CN115260681A - Impact-resistant flame-retardant decorative film and preparation method thereof - Google Patents
Impact-resistant flame-retardant decorative film and preparation method thereof Download PDFInfo
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- CN115260681A CN115260681A CN202211197821.XA CN202211197821A CN115260681A CN 115260681 A CN115260681 A CN 115260681A CN 202211197821 A CN202211197821 A CN 202211197821A CN 115260681 A CN115260681 A CN 115260681A
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- 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 37
- 239000003063 flame retardant Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000945 filler Substances 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000003085 diluting agent Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000004014 plasticizer Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 31
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 12
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000005273 aeration Methods 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- MLSZIADXWDYFKM-UHFFFAOYSA-N 1-dichlorophosphorylethene Chemical compound ClP(Cl)(=O)C=C MLSZIADXWDYFKM-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 238000003490 calendering Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 9
- 229910002804 graphite Inorganic materials 0.000 abstract description 6
- 239000010439 graphite Substances 0.000 abstract description 6
- 238000002679 ablation Methods 0.000 abstract description 5
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 230000035515 penetration Effects 0.000 abstract 1
- 239000004800 polyvinyl chloride Substances 0.000 description 44
- 229920000915 polyvinyl chloride Polymers 0.000 description 44
- 239000000463 material Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000006467 substitution reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical group C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 4
- BJAJDJDODCWPNS-UHFFFAOYSA-N dotp Chemical group O=C1N2CCOC2=NC2=C1SC=C2 BJAJDJDODCWPNS-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 125000005499 phosphonyl group Chemical group 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005276 aerator Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical group ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/22—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an impact-resistant flame-retardant decorative film and a preparation method thereof, belonging to the technical field of high polymer materials. The decorative film comprises the following components in parts by weight: 80-100 parts of ammoniated PVC resin, 5-8 parts of modified filler, 0.1-0.15 part of catalyst, 7-10 parts of diluent, 22-28 parts of plasticizer, 0.6-1 part of antioxidant and 2.5-4 parts of flatting agent; the modified filler contains phosphide, organic silicon and inorganic graphite, when ablation occurs, the modified filler and a PVC matrix form an ablation-resistant layer to hinder the penetration of combustion, the flame-retardant PVC film has an excellent flame-retardant effect, no obvious molten drop appears in an ablation test, the modified filler and the PVC matrix are in a covalent bond form to obviously reinforce PVC, and the tensile property and the impact resistance of the film are obviously superior to those of the existing PVC-based decorative film.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an impact-resistant flame-retardant decorative film and a preparation method thereof.
Background
The decorative film is a novel decorative material prepared by using high-molecular polymer as a raw material and adding various auxiliaries, calendering and compounding, can be compounded with base materials such as wood, plastic plates, aluminum plates, iron plates and the like to prepare a multipurpose decorative material, is widely applied to surface decoration of household appliances, sound equipment, interior decoration of airplanes, ships and trains, and is a mainstream material of the decorative film by taking comprehensive properties such as wear resistance, high toughness, high processability and the like of PVC (polyvinyl chloride).
With the improvement of safety consciousness of people, the fireproof requirement of building materials is gradually improved, and the decorative film is used as a surface decorative material, is directly contacted with flame in the case of fire and needs to have good flame retardant effect; various flame-retardant film products are derived in the prior art, and organic or inorganic flame retardants are usually added into PVC resin to improve the overall flame retardance of PVC, for example, a Chinese patent with the application number of 201910497139.4 discloses an impact-resistant high-efficiency flame-retardant decorative film and a preparation method thereof.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the invention aims to provide an impact-resistant flame-retardant decorative film and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
an impact-resistant flame-retardant decorative film comprises the following components in parts by weight: 80-100 parts of ammoniated PVC resin, 5-8 parts of modified filler, 0.1-0.15 part of catalyst, 7-10 parts of diluent, 22-28 parts of plasticizer, 0.6-1 part of antioxidant and 2.5-4 parts of leveling agent.
The modified filler is prepared by the following method:
step A1: uniformly mixing graphite powder and potassium permanganate, adding water for ultrasonic dispersion to completely dissolve potassium permanganate, uniformly dispersing graphite powder in water to form turbid liquid, then adding nitric acid to adjust the pH value to 3-4, heating to 90-95 ℃ for reflux, dropwise adding hydrogen peroxide in a stirring state, stirring for reflux reaction for 2-3 hours, centrifugally washing precipitates after the reaction is finished until the pH value of a washing solution is not lower than 6, then drying the precipitates, generating a large number of oxygen-containing groups on the surface of the graphite powder under an acidic oxidation condition, enlarging graphite sheets, and showing a porous expanded state to prepare expanded graphite powder;
further, the graphite powder is selected from flaky graphite with the fineness of not less than 500 meshes.
Further, the use amount ratio of the graphite powder, the potassium permanganate and the hydrogen peroxide is 100g:3.8-4.5g:0.2-0.3g.
Step A2: mixing gamma-aminopropyltriethoxysilane and DMF, adding the mixture into a reaction kettle provided with an aerator pipe, heating the mixture to 62-75 ℃, introducing ammonia gas into the reaction kettle through the aerator pipe, slowly adding vinyl phosphonic chloride into the reaction kettle until no hydrogen chloride is discharged, and performing substitution reaction on high-activity amino groups in the gamma-aminopropyltriethoxysilane and phosphoryl chloride groups to prepare a modified solution;
further, the dosage ratio of the gamma-aminopropyltriethoxysilane, the vinyl phosphonic chloride and the DMF is 2.05-2.1mol:1mol:180-220mL.
Further, the aeration ratio of ammonia gas was 0.15 to 0.2vvm, and the ammonia gas was used after drying.
Step A3: adding the modified liquid, the expanded graphite powder and deionized water into a reaction kettle for ultrasonic dispersion, adding sodium hydroxide to adjust the pH value to 8-9, heating to 40-48 ℃, stirring for reaction for 3-5h, hydrolyzing siloxane at the end of a substitution reaction product in the modified liquid into silanol, then condensing with oxygen-containing groups on the surface of the expanded graphite powder, grafting the substitution product to the surface of the expanded graphite powder, centrifuging after the reaction is finished, washing precipitate with water, drying the precipitate, and preparing the modified filler.
Further, the dosage ratio of the modified liquid, the expanded graphite powder and the deionized water is 100mL:6-8g:10-15mL.
The preparation method of the ammoniated PVC resin comprises the following steps: adding PVC master batch and cyclohexanone into an internal mixing kettle, heating to 110-120 ℃ under the protection of nitrogen, internally mixing until the PVC master batch is completely dissolved, introducing flowing nitrogen to reduce the temperature of a mixture in the internal mixing kettle to 85 ℃, adding p-aminophenol, keeping the temperature, stirring and reacting for 60-80min, substituting sulfydryl in the p-aminophenol with-Cl groups on a PVC side chain, and introducing amino to the PVC side chain to prepare the ammoniated PVC resin.
Further, the dosage ratio of the PVC master batch to the p-aminophenol to the cyclohexanone is 100g:1.1-1.5g:70-80mL.
Further, the catalyst is selected from aluminum trichloride.
Further, the diluent is selected from diluent OS-20.
Further, the plasticizer is selected from DOTP.
Further, the antioxidant is selected from antioxidant CA.
Further, the leveling agent is selected from leveling agents JF-804.
The preparation method of the impact-resistant flame-retardant decorative film specifically comprises the following steps:
step S1: uniformly mixing the modified filler, a catalyst, a diluent and an antioxidant, adding the mixture and the ammoniated PVC resin into an internal mixing kettle, heating to 95 ℃, controlling the stirring speed to be 360rpm, carrying out stirring reaction for 40-60min, carrying out addition reaction on double bonds on the modified filler and the ammoniated PVC resin, and connecting the modified filler and the ammoniated PVC resin in a covalent bond manner to prepare raw rubber;
step S2: adding plasticizer and leveling agent into raw rubber, mixing, and stirring at 110 deg.C for 20min to obtain cooked rubber;
and step S3: and (3) placing the aged rubber in a calender for extrusion to form a film after vacuum defoaming treatment, and then sequentially cooling, sizing and hot-press forming to prepare the impact-resistant flame-retardant decorative film.
Has the advantages that:
1. the invention adds a modified filler in a PVC matrix, and carries out substitution reaction on gamma-aminopropyltriethoxysilane and vinyl phosphonic chloride in an anhydrous environment to obtain a substitution product, namely a phosphorus-silicon compound, wherein the end part of a molecule of the phosphorus-silicon compound contains siloxane groups, the molecule of the phosphorus-silicon compound contains double bonds in the Shanghai, then the siloxane at the end part is hydrolyzed into silanol under an alkaline water-containing condition, then the silanol is condensed with oxygen-containing groups on the surface of expanded graphite powder, and the substitution product is grafted to the surface of the expanded graphite powder.
2. According to the invention, para-aminophenol is adopted to modify PVC, amino is introduced to a PVC side chain through a substitution reaction of sulfydryl in the para-aminophenol and a-Cl group on the PVC side chain to prepare ammoniated PVC resin, then aluminum trichloride is used as a catalyst, double bonds in modified filler and amino in the ammoniated PVC resin are added, and the modified filler and the ammoniated PVC resin are connected in a covalent bond mode.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment of the preparation of the impact-resistant flame-retardant decorative film comprises the following specific implementation processes:
1) Preparation of modified Filler
a1, taking graphite powder, which is provided by a certain graphite company Limited in Henan, wherein the graphite powder is flaky graphite and has the fineness of 500 meshes, the following embodiments are selected from the same batch of raw materials, potassium permanganate is taken again, the potassium permanganate and the graphite powder are added into an airflow powder mixer to be uniformly mixed, water is added according to the solid-to-liquid ratio of 1: 3.8g:0.2g;
a2, installing an aeration pipe at the bottom of a reaction kettle, installing an exhaust pipe at the top, communicating the exhaust pipe with a hydrogen chloride detector, adding gamma-aminopropyltriethoxysilane (provided by Jeccard chemical Co., ltd., hangzhou, the same raw materials are adopted in the following examples) and DMF (N, N-dimethylformamide) into the reaction kettle, uniformly mixing, heating to 62 ℃, introducing ammonia gas from the aeration pipe at an air introduction ratio of 0.15vvm, drying the ammonia gas by using a drying pipe before introduction, slowly adding vinyl phosphonyl chloride (an analytical pure reagent provided by Shanghai reagent Co., ltd., the same raw materials are adopted in the following examples), keeping the temperature for reaction until no obvious hydrogen chloride is discharged, and preparing a modified solution, wherein in the above reactions, the dosage ratio of the gamma-aminopropyltriethoxysilane, the vinyl phosphonyl chloride and the DMF is 2.05mol:1mol:180mL;
a3, adding the modified liquid, the expanded graphite powder and deionized water into a reaction kettle, performing ultrasonic dispersion for 15min at 33kHz, adding sodium hydroxide to adjust the pH value to 8, heating to 48 ℃, stirring for reaction for 5h, centrifuging after the reaction is finished, taking precipitate, washing with water, centrifuging, taking precipitate, placing the precipitate in a drying box, and drying for 2h at 60 ℃ to obtain the modified filler, wherein in the above reaction, the dosage ratio of the modified liquid, the expanded graphite powder and the deionized water is 100mL:6g:10mL.
2) Preparation of ammoniated PVC resin
Adding PVC master batch (commercially available raw materials, provided by Shanghai Yiwang New materials Co., ltd., average molecular weight is about 20000, and the same batch of raw materials are adopted in the following examples) and cyclohexanone into an internal mixing kettle, introducing nitrogen to discharge internal air, keeping in a nitrogen protection condition, heating to 110 ℃, carrying out internal mixing until the PVC master batch is completely dissolved, introducing flowing normal-temperature nitrogen to reduce the temperature until the temperature of a mixed material in the internal mixing kettle is reduced to 85 ℃, adding p-aminophenol, carrying out heat preservation stirring reaction for 80min, and preparing ammoniated PVC resin, wherein in the above reaction, the dosage ratio of the PVC master batch to the p-aminophenol to the cyclohexanone is 100g:1.1g:70mL.
3) Preparation of impact-resistant flame-retardant decorative film
s1, preparing materials: the following raw materials were taken in parts by weight (in this example, the amount was controlled to 1 part =1g to meet the experimental requirements, as in the following examples):
the aminated PVC resin prepared in this example: 100 parts of (A);
modified filler prepared in this example: 5 parts of a mixture;
catalyst: 0.1 part of aluminum trichloride;
diluent agent: diluent OS-20,7 parts;
plasticizer: DOTP (dioctyl terephthalate), 28 parts;
antioxidant: 0.6 part of antioxidant CA;
leveling agent: 2.5 parts of a leveling agent JF-804;
s2, preparing raw rubber:
adding the modified filler, the catalyst, the diluent and the antioxidant into a stirrer, stirring and mixing at 600rpm for 20min, adding the mixture and the ammoniated PVC resin into an internal mixing kettle, heating to 95 ℃, controlling the stirring speed to be 360rpm, and stirring and reacting for 40min to prepare raw rubber;
s3, preparing the boiled glue
Adding plasticizer and leveling agent into the raw rubber, mixing, and stirring at 110 deg.C for 20min to obtain cooked rubber;
s4, rolling to form a film
And (3) defoaming the cured adhesive under 5mmHg in vacuum for 5min, discharging to a calender, controlling the extrusion pressure to be 0.8MPa, extruding the cured adhesive into a film, naturally cooling and shaping, and then placing the film in a hot press for roll forming to prepare the impact-resistant flame-retardant decorative film.
Example 2
The embodiment of the preparation of the impact-resistant flame-retardant decorative film comprises the following specific implementation processes:
1) Preparation of modified Filler
a1, fetching stone powdered ink and potassium permanganate, adding the two into an airflow powder mixer, uniformly mixing, adding water according to a solid-liquid ratio of 1: 4.5g:0.3g;
a2, taking a reaction kettle, installing an aeration pipe at the bottom of the reaction kettle, installing an exhaust pipe at the top of the reaction kettle, communicating the exhaust pipe with a hydrogen chloride detector, adding gamma-aminopropyltriethoxysilane and DMF into the reaction kettle, uniformly mixing, heating to 75 ℃, introducing ammonia gas from the aeration pipe at an air introduction ratio of 0.2vvm, drying the ammonia gas by using a drying pipe before introducing the ammonia gas, slowly adding vinyl phosphonyl chloride into the reaction kettle, carrying out heat preservation reaction until no obvious hydrogen chloride is discharged, and preparing a modified solution, wherein in the above reactions, the dosage ratio of the gamma-aminopropyltriethoxysilane, the vinyl phosphonyl chloride and the DMF is 2.1mol:1mol:220mL;
a3, adding the modified liquid, the expanded graphite powder and deionized water into a reaction kettle, performing ultrasonic dispersion for 15min at 33kHz, adding sodium hydroxide to adjust the pH value to 9, heating to 40 ℃, stirring for reaction for 3h, centrifuging after the reaction is finished, taking precipitate, washing with water, centrifuging, taking precipitate, placing the precipitate in a drying box, and drying for 2h at 60 ℃ to obtain the modified filler, wherein in the above reaction, the dosage ratio of the modified liquid, the expanded graphite powder and the deionized water is 100mL:8g:15mL.
2) Preparation of ammoniated PVC resin
Adding PVC master batch and cyclohexanone into an internal mixing kettle, introducing nitrogen to discharge internal air, keeping under the nitrogen protection condition, heating to 110-120 ℃, mixing until the PVC master batch is completely dissolved, introducing flowing normal-temperature nitrogen to cool until the temperature of a mixture in the internal mixing kettle is reduced to 85 ℃, adding p-aminophenol, keeping the temperature and stirring for reaction for 60min to prepare ammoniated PVC resin, wherein the dosage ratio of the PVC master batch to the p-aminophenol to the cyclohexanone is 100g:1.5g:80mL.
3) Preparation of impact-resistant flame-retardant decorative film
s1, preparing materials: the raw materials are as follows according to the parts by weight:
the aminated PVC resin prepared in this example: 80 parts of a binder;
modified filler prepared in this example: 8 parts;
catalyst: 0.15 part of aluminum trichloride;
diluent agent: 10 parts of diluent OS-20;
plasticizer: DOTP,22 parts;
antioxidant: 1 part of antioxidant CA;
leveling agent: 4 parts of a leveling agent JF-804;
s2, preparing raw rubber:
adding the modified filler, the catalyst, the diluent and the antioxidant into a stirrer, stirring and mixing at 600rpm for 20min, adding the mixture and the ammoniated PVC resin into an internal mixing kettle, heating to 95 ℃, controlling the stirring speed to be 360rpm, and stirring and reacting for 60min to prepare raw rubber;
s3, preparing the boiled glue
Adding plasticizer and leveling agent into the raw rubber, mixing, and stirring at 110 deg.C for 20min to obtain cooked rubber;
s4, calendering to form a film
And (3) defoaming the cured adhesive under 5mmHg in vacuum for 5min, discharging the cured adhesive to a calender, controlling the extrusion pressure to be 0.8MPa, extruding the cured adhesive into a film, naturally cooling and shaping the film, and then placing the film in a hot press for roll forming to prepare the impact-resistant flame-retardant decorative film.
Example 3
The embodiment of the preparation of the impact-resistant flame-retardant decorative film comprises the following specific implementation processes:
1) Preparation of modified Filler
a1, fetching graphite powder and potassium permanganate, adding the graphite powder and the potassium permanganate into an airflow powder mixer, uniformly mixing, adding water according to a solid-to-liquid ratio of 1: 4.2g:0.25g;
a2, mounting an aeration pipe at the bottom of a reaction kettle, mounting an exhaust pipe at the top, communicating the exhaust pipe with a hydrogen chloride detector, adding gamma-aminopropyltriethoxysilane and DMF into the reaction kettle, uniformly mixing, heating to 70 ℃, introducing ammonia gas from the aeration pipe at an air introduction ratio of 0.18vvm, drying the ammonia gas by using a drying pipe before introducing the ammonia gas, slowly adding vinylphosphonic chloride into the reaction kettle, performing heat preservation reaction until no obvious hydrogen chloride is discharged, and preparing a modified solution, wherein in the above reaction, the dosage ratio of the gamma-aminopropyltriethoxysilane to the vinylphosphonic chloride to the DMF is 2.08mol:1mol:200mL;
a3, adding the modified liquid, the expanded graphite powder and deionized water into a reaction kettle, performing ultrasonic dispersion for 15min at 33kHz, adding sodium hydroxide to adjust the pH value to 9, heating to 45 ℃, stirring for reaction for 4h, centrifuging after the reaction is finished, taking the precipitate, washing with water, centrifuging, taking the precipitate, placing the precipitate in a drying box, and drying for 2h at 60 ℃ to prepare the modified filler, wherein in the above reaction, the dosage ratio of the modified liquid, the expanded graphite powder and the deionized water is 100mL:7g:12mL.
2) Preparation of ammoniated PVC resin
Adding PVC master batches and cyclohexanone into an internal mixing kettle, introducing nitrogen to discharge internal air, keeping under the nitrogen protection condition, heating to 120 ℃, mixing until the PVC master batches are completely dissolved, introducing flowing normal-temperature nitrogen to cool until the temperature of a mixture in the internal mixing kettle is reduced to 85 ℃, adding p-aminophenol, keeping the temperature and stirring for reaction for 70min to prepare ammoniated PVC resin, wherein the dosage ratio of the PVC master batches to the p-aminophenol to the cyclohexanone is 100g:1.3g:75mL.
3) Preparation of impact-resistant flame-retardant decorative film
s1, preparing materials: the raw materials are taken according to the parts by weight:
the aminated PVC resin prepared in this example: 90 parts of;
modified filler prepared in this example: 7 parts;
catalyst: 0.13 part of aluminum trichloride;
diluent agent: diluent OS-20,8 parts;
plasticizer: DOTP,26 parts;
antioxidant: 0.8 part of antioxidant CA;
leveling agent: 3.4 parts of flatting agent JF-804;
s2, preparing raw rubber:
adding the modified filler, the catalyst, the diluent and the antioxidant into a stirrer, stirring and mixing at 600rpm for 20min, adding the mixture and the ammoniated PVC resin into an internal mixing kettle, heating to 95 ℃, controlling the stirring speed to be 360rpm, and stirring and reacting for 50min to prepare raw rubber;
s3, preparing the boiled glue
Adding plasticizer and leveling agent into raw rubber, mixing, and stirring at 110 deg.C for 20min to obtain cooked rubber;
s4, calendering to form a film
And (3) defoaming the cured adhesive under 5mmHg in vacuum for 5min, discharging the cured adhesive to a calender, controlling the extrusion pressure to be 0.8MPa, extruding the cured adhesive into a film, naturally cooling and shaping the film, and then placing the film in a hot press for roll forming to prepare the impact-resistant flame-retardant decorative film.
Comparative example 1
The method for preparing the impact-resistant flame-retardant decorative film in the comparative example is the same as that for preparing the impact-resistant flame-retardant decorative film in the example 3, the modified filler is replaced by the composite reinforcer with the same weight fraction, and the composite reinforcer comprises the following components: the expanded graphite powder, nanosilica and liquid flame retardant FR2003, prepared according to example 3, were mixed in a weight ratio of 1.8.
Comparative example 2
The comparative example is a decorative film prepared by the method provided by the Chinese patent application number 201910497139.4.
Samples of the decorative films prepared in the examples 1 to 3 and the comparative examples 1 to 2 are taken and tested for mechanical property and flame retardant property, and the specific test method is as follows:
performing tensile property test according to GB/T1041.1-2018 standard, and testing by using a KEN series electronic universal tester at room temperature at a test speed of 10mm/min;
performing impact performance test according to GB/T21189-2007 standard, adopting JJ-20 impact resistance instrument test, adopting A type gap;
performing flame retardant performance test according to GB/T2406.2-2009 standard, and testing by adopting an F101 limiting oxygen index tester;
performing combustion performance test according to GB/T2408-2008 standard, and testing by using a UL94 horizontal vertical combustion tester with the model of CZF-5;
specific test data are shown in table 1:
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Tensile strength/MPa | 37.21 | 34.87 | 37.16 | 24.71 | 26.15 |
| Impact strength/KJ · m -2 | 50.62 | 50.03 | 52.46 | 39.71 | 34.58 |
| Limiting oxygen index/% | 27.9 | 31.1 | 30.6 | 21.4 | 23.7 |
| UL-94 | V-0 | V-0 | V-0 | V-0 | V-1 |
| Droplet condition | Without molten drop | Without molten drop | Without molten drop | Micro molten drop | Micro molten drop |
As can be seen from the data in Table 1, the decorative films prepared according to the present invention have tensile strengths of 34.87 to 37.21MPa and impact strengths of 50.03 to 52.46KJ/m 2 The mechanical property is superior to that of the existing PVC-based decorative film, and the PVC is efficiently strengthened due to the covalent bond between the modified filler and the PVC matrix; the limited oxygen index is 27.9-31.1%, no obvious molten drop exists in a combustion test, the flame retardant grade reaches V-0 grade, and due to the fact that the modified filler contains phosphide, organic silicon and inorganic graphite, when ablation occurs, the modified filler and a PVC matrix form an ablation-resistant layer to hinder the combustion from going deep.
In the description of the specification, reference to the description of "one embodiment," "an example," "a specific example" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (8)
1. The impact-resistant flame-retardant decorative film is characterized by comprising the following components in parts by weight: 80-100 parts of ammoniated PVC resin, 5-8 parts of modified filler, 0.1-0.15 part of catalyst, 7-10 parts of diluent, 22-28 parts of plasticizer, 0.6-1 part of antioxidant and 2.5-4 parts of flatting agent;
the modified filler is prepared by the following method:
step A1: adding water into graphite powder and potassium permanganate, performing ultrasonic dispersion, adjusting the pH value to 3-4 with nitric acid, heating to 90-95 ℃, refluxing, dropwise adding hydrogen peroxide while stirring, performing reflux reaction for 2-3h, centrifuging after the reaction is finished, taking precipitate, washing, and drying to obtain expanded graphite powder;
step A2: mixing gamma-aminopropyltriethoxysilane with DMF, heating to 62-75 deg.C, introducing ammonia gas while adding vinylphosphonyl chloride until no hydrogen chloride is discharged to obtain modified solution;
step A3: and (3) taking the modified liquid, the expanded graphite powder and deionized water for ultrasonic dispersion, adjusting the pH value to 8-9 by using sodium hydroxide, heating to 40-48 ℃, stirring for reaction for 3-5 hours, centrifuging after the reaction is finished, taking the precipitate, washing and drying to prepare the modified filler.
2. The impact-resistant flame-retardant decorative film according to claim 1, wherein the ratio of the graphite powder to the potassium permanganate to the hydrogen peroxide is 100g:3.8-4.5g:0.2-0.3g.
3. The impact-resistant flame-retardant decorative film according to claim 2, wherein the amount ratio of gamma-aminopropyltriethoxysilane, vinylphosphonic chloride and DMF is 2.05-2.1mol:1mol:180-220mL, and the aeration ratio of ammonia gas is 0.15-0.2vvm.
4. The impact-resistant flame-retardant decorative film according to claim 3, wherein the amount ratio of the modifying liquid to the expanded graphite powder to the deionized water is 100mL:6-8g:10-15mL.
5. The impact-resistant flame-retardant decorative film according to claim 1, wherein the preparation method of the ammoniated PVC resin comprises the following steps: heating PVC master batch and cyclohexanone to 110-120 ℃ under the protection of nitrogen, banburying until the PVC master batch is completely dissolved, introducing nitrogen, cooling to 85 ℃, adding p-aminophenol, keeping the temperature, stirring and reacting for 60-80min to obtain the ammoniated PVC resin.
6. The impact-resistant flame-retardant decorative film according to claim 5, wherein the PVC masterbatch, the p-aminophenol and the cyclohexanone are used in a ratio of 100g:1.1-1.5g:70-80mL.
7. The impact-resistant flame-retardant decorative film according to claim 5, wherein the catalyst is aluminum trichloride.
8. The method for preparing the impact-resistant flame-retardant decorative film according to claim 1, which is characterized by comprising the following steps:
step S1: mixing the modified filler, the catalyst, the diluent and the antioxidant, heating the mixture with ammoniated PVC resin to 95 ℃, controlling the stirring speed to be 360rpm, and stirring and reacting for 40-60min to prepare raw rubber;
step S2: adding plasticizer and leveling agent into the raw rubber, mixing, and stirring at 110 deg.C for 20min to obtain cooked rubber;
and step S3: and performing vacuum defoaming treatment on the aged rubber, calendering to form a film, and then sequentially cooling, shaping and hot-press forming to prepare the impact-resistant flame-retardant decorative film.
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| CN117534899A (en) * | 2024-01-09 | 2024-02-09 | 河南云瀚实业有限公司 | Cold-resistant halogen-free flame-retardant polyolefin cable material and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116728924A (en) * | 2023-06-14 | 2023-09-12 | 广东瀚泰装饰材料有限公司 | PVC decorative film containing thermal transfer printing gold and silver patterns |
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| CN117534899A (en) * | 2024-01-09 | 2024-02-09 | 河南云瀚实业有限公司 | Cold-resistant halogen-free flame-retardant polyolefin cable material and preparation process thereof |
| CN117534899B (en) * | 2024-01-09 | 2024-03-19 | 河南云瀚实业有限公司 | Cold-resistant halogen-free flame-retardant polyolefin cable material and preparation process thereof |
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Application publication date: 20221101 |