process, so that the wettability of the three-dimensional carbon felt is improved, the interfacial compatibility between the three-dimensional structure and the high polymer material is enhanced, and the prepared composite material has excellent mechanical property, flame retardance and smoke suppression performance.
The method comprises the following specific steps: firstly, adding dimethylbenzene with the volume three times that of PP resin into a beaker, then gradually adding the PP resin, heating and stirring, controlling the heating temperature between 120 ℃ and 140 ℃, and adding the three-dimensional zinc stannate-loaded carbon felt into the dissolved PP resin after the PP resin is dissolved (a large amount of bubbles are generated); and then drying the xylene solvent to obtain the three-dimensional zinc stannate-loaded carbon felt PP system composite material, namely the flame-retardant smoke-suppressing polymer composite material.
S4: and further cutting or hot-pressing the flame-retardant smoke-suppressing polymer composite material to finally prepare the three-dimensional zinc stannate-loaded carbon felt PP composite material, namely a flame-retardant smoke-suppressing polymer composite material finished product.
The flame-retardant smoke-suppressing polymer composite material prepared by the method is characterized in that a three-dimensional carbon felt is used as a dispersion template, dipping coating evaporation self-assembly is utilized, zinc stannate is uniformly dispersed and loaded in a three-dimensional structure of the three-dimensional carbon felt, a three-dimensional carbon felt preform with flame-retardant smoke-suppressing network frameworks which are mutually overlapped to form the carbon felt is constructed, and matrix resin PP is infused into the three-dimensional network frameworks in an in-situ vacuum manner, so that a composite material system taking the three-dimensional carbon felt preform as a framework and the matrix resin PP as reinforcing filler is obtained.
Referring to fig. 1, a SEM characterization of the backbone and matrix of the raw materials and intermediate materials used in this example is shown to illustrate the micro-network structure of the final composite. The SEM image on the left side is the matrix resin, and regular wrinkles appear on the surface, which is generated by brittle fracture of liquid nitrogen; the middle is an SEM image of the three-dimensional carbon felt, polyimide-based carbon fibers in the three-dimensional carbon felt are staggered, a three-dimensional network structure is formed, and the surface is smooth; the right graph shows the three-dimensional carbon felt loaded with zinc stannate by adopting the coprecipitation method, and the zinc stannate is loaded on the surface of the fiber and forms a flame-retardant smoke-suppressing three-dimensional network together with the three-dimensional carbon felt. As can be seen from the right graph, the three-dimensional zinc stannate-loaded carbon felt PP composite material prepared in this embodiment is a composite material system that uses a three-dimensional carbon felt preform as a skeleton, uses matrix resin PP as a reinforcing filler, and uniformly distributes zinc stannate throughout the three-dimensional frame.
The flame-retardant smoke-suppressing polymer PP composite material sample prepared in the embodiment is subjected to mechanical property test, limiting oxygen index test, UL-94 vertical burning test and smoke density test, and the burning and mechanical test results of the composite material are shown in Table 1.
Example 2
The flame-retardant smoke-suppressing polymer composite material and the preparation method thereof provided in this embodiment are basically the same as those in embodiment 1, and are different in that:
the composite material is prepared from three-dimensional carbon felt, zinc hydroxystannate and PP monomers, and the mass percentages of the three are as follows: 15%, 10% and 75%.
The samples were subjected to mechanical property testing, limiting oxygen index testing, UL-94 vertical burning testing, smoke density testing and SEM characterization, and the results are shown in the table.
According to the embodiment of the invention, the three-dimensional carbon felt is better in wettability by generating the interfacial interaction between the three-dimensional carbon felt and the resin in the in-situ polymerization process, so that the interfacial compatibility between the three-dimensional structure and the high polymer material is enhanced, and the prepared composite material has excellent mechanical and flame-retardant and smoke-suppressing properties.
Example 3
The flame-retardant smoke-suppressing polymer composite material and the preparation method thereof provided by the embodiment of the invention are basically the same as those of the embodiments 1 and 2, and are different in that:
the composite material is prepared from a three-dimensional carbon felt, zinc stannate and PS, and the mass percentages of the three materials are as follows: 12.5%, 8.5% and 79%.
The three-dimensional carbon felt is polyacrylonitrile carbon fiber with carboxyl or hydroxyl active groups on the surface, and the fibers are mutually overlapped in a three-dimensional space to form the carbon felt, wherein the diameter of the fibers is 15-20 mu m.
The step S2 is to prepare a three-dimensional zinc stannate-loaded carbon felt preform by adopting a coprecipitation method;
and step S3, the preparation process of the three-dimensional zinc-stannate-loaded carbon felt PS composite material is that the three-dimensional zinc-stannate-loaded carbon felt PS composite material is prepared by in-situ polymerization of PS. The method comprises the following steps:
firstly, mixing a three-dimensional zinc stannate-loaded carbon felt with a styrene monomer, magnetically stirring at room temperature for a period of time, adding a certain amount of dibenzoyl peroxide as an initiator into the mixed solution, pouring the mixed solution into a three-neck flask after the initiator is stirred and dissolved, and stirring at 90 ℃ for condensation reflux to initiate polymerization; when polymerized to a viscous state, the condenser was removed and stirred slowly for a period of time to discharge styrene monomer that was not polymerized. And then taking down the three-mouth bottle, rapidly pouring out the initial polymerization product, placing the initial polymerization product in a container, putting the container into a 90 ℃ drying oven, and continuing to polymerize until the reaction is complete, thus finally obtaining the three-dimensional zinc stannate-loaded carbon felt PS composite material.
According to the embodiment, the three-dimensional carbon felt is better in wettability by generating interface interaction between the three-dimensional carbon felt and the resin in the in-situ polymerization process, so that the interface compatibility of the three-dimensional structure and the high polymer material is enhanced, and the prepared composite material has excellent mechanical property, flame retardance and smoke suppression performance.
See fig. 2: the SEM image on the left side is the matrix resin, and regular wrinkles appear on the surface, which is generated by brittle fracture of liquid nitrogen; the SEM image of the three-dimensional carbon felt is arranged in the middle, so that the polyacrylonitrile carbon fibers in the three-dimensional carbon felt are staggered to form a three-dimensional network structure, and the surface is smooth; the right graph shows a three-dimensional carbon felt loaded with zinc hydroxystannate by a hydrothermal synthesis method, and the zinc hydroxystannate is loaded on the surface of the fiber and forms a flame-retardant smoke-suppressing three-dimensional network together with the three-dimensional carbon felt.
The test results of mechanical properties, limiting oxygen index, UL-94 vertical burn test, smoke density test were carried out on the samples of the composite materials of this example and are shown in table 1.
Example 4
The flame-retardant smoke-suppressing polymer composite material and the preparation method thereof provided by the embodiment of the invention are basically the same as those of the embodiment 1, and the difference is that:
the composite material is prepared from three-dimensional carbon felt, zinc hydroxystannate and PVC, and the mass percentages of the three are as follows: 12.5%, 7.5% and 80%.
The three-dimensional carbon felt is petroleum asphalt-based carbon fiber with carboxyl or hydroxyl active groups on the surface, all the fibers are mutually overlapped in a three-dimensional space to form the carbon felt, and the diameter of the fibers is 5-10 mu m.
The zinc hydroxystannate is prepared by a hydrothermal synthesis method;
the preparation process of the three-dimensional zinc hydroxystannate carbon felt PVC composite material comprises the following steps of: adding a proper amount of deionized water, a proper amount of dispersing agent, initiator and other auxiliary agents, vinyl chloride monomer and three-dimensional zinc stannate-loaded carbon felt into a polymerization reaction kettle, controlling the reaction temperature to be 60 ℃, adding a terminator when the reaction pressure is reduced to a specified pressure, and discharging; and (5) cleaning and drying to obtain the composite material.
In the step S3, the three-dimensional zinc hydroxystannate carbon felt PVC composite material is prepared by in-situ polymerization of PVC, and the three-dimensional carbon felt wettability is improved by generating interface interaction between the three-dimensional carbon felt and matrix resin in the in-situ polymerization process, so that the interface compatibility of a three-dimensional structure and a matrix resin high polymer material is enhanced, and the prepared composite material has excellent mechanical property, flame retardance and smoke suppression performance.
The composite material samples prepared in this example were subjected to mechanical property test, limiting oxygen index test, UL-94 vertical combustion test, smoke density test, and the results are shown in table 1.
Table 1: composite material combustion and mechanical test results obtained for each example material sample:
as can be seen from Table 1, the flame-retardant smoke-suppressing polymer composite material containing the three-dimensional network skeleton structure prepared by the embodiments of the invention can obviously improve the flame retardance, smoke suppressing performance and mechanical property of the composite material. The flame retardant property of the composite material prepared by each embodiment can reach V-0, the limiting oxygen index is more than 36%, and meanwhile, the mechanical property (tensile strength) of the composite material is obviously improved, so that the composite material has balanced and excellent material properties.
The invention mainly introduces a three-dimensional carbon felt, utilizes the structural characteristics that fibers in a three-dimensional carbon felt preform are mutually overlapped to form the carbon felt, synchronously improves components, proportions and a preparation process, utilizes dip coating evaporation self-assembly to introduce zinc stannate, constructs a three-dimensional flame-retardant smoke-suppressing network framework, and prepares the composite material through in-situ vacuum infusion or in-situ polymerization of matrix resin. The composite material prepared by the invention has excellent flame retardance, smoke suppression and mechanical properties, and can be widely applied to the flame retardance field.
It should be noted that, referring to the specific formulation, the value range of the chemical formula parameter, and the specific conditions of the preparation process in the above embodiments, other embodiments may specifically select different components, proportions, and process conditions within the scope of the present invention, for example: the three-dimensional carbon felt can also be one or more of viscose-based carbon fibers, vapor-phase growth carbon fibers and various carbon fibers with carboxyl or hydroxyl active groups on the surface, and the technical effects of the invention can be realized.
The foregoing drawings and examples illustrate the present invention in detail, and it is to be understood that the present invention is not limited to the embodiments described above, but is intended to be within the scope of the present invention for a person skilled in the art to understand the present invention and practice the present invention accordingly.
Claims (6)
1. The preparation method of the flame-retardant smoke-suppressing polymer composite material is characterized by comprising the following steps of:
s1: the preparation method comprises the following steps of: 10-15% of a three-dimensional carbon felt, 5-10% of zinc stannate and 75-85% of matrix resin;
the three-dimensional carbon felt is one or two or more of polyacrylonitrile carbon fiber, petroleum asphalt-based carbon fiber, viscose-based carbon fiber, vapor-phase growth carbon fiber and polyimide-based carbon fiber with carboxyl or hydroxyl active groups on the surface; the fibers are mutually overlapped in the three-dimensional space to form a carbon felt, and the diameter of the fibers is 5-20 mu m;
the matrix resin is one of PP, PVC, PS resins;
s2: loading zinc stannate on the three-dimensional carbon felt through a coprecipitation method, a hydrothermal synthesis method or a homogeneous precipitation method to prepare a three-dimensional zinc stannate loaded carbon felt preform, wherein the zinc stannate loaded carbon felt preform accounts for 15-25% of the total weight of the final composite material;
s21: ultrasonic soaking the three-dimensional carbon felt in a solution of ethanol and acetone for 40min, taking out and drying to obtain a three-dimensional carbon felt A with a clean surface and active groups;
s22: adding the three-dimensional carbon felt A into a solution system of zinc stannate prepared in advance, preparing a three-dimensional zinc stannate-loaded carbon felt preform by adopting a coprecipitation method or a hydrothermal synthesis method or a homogeneous precipitation method, taking out, drying and reserving;
s3: and (3) carrying out vacuum infusion or in-situ polymerization on the three-dimensional zinc stannate-loaded carbon felt preform to obtain the flame-retardant smoke-suppressing polymer composite material with the zinc stannate loaded by the three-dimensional carbon felt.
2. The method for preparing the flame retardant and smoke suppressant polymer composite according to claim 1, further comprising the steps of:
s4: and further cutting or hot-pressing the prepared flame-retardant smoke-suppression polymer composite material to finally prepare the flame-retardant smoke-suppression polymer composite material.
3. The method for preparing the flame-retardant smoke-suppressing polymer composite material according to claim 1, wherein,
the matrix resin in the step S3 is PVC, and specifically comprises the following steps:
s32: adding deionized water, a dispersing agent, an initiator, a vinyl chloride monomer and a three-dimensional zinc stannate carbon felt loaded in a polymerization reaction kettle, controlling the reaction temperature to be 60 ℃, adding a terminator when the reaction pressure is reduced to a specified pressure, discharging, cleaning and drying to obtain the three-dimensional zinc stannate carbon felt loaded PVC system composite material, namely the flame-retardant smoke-suppressing polymer composite material.
4. The method for preparing the flame-retardant smoke-suppressing polymer composite material according to claim 1, wherein,
the matrix resin in the step S3 is PS, and specifically comprises the following steps:
s33: mixing a three-dimensional zinc stannate-loaded carbon felt with a styrene PS monomer, magnetically stirring at room temperature for a period of time, adding dibenzoyl peroxide into the mixed solution as an initiator, pouring the mixed solution into a three-neck flask after the initiator is stirred and dissolved, and stirring at 90 ℃ and condensing and refluxing to initiate polymerization; when the polymerization is to be sticky, the condensing tube is taken down and stirred slowly for a period of time to discharge styrene monomer which is not polymerized; and then taking down the three-mouth bottle, rapidly pouring out the initial polymerization product, placing the initial polymerization product into a container, and placing the container into a 90 ℃ drying oven for continuous polymerization until the reaction is complete, thus obtaining the three-dimensional zinc stannate-loaded carbon felt composite material, namely the flame-retardant smoke-suppressing polymer composite material.
5. The method for preparing the flame-retardant smoke-suppressing polymer composite material according to claim 1, wherein,
the zinc stannate is one of zinc stannate or zinc hydroxystannate or a compound of the zinc stannate and the zinc hydroxystannate, and is prepared by adopting a coprecipitation method, a hydrothermal synthesis method or a homogeneous precipitation method.
6. A flame-retardant smoke-suppressing polymer composite material prepared by the method of any one of claims 1-5 is characterized in that a three-dimensional carbon felt is used as a dispersion template, dipping coating evaporation is utilized for self-assembly, zinc stannate is uniformly dispersed and loaded in a three-dimensional structure of the three-dimensional carbon felt, a three-dimensional carbon felt preform with flame-retardant smoke-suppressing network frameworks which are mutually overlapped to form the carbon felt is constructed, and then in-situ vacuum infusion or in-situ polymerization is carried out on the three-dimensional network frameworks, so that a composite material system which takes the three-dimensional carbon felt preform as a framework and takes the matrix resin as a reinforcing filler is obtained.
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