CN115895182A - Flame-retardant toughened modified phenolic resin film and preparation method thereof - Google Patents
Flame-retardant toughened modified phenolic resin film and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of high polymer materials, and provides a flame-retardant toughened modified phenolic resin film and a preparation method thereof, wherein the flame-retardant toughened modified phenolic resin film at least comprises the following materials in parts by mass: 50-90 parts of phenolic resin, 10-50 parts of benzoxazine resin, 50-100 parts of polyvinyl butyral, 10-30 parts of reactive phosphorus flame retardant and 5-10 parts of synergistic flame retardant; firstly, dissolving polyvinyl butyral by absolute ethyl alcohol, then adding phenolic resin, benzoxazine resin, reactive phosphorus flame retardant and synergistic flame retardant, fully stirring and dissolving the mixed solution, uniformly mixing, and preparing the flame-retardant toughening modified phenolic resin film by adopting a coating process, wherein the microstructure of the film presents multi-scale and multi-level toughening and flame retardance, so that the toughening and flame-retardant effects of the phenolic resin are realized.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, relates to a modified phenolic resin preparation technology, and particularly relates to a flame-retardant toughened modified phenolic resin film and a preparation method thereof.
Background
The phenolic resin (PF) has the characteristics of low price, electric insulation, low toxicity, low smoke, good bonding property and the like, and is widely applied to the fields of armor protection, vehicle engineering and aerospace, but the traditional phenolic resin has the defects of high brittleness, low toughness and tensile strength, low interlaminar strength, delamination resistance, weak impact resistance and the like; although the oxygen index of the phenolic resin is about 28%, the phenolic resin cannot meet the flame retardant requirement in the fields of ship protection, aerospace and the like which have strict requirements on low-smoke flame retardant property of materials, and further wide application of the phenolic resin is limited.
Zhang Liqing (heat resistance and toughening property [ J ] of polyvinyl butyral modified phenolic resin, science and engineering of high molecular materials, 2021, (37) 6. Because the oxygen index of PVB is only about 17 percent, the flame retardance is obviously reduced after toughening modification.
Guo Jintang (research on flame retardance and toughening of phenolic resin [ J ]. Combustion science and technology, 2003, (9) 2: 104-107.) in phenolic resin synthesis, by adding nonylphenol to partially replace phenol, the toughness of phenolic foam can be obviously increased under the condition of basically unchanged flame retardant property.
The above problems of high toughness and high flame retardancy of phenolic resin are not solved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a flame-retardant toughening modified phenolic resin film and a preparation method thereof, and solves the problem that the phenolic resin is difficult to combine high toughness and high flame retardance.
The purpose of the invention is realized as follows: polyvinyl butyral (PVB) is used as a modifier, and when the modified phenolic resin is heated and cured, hydroxymethyl in phenolic resin molecules and hydroxyl in PVB molecules are subjected to dehydration condensation reaction to obtain a PVB-phenolic resin graft copolymer, so that the network compactness of the phenolic resin is reduced, and the toughness of the phenolic resin is improved; the phosphorus flame retardant and phenolic resin are subjected to chemical reaction, and a molecular chain segment or a structure with flame retardant property is introduced in the synthesis of the phenolic resin, so that the phenolic resin is endowed with permanent flame retardant property; the synergistic flame retardant is adopted, so that the reaction with the phenolic resin can be realized, and the combustion carbon forming rate of the phenolic resin can be obviously improved; the benzoxazine resin and the phenolic resin can be mutually used as curing agents, and can form a Mannich bridge structure with the phenolic hydroxyl of the linear phenolic after the ring opening of the benzoxazine resin, so that the toughness of a phenolic resin system is increased, and meanwhile, the flame retardance and the heat resistance of the system are improved to some extent due to the formation of a complex cross-linked network structure.
The invention adopts the following specific technical scheme:
the flame-retardant toughened modified phenolic resin film at least comprises the following materials in parts by mass:
the sum of the phenolic resin and the benzoxazine resin is 100 parts by mass.
The invention relates to a flame-retardant toughening modified phenolic resin film, wherein the phenolic resin is liquid alkali-catalyzed phenolic resin.
Preferably, the liquid alkali-catalyzed phenolic resin is one of S157 and PF 9601.
The invention relates to a flame-retardant toughening modified phenolic resin film, wherein the benzoxazine resin is liquid benzoxazine resin.
Preferably, the liquid benzoxazine resin is bisphenol F type benzoxazine resin LZ96 or LZ 24.
Preferably, the reactive phosphorus flame retardant is 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ) and/or [ (6-oxy- (6H) -dibenzo- (CE) (1,2) -phosphapham-6-one) methyl ] -butanedioic acid (DOPO-DDP).
Preferably, the synergistic flame retardant is tannic acid and/or hydroxyethylidene diphosphonic acid (HEDP).
The invention relates to a preparation method of a flame-retardant toughened modified phenolic resin film, which comprises the following specific steps:
1) Weighing various materials according to a formula ratio, dissolving a toughening agent polyvinyl butyral in absolute ethyl alcohol, wherein the mass ratio of the toughening agent to the absolute ethyl alcohol is 1:8-1, and fully stirring until a mixed solution is uniform and transparent;
2) Adding phenolic resin and benzoxazine resin into the solution obtained in the step 1), and continuously stirring until the phenolic resin and the benzoxazine resin are uniformly mixed;
3) Adding the reactive phosphorus flame retardant and the synergistic flame retardant into the solution obtained in the step 2), and continuously stirring until the mixture is uniformly mixed to obtain a modified phenolic resin mixed solution;
4) The modified phenolic resin mixed solution is coated on a smooth stainless steel plate smoothly, and the coating surface density is not less than 1kg/m 2 And (3) ventilating and drying at normal temperature for not less than 4h, then precuring at 80-100 ℃ for 10-30 min, cooling and stripping to obtain the flame-retardant toughened modified phenolic resin film.
The peel strength of the flame-retardant toughened modified phenolic resin film related to the invention and a smooth stainless steel plate is 12-20N/cm; after the phenolic resin is completely cured, compared with pure phenolic resin, the maximum deflection is improved by 70%, and the toughness of the phenolic resin is obviously improved; the oxygen index is not less than 30%, and the flame retardance is obviously improved; can be used in the fields of ship protective armor, lining armor, high-temperature resistant bonding materials, corrosion-resistant materials and the like.
The preparation method comprises the steps of firstly dissolving a proper amount of toughening agent polyvinyl butyral by absolute ethyl alcohol, then adding a certain proportion of phenolic resin, benzoxazine resin, reactive phosphorus flame retardant and synergistic flame retardant, fully stirring, dissolving and uniformly mixing the mixed solution, obtaining an uncrosslinked and cured film by a coating process, and controlling the precuring crosslinking degree of a precuring temperature regulation and control system to enable the microstructure to present multi-scale and multi-level toughening and flame retardance, so that the toughening and flame retardance effects of the phenolic resin are realized at the same time, and the method is suitable for batch production.
Detailed Description
The present invention will be further described with reference to the following examples, but the technical solution of the present invention is not limited to the specific embodiments listed below. The invention is not limited to the embodiments described above, but rather, various modifications and changes may be made by those skilled in the art without departing from the scope of the invention.
Example one
The flame-retardant toughened modified phenolic resin film comprises the following materials in parts by mass:
50 parts of S157 phenolic resin, 50 parts of LZ96 benzoxazine resin, 50 parts of polyvinyl butyral (PVB) toughening agent, 10 parts of reactive phosphorus flame retardant DOPO-HQ and 5 parts of synergistic flame retardant tannic acid.
A preparation method of a flame-retardant toughening modified phenolic resin film comprises the following specific steps:
1) Weighing 50 parts of polyvinyl butyral (PVB), dissolving in 400 parts of absolute ethyl alcohol, and fully stirring until the solution is uniform and transparent;
2) Weighing 50 parts of S157 phenolic resin and 50 parts of LZ96 benzoxazine resin, adding into the solution in the step 1), and fully stirring until the mixture is uniformly mixed;
3) Sequentially weighing 10 parts of DOPO-HQ and 5 parts of tannic acid, adding into the solution obtained in the step 2), and fully stirring until the components are uniformly mixed to obtain a modified phenolic resin mixed solution;
4) The modified phenolic resin mixed solution is coated on a smooth stainless steel plate smoothly, and the coating surface density is 1kg/m 2 And (3) ventilating and drying for 4h at normal temperature, then precuring for 35min at 80 ℃, cooling and stripping to prepare the flame-retardant toughening modified phenolic resin film.
The flame-retardant toughened modified phenolic resin film prepared by the embodiment has stable property under the normal-temperature storage condition, is a ginger-yellow soft elastic film, has the film thickness of 0.32mm, and has the peel strength between the film and a smooth stainless steel plate of 15.9N/cm. The limiting oxygen index of the material after the resin film is heated and cured is 32.2 percent, and the maximum deflection is 19.5mm (the maximum deflection of pure phenolic resin is 8.6 mm).
Example two
The flame-retardant toughened modified phenolic resin film comprises the following materials in parts by mass:
62 parts of S157 phenolic resin, 38 parts of LZ24 benzoxazine resin, 60 parts of polyvinyl butyral (PVB) toughening agent, 20 parts of reactive phosphorus flame retardant DOPO-HQ and 7 parts of synergistic flame retardant tannic acid.
A preparation method of a flame-retardant toughening modified phenolic resin film comprises the following specific steps:
1) Weighing 60 parts of polyvinyl butyral (PVB), dissolving in 500 parts of absolute ethyl alcohol, and fully stirring until the solution is uniform and transparent;
2) Weighing 62 parts of S157 phenolic resin and 38 parts of LZ24 benzoxazine resin, adding into the solution obtained in the step 1), and fully stirring until the mixture is uniformly mixed;
3) Sequentially weighing 20 parts of DOPO-HQ and 7 parts of tannic acid, adding into the solution obtained in the step 2), and fully stirring until the mixture is uniformly mixed to obtain a modified phenolic resin mixed solution;
4) The mixed solution of the modified phenolic resin is coated on a smooth stainless steel plate smoothly, and the coating surface density is 1.1kg/m 2 And (3) ventilating and drying for 5h at normal temperature, then precuring for 20min at 90 ℃, cooling and stripping to obtain the flame-retardant toughening modified phenolic resin film.
The flame-retardant toughened modified phenolic resin film prepared in the embodiment has stable property under normal-temperature storage conditions, is a ginger-yellow soft elastic film, has a film thickness of 0.33mm, and has a peel strength of 13.8N/cm with respect to a smooth stainless steel plate. The limiting oxygen index of the material after the resin film is heated and cured is 33.4 percent, and the maximum deflection is 14.7mm (the maximum deflection of pure phenolic resin is 8.6 mm).
EXAMPLE III
The flame-retardant toughened modified phenolic resin film comprises the following materials in parts by mass:
58 parts of PF9601 phenolic resin, 42 parts of LZ96 benzoxazine resin, 64 parts of polyvinyl butyral (PVB) toughening agent, 10 parts of reactive phosphorus flame retardant DOPO-DDP and 5 parts of synergistic flame retardant HEDP.
A preparation method of a flame-retardant toughening modified phenolic resin film comprises the following specific steps:
1) Weighing 64 parts of polyvinyl butyral (PVB), dissolving in 600 parts of absolute ethyl alcohol, and fully stirring until the solution is uniform and transparent;
2) Weighing 58 parts of PF9601 phenolic resin and 42 parts of LZ96 benzoxazine resin, adding into the solution obtained in the step 1), and fully stirring until the mixture is uniformly mixed;
3) Sequentially weighing 10 parts of DOPO-DDP and 5 parts of HEDP, adding into the solution obtained in the step 2), and fully stirring until the mixture is uniformly mixed to obtain a modified phenolic resin mixed solution;
4) The mixed solution of the modified phenolic resin is coated on a smooth stainless steel plate smoothly, and the coating surface density is 1.1kg/m 2 And (3) ventilating and drying for 6.5h at normal temperature, then precuring for 25min at 85 ℃, cooling and stripping to prepare the flame-retardant toughening modified phenolic resin film.
The flame-retardant toughened modified phenolic resin film prepared by the embodiment has stable property under the normal-temperature storage condition, is a ginger-yellow soft elastic film, has the film thickness of 0.32mm, and has the peel strength between the film and a smooth stainless steel plate of 20N/cm. The limiting oxygen index of the material after the resin film is heated and cured is 31.2 percent, and the maximum deflection is 21.5mm (the maximum deflection of pure phenolic resin is 8.6 mm).
Example four
The flame-retardant toughened modified phenolic resin film comprises the following materials in parts by mass:
77 parts of PF9601 phenolic resin, 23 parts of LZ96 benzoxazine resin, 90 parts of polyvinyl butyral (PVB) toughening agent, 15 parts of reactive phosphorus flame retardant DOPO-HQ,5 parts of DOPO-DDP and 10 parts of synergistic flame retardant tannic acid.
A preparation method of a flame-retardant toughening modified phenolic resin film comprises the following specific steps:
1) Weighing 90 parts of polyvinyl butyral (PVB), dissolving in 1000 parts of absolute ethyl alcohol, and fully stirring until the solution is uniform and transparent;
2) Weighing 77 parts of PF9601 phenolic resin and 23 parts of LZ96 benzoxazine resin, adding into the solution obtained in the step 1), and fully stirring until the mixture is uniformly mixed;
3) Weighing 15 parts of DOPO-HQ,5 parts of DOPO-DDP and 5 parts of tannic acid in sequence, adding the mixture into the solution obtained in the step 2), and fully stirring until the mixture is uniformly mixed to obtain a modified phenolic resin mixed solution;
4) The mixed solution of the modified phenolic resin is coated on a smooth stainless steel plate smoothly, and the coating surface density is 1.3kg/m 2 And (3) ventilating and drying for 5.5h at normal temperature, then precuring for 20min at 90 ℃, cooling and stripping to prepare the flame-retardant toughening modified phenolic resin film.
The flame-retardant toughened modified phenolic resin film prepared in the embodiment has stable property under normal-temperature storage conditions, is a ginger-yellow soft elastic film, has a film thickness of 0.25mm, and has a peel strength of 14.7N/cm with respect to a smooth stainless steel plate. The limiting oxygen index of the material after the resin film is heated and cured is 34.1 percent, and the maximum deflection is 17.4mm (the maximum deflection of pure phenolic resin is 8.6 mm).
EXAMPLE five
The flame-retardant toughened modified phenolic resin film comprises the following materials in parts by mass:
90 parts of PF9601 phenolic resin, 10 parts of LZ24 benzoxazine resin, 100 parts of polyvinyl butyral (PVB) toughening agent, 15 parts of reactive phosphorus flame retardant DOPO-HQ,15 parts of DOPO-DDP,5 parts of synergistic flame retardant tannic acid and 5 parts of HEDP.
A preparation method of a flame-retardant toughening modified phenolic resin film comprises the following specific steps:
1) Weighing 100 parts of polyvinyl butyral (PVB), dissolving in 1200 parts of absolute ethyl alcohol, and fully stirring until the solution is uniform and transparent;
2) Weighing 90 parts of PF9601 phenolic resin and 10 parts of LZ96 benzoxazine resin, adding into the solution in the step 1), and fully stirring until the mixture is uniformly mixed;
3) Weighing 15 parts of DOPO-HQ,15 parts of DOPO-DDP,5 parts of tannic acid and 5 parts of HEDP in sequence, adding the mixture into the solution obtained in the step 2), and fully stirring the mixture until the mixture is uniformly mixed to obtain a modified phenolic resin mixed solution;
4) The mixed solution of the modified phenolic resin is coated on a smooth stainless steel plate smoothly, and the coating surface density is 1.2kg/m 2 And (3) drying for 5h at normal temperature in a ventilating way, then pre-curing for 15min at 100 ℃, cooling and stripping to obtain the flame-retardant toughening modified phenolic resin film.
The flame-retardant toughened modified phenolic resin film prepared in the embodiment has stable property under normal-temperature storage conditions, is a ginger-yellow soft elastic film, has a film thickness of 0.23mm, and has a peel strength of 13.4N/cm with respect to a smooth stainless steel plate. The limiting oxygen index of the material after the resin film is heated and cured is 30.5 percent, and the maximum deflection is 14.9mm (the maximum deflection of pure phenolic resin is 8.6 mm).
EXAMPLE six
The flame-retardant toughened modified phenolic resin film comprises the following materials in parts by mass:
65 parts of PF9601 phenolic resin, 35 parts of LZ24 benzoxazine resin, 80 parts of polyvinyl butyral (PVB) toughening agent, 30 parts of reactive phosphorus flame retardant DOPO-DDP and 5 parts of synergistic flame retardant tannic acid.
A preparation method of a flame-retardant toughening modified phenolic resin film comprises the following specific steps:
1) Weighing 80 parts of polyvinyl butyral (PVB), dissolving in 800 parts of absolute ethyl alcohol, and fully stirring until the solution is uniform and transparent;
2) Weighing 65 parts of PF9601 phenolic resin and 35 parts of LZ24 benzoxazine resin, adding into the solution obtained in the step 1), and fully stirring until the mixture is uniformly mixed;
3) Weighing 30 parts of DOPO-DDP and 5 parts of tannic acid in sequence, adding into the solution obtained in the step 2), and fully stirring until the mixture is uniformly mixed to obtain a modified phenolic resin mixed solution;
4) The modified phenolic resin mixed solution is coated on a smooth stainless steel plate to be flat, and the coating surface density is 1.4kg/m 2 And (3) ventilating and drying for 7.5h at normal temperature, then precuring for 30min at 85 ℃, cooling and stripping to prepare the flame-retardant toughened modified phenolic resin film.
The flame-retardant toughened modified phenolic resin film prepared in the embodiment has stable property under normal-temperature storage conditions, is a ginger-yellow soft elastic film, has a film thickness of 0.33mm, and has a peel strength of 17.1N/cm with respect to a smooth stainless steel plate. The limiting oxygen index of the material after the resin film is heated and cured is 34.8 percent, and the maximum deflection is 17.8mm (the maximum deflection of pure phenolic resin is 8.6 mm).
EXAMPLE seven
The flame-retardant toughened modified phenolic resin film comprises the following materials in parts by mass:
80 parts of S157 phenolic resin, 20 parts of LZ96 benzoxazine resin, 80 parts of polyvinyl butyral (PVB) toughening agent, 5 parts of reactive phosphorus flame retardant DOPO-HQ,15 parts of DOPO-DDP and 8 parts of synergistic flame retardant HEDP.
A preparation method of a flame-retardant toughening modified phenolic resin film comprises the following specific steps:
1) Weighing 80 parts of polyvinyl butyral (PVB), dissolving in 900 parts of absolute ethyl alcohol, and fully stirring until the solution is uniform and transparent;
2) Weighing 80 parts of S157 phenolic resin and 20 parts of LZ96 benzoxazine resin, adding into the solution in the step 1), and fully stirring until the mixture is uniformly mixed;
3) Weighing 5 parts of DOPO-HQ,15 parts of DOPO-DDP and 5 parts of HEDP in sequence, adding into the solution obtained in the step 2), and fully stirring until the mixture is uniformly mixed to obtain a modified phenolic resin mixed solution;
4) The modified phenolic resin mixed solution is coated on a smooth stainless steel plate smoothly, and the coating surface density is 1.3kg/m 2 And (3) ventilating and drying for 6h at normal temperature, then precuring for 25min at 85 ℃, cooling and stripping to obtain the flame-retardant toughening modified phenolic resin film.
The flame-retardant toughened modified phenolic resin film prepared in the embodiment has stable property under normal-temperature storage conditions, is a ginger-yellow soft elastic film, has a film thickness of 0.26mm, and has a peel strength of 14.0N/cm with respect to a smooth stainless steel plate. The limiting oxygen index of the material after the resin film is heated and cured is 33.5 percent, and the maximum deflection is 16.8mm (the maximum deflection of pure phenolic resin is 8.6 mm).
Example eight
The flame-retardant toughened modified phenolic resin film comprises the following materials in parts by mass: 60 parts of PF9601 phenolic resin, 40 parts of LZ24 benzoxazine resin, 70 parts of polyvinyl butyral (PVB) toughening agent, 20 parts of reactive phosphorus flame retardant DOPO-DDP,3 parts of synergistic flame retardant tannic acid and 7 parts of HEDP.
A preparation method of a flame-retardant toughening modified phenolic resin film comprises the following specific steps:
1) Weighing 70 parts of polyvinyl butyral (PVB), dissolving in 650 parts of absolute ethyl alcohol, and fully stirring until the solution is uniform and transparent;
2) Weighing 60 parts of PF9601 phenolic resin and 40 parts of LZ24 benzoxazine resin, adding into the solution obtained in the step 1), and fully stirring until the mixture is uniformly mixed;
3) Sequentially weighing 20 parts of DOPO-DDP,3 parts of tannic acid and 7 parts of HEDP, adding into the solution obtained in the step 2), and fully stirring until the mixture is uniformly mixed to obtain a modified phenolic resin mixed solution;
4) The mixed solution of the modified phenolic resin is coated on a smooth stainless steel plate to be flat,the coating surface density was 1.6kg/m 2 And (3) ventilating and drying for 8h at normal temperature, then precuring for 20min at 95 ℃, cooling and stripping to obtain the flame-retardant toughening modified phenolic resin film.
The flame-retardant toughened modified phenolic resin film prepared in the embodiment has stable property under normal-temperature storage conditions, is a ginger-yellow soft elastic film, has a film thickness of 0.39mm, and has a peel strength of 14.5N/cm with respect to a smooth stainless steel plate. The limiting oxygen index of the material after the resin film is heated and cured is 33.0 percent, and the maximum deflection is 18.5mm (the maximum deflection of pure phenolic resin is 8.6 mm).
Example nine
The flame-retardant toughened modified phenolic resin film comprises the following materials in parts by mass: 90 parts of S157 phenolic resin, 10 parts of LZ24 benzoxazine resin, 90 parts of polyvinyl butyral (PVB) toughening agent, 10 parts of reactive phosphorus flame retardant DOPO-HQ,10 parts of DOPO-DDP and 10 parts of synergistic flame retardant HEDP.
A preparation method of a flame-retardant toughening modified phenolic resin film comprises the following specific steps:
1) Weighing 90 parts of polyvinyl butyral (PVB), dissolving in 1080 parts of absolute ethyl alcohol, and fully stirring until the solution is uniform and transparent;
2) Weighing 90 parts of S157 phenolic resin and 10 parts of LZ24 benzoxazine resin, adding into the solution obtained in the step 1), and fully stirring until the mixture is uniformly mixed;
3) Sequentially weighing 10 parts of DOPO-HQ,10 parts of DOPO-DDP and 10 parts of HEDP, adding into the solution obtained in the step 2), and fully stirring until the mixture is uniformly mixed to obtain a modified phenolic resin mixed solution;
4) The modified phenolic resin mixed solution is coated on a smooth stainless steel plate to be flat, and the coating surface density is 1.4kg/m 2 And (3) ventilating and drying for 5.5h at normal temperature, then precuring for 15min at 95 ℃, cooling and stripping to prepare the flame-retardant toughening modified phenolic resin film.
The flame-retardant toughened modified phenolic resin film prepared in the embodiment has stable property under normal-temperature storage conditions, is a ginger-yellow soft elastic film, has a film thickness of 0.27mm, and has a peel strength of 12N/cm with respect to a smooth stainless steel plate. The limiting oxygen index of the material after the resin film is heated and cured is 31.3 percent, and the maximum deflection is 16mm (the maximum deflection of pure phenolic resin is 8.6 mm).
Example ten
The flame-retardant toughened modified phenolic resin film comprises the following materials in parts by mass:
72 parts of S157 phenolic resin, 28 parts of LZ96 benzoxazine resin, 70 parts of polyvinyl butyral (PVB) toughening agent, 30 parts of reactive phosphorus flame retardant DOPO-HQ,5 parts of synergistic flame retardant tannic acid and 5 parts of HEDP.
A preparation method of a flame-retardant toughening modified phenolic resin film comprises the following specific steps:
1) Weighing 70 parts of polyvinyl butyral (PVB), dissolving in 700 parts of absolute ethyl alcohol, and fully stirring until the solution is uniform and transparent;
2) Weighing 72 parts of S157 phenolic resin and 28 parts of LZ96 benzoxazine resin, adding into the solution obtained in the step 1), and fully stirring until the mixture is uniformly mixed;
3) Sequentially weighing 30 parts of DOPO-HQ,5 parts of tannic acid and 5 parts of HEDP, adding into the solution obtained in the step 2), and fully stirring until the mixture is uniformly mixed to obtain a modified phenolic resin mixed solution;
4) The modified phenolic resin mixed solution is coated on a smooth stainless steel plate to be flat, and the coating surface density is 1.2kg/m 2 And (3) ventilating and drying for 6h at normal temperature, then precuring for 10min at 100 ℃, cooling and stripping to obtain the flame-retardant toughened modified phenolic resin film.
The flame-retardant toughened modified phenolic resin film prepared in the embodiment has stable property under normal-temperature storage conditions, is a ginger-yellow soft elastic film, has a film thickness of 0.30mm, and has a peel strength of 15.9N/cm with respect to a smooth stainless steel plate. The limiting oxygen index of the material after the resin film is heated and cured is 34.3 percent, and the maximum deflection is 17.4mm (the maximum deflection of pure phenolic resin is 8.6 mm).
Claims (7)
1. The flame-retardant toughened modified phenolic resin film is characterized in that: the material composition at least comprises the following components in parts by mass:
the sum of the phenolic resin and the benzoxazine resin is 100 parts by mass; the phenolic resin is liquid alkali-catalyzed phenolic resin; the benzoxazine resin is liquid benzoxazine resin.
2. The flame-retardant toughened modified phenolic resin film as claimed in claim 1, wherein: the liquid alkali-catalyzed phenolic resin is one of S157 and PF 9601.
3. The flame-retardant toughened modified phenolic resin film as claimed in claim 1, wherein: the liquid benzoxazine resin is bisphenol F type benzoxazine resin LZ96 or LZ 24.
4. The flame-retardant toughened modified phenolic resin film as claimed in claim 1, wherein: the reactive phosphorus flame retardant is one or a mixed system of DOPO-HQ and DOPO-DDP.
5. The flame-retardant toughened modified phenolic resin film as claimed in claim 1, wherein: the synergistic flame retardant is one or a mixed system of tannic acid and HEDP.
6. The preparation method of the flame-retardant toughened modified phenolic resin film as claimed in claim 1, wherein: the method comprises the following specific steps:
1) Weighing various materials according to a formula ratio, dissolving polyvinyl butyral in absolute ethyl alcohol, wherein the mass ratio of the polyvinyl butyral to the absolute ethyl alcohol is 1:8-1, and fully stirring until a mixed solution is uniform and transparent;
2) Adding phenolic resin and benzoxazine resin into the solution obtained in the step 1), and continuously stirring until the phenolic resin and the benzoxazine resin are uniformly mixed;
3) Adding the reactive phosphorus flame retardant and the synergistic flame retardant into the solution obtained in the step 2), and continuously stirring until the mixture is uniformly mixed to obtain a modified phenolic resin mixed solution;
4) And (3) coating the modified phenolic resin mixed solution on a smooth stainless steel plate flatly, ventilating and drying at normal temperature for not less than 4h, then precuring at 80-100 ℃ for 10-30 min, cooling and stripping to obtain the flame-retardant toughened modified phenolic resin film.
7. The preparation method of the flame-retardant toughened modified phenolic resin film as claimed in claim 6, wherein: in the step 4), the coating surface density of the modified phenolic resin mixed solution is not less than 1kg/m 2 。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117165028A (en) * | 2023-09-06 | 2023-12-05 | 江苏耀鸿电子有限公司 | Halogen-free heat-resistant phenolic resin copper-clad plate and forming process thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117165028A (en) * | 2023-09-06 | 2023-12-05 | 江苏耀鸿电子有限公司 | Halogen-free heat-resistant phenolic resin copper-clad plate and forming process thereof |
| CN117165028B (en) * | 2023-09-06 | 2024-03-22 | 江苏耀鸿电子有限公司 | Halogen-free heat-resistant phenolic resin copper-clad plate and forming process thereof |
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