CN112126172A - Reinforced toughened flame-retardant rigid polyvinyl chloride foam material and preparation method thereof - Google Patents
Reinforced toughened flame-retardant rigid polyvinyl chloride foam material and preparation method thereof Download PDFInfo
- Publication number
- CN112126172A CN112126172A CN202010999336.9A CN202010999336A CN112126172A CN 112126172 A CN112126172 A CN 112126172A CN 202010999336 A CN202010999336 A CN 202010999336A CN 112126172 A CN112126172 A CN 112126172A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- parts
- polyvinyl chloride
- foam material
- rigid polyvinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0028—Use of organic additives containing nitrogen
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/10—Rigid foams
-
- 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
- C08J2327/02—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 not modified by chemical after-treatment
- C08J2327/04—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 not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
Abstract
The invention relates to a reinforced and toughened flame-retardant rigid polyvinyl chloride foam material and a preparation method thereof, wherein the reinforced and toughened flame-retardant rigid polyvinyl chloride foam material comprises the following raw materials in parts by weight: 100 parts of PVC resin, 60-80 parts of isocyanate, 20-30 parts of anhydride, 2-6 parts of initiator, 1-3 parts of foaming agent, 2-5 parts of stabilizer and 1-6 parts of flame retardant toughening agent, wherein the flame retardant toughening agent is hydroxyl stannic acid metal salt loaded graphene oxide. Compared with the prior art, the rigid polyvinyl chloride foam material prepared by the invention has excellent flame retardant property and mechanical property and low smoke generation amount during combustion.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a reinforced and toughened flame-retardant rigid polyvinyl chloride foam material and a preparation method thereof.
Background
The rigid polyvinyl chloride (RPVC) foam material has the advantages of good flame retardance, good chemical resistance and corrosion resistance, good heat-insulating property, low cost and the like, and is widely applied to the fields of heat insulation, sound insulation, shock resistance and the like. Rigid polyvinyl chloride foams are generally less flexible due to the rigidity of the molecular chains. Therefore, the rigid polyvinyl chloride foam material needs to be subjected to reinforcing, toughening and modifying in many application occasions. The toughening modifier commonly used for RPVC foams mainly comprises micromolecular toughening modifiers (such as glycidyl methacrylate and phthalate) and macromolecular toughening agents (such as polyurethane, nitrile rubber and the like). The effect of Glycidyl Methacrylate (GMA) on crosslinked rigid PVC foams is reported in the literature [ Duchen et al, plastics industry, 2020, 48 (5): 107-111 DEG, the glycidyl methacrylate has better reinforcing and toughening effects on the cross-linked rigid PVC foam. In addition, the modification by crosslinking is one of the methods for modifying rigid polyvinyl chloride foam. The method is that appropriate amount of unsaturated compounds (such as isocyanate, anhydride, etc.) are added into the PVC foaming formula as cross-linking agent, and cross-linked network is generated in the foaming process, thereby improving the mechanical strength and heat resistance of the rigid polyvinyl chloride foam [ an improved cross-linked polyvinyl chloride structural foam and its preparation method, Chinese patent No. CN201810765269.7 ].
However, the toughening modifiers of the conventional rigid polyvinyl chloride foams are flammable, and the addition of the toughening modifiers can generally reduce the flame retardant property of the rigid polyvinyl chloride foams; the flame retardant properties of the RPVC foam are not improved by crosslinking modification.
Disclosure of Invention
The invention aims to solve the problem of poor flame retardance of a rigid polyvinyl chloride foam material during reinforcing and toughening, and provides a reinforcing and toughening flame-retardant rigid polyvinyl chloride foam material and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a reinforced and toughened flame-retardant rigid polyvinyl chloride foam material comprises the following raw materials in parts by weight: 100 parts of PVC resin, 60-80 parts of isocyanate, 20-30 parts of anhydride, 2-6 parts of initiator, 1-3 parts of foaming agent, 2-5 parts of stabilizer and 1-6 parts of flame retardant toughening agent, wherein the flame retardant toughening agent is hydroxyl stannic acid metal salt loaded graphene oxide.
Preferably, the PVC resin is PVC paste resin, and the K value is between 70 and 80.
Preferably, the isocyanate is selected from any one of toluene diisocyanate, diphenylmethane diisocyanate or polyphenyl polymethylene polyisocyanate, and polyphenyl polymethylene polyisocyanate is further preferred.
Preferably, the acid anhydride is selected from any one of phthalic anhydride, tetrahydrophthalic anhydride or methylhexahydrophthalic anhydride, and more preferably methylhexahydrophthalic anhydride.
Preferably, the initiator is azobisisobutyronitrile.
Preferably, the blowing agent is azodicarbonamide.
Preferably, the stabilizer is selected from one or more of barium stearate, zinc stearate or calcium stearate.
Preferably, the flame retardant toughening agent is selected from one or more of copper hydroxystannate-loaded graphene oxide, cobalt hydroxystannate-loaded graphene oxide, zinc hydroxystannate-loaded graphene oxide, strontium hydroxystannate-loaded graphene oxide or barium hydroxystannate-loaded graphene oxide.
Preferably, the hydroxyl stannic acid metal salt-loaded graphene oxide flame retardant is prepared by the following method:
(1) graphene oxide was synthesized by a modified Hummers method: mixing graphite with NaNO3Adding H in ice water bath2SO4After low-temperature intercalation oxidation, potassium permanganate is added, then stirring is carried out, and H is added2SO4The solution is reacted and then H is added2O2Carrying out reaction; adding water to continue reacting, then, centrifugally washing the obtained graphene oxide by using HCl and water until sulfate ions in the graphene oxide are cleaned, drying, and then, dispersing the graphene oxide in a deionized water solution to obtain a graphene oxide aqueous solution;
(2) carrying out ultrasonic treatment on a graphene oxide aqueous solution, adding water into metal salt (chloride, sulfate or nitrate), fully stirring and dissolving, and adding the obtained solution and the graphene oxide aqueous solution into a reaction container for reaction;
(3) dissolving stannate trihydrate (such as sodium stannate trihydrate) in water with stirring, wherein the molar ratio of the stannate trihydrate to the metal salt is 1: 1, the ratio of the addition amount of water to the use amount of stannate trihydrate is 20-50ml/g), adding an aqueous solution of stannate trihydrate into a reaction container, reacting at room temperature, filtering, washing and drying a product to obtain the hydroxyl stannate metal salt loaded graphene oxide.
The preparation method of the reinforced toughened flame-retardant rigid polyvinyl chloride foam material specifically comprises the following steps: weighing polyvinyl chloride resin, isocyanate, anhydride, an initiator, a foaming agent, a stabilizer and a flame retardant toughening agent according to a ratio, stirring and mixing uniformly, adding into a mold, crosslinking and curing for 0.5-1h under the conditions that the temperature of the mold is 170-.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the hydroxyl stannic acid metal salt loaded graphene oxide is added into the rigid polyvinyl chloride foam as a flame retardant toughening agent, and the dosage of the hydroxyl stannic acid metal salt loaded graphene oxide is controlled, so that the prepared rigid polyvinyl chloride foam material not only has excellent flame retardant property, but also has a greatly reduced smoke generation amount during combustion; in addition, the hard polyvinyl chloride foam material added with the hydroxyl stannic acid metal salt loaded graphene oxide has good mechanical properties.
The graphene oxide has stronger van der Waals force between the sheet layers and is easy to agglomerate in the polymer, the hydroxyl stannic acid metal salt is loaded on the surface of the graphene oxide sheet layer to block the agglomeration of the graphene oxide, so that the graphene oxide can be uniformly dispersed in the rigid polyvinyl chloride foam material, and meanwhile, the hydroxyl stannic acid metal salt also has better flame retardant and smoke suppression effects, so that the graphene oxide modified rigid polyvinyl chloride foam material loaded with the hydroxyl stannic acid metal salt not only has excellent flame retardant property and mechanical property, but also has low smoke generation amount during combustion.
Drawings
FIG. 1 is a transmission electron microscope image of cobalt hydroxystannate-loaded graphene oxide;
FIG. 2 is a transmission electron microscope image of zinc hydroxystannate loaded graphene oxide;
fig. 3 is a transmission electron microscope image of copper hydroxystannate-loaded graphene oxide.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
The preparation method of the hydroxyl copper stannate loaded graphene oxide comprises the following steps:
synthesizing graphene oxide by an improved Hummers method, namely 2g of graphite and 2g of NaNO3Adding into a three-necked flask, and slowly adding 80ml H under ice-water bath2SO4After low-temperature intercalation oxidation for 2H, slowly adding 10g of potassium permanganate, stirring for 2H at 35 ℃, and slowly dropwise adding 5% of H2SO4200ml of the solution (red) are added and reacted for 2H at 60 ℃, and then a certain amount of H is added2O2Reacting at 90 ℃ for 1h, finally adding 1L of distilled water, continuing to react for 1h until the system is golden yellow, then centrifugally washing the obtained graphene oxide by using 5% HCl and distilled water until sulfate ions in the graphene oxide are washed, drying, and then dispersing the graphene oxide in a deionized water solution to obtain a graphene oxide solution (7 mg/ml); carrying out ultrasonic treatment on 170ml of graphene oxide aqueous solution for 1h, adding the solution into a reaction vessel with stirring, reacting for 1h, stirring and dissolving 2.5g of copper sulfate pentahydrate in 100ml of deionized water, adding the solution into the reaction vessel, stirring and dissolving 10.67g of sodium stannate trihydrate in 100ml of deionized water, adding the solution into the reaction vessel, reacting for 24h under stirring, filtering, washing and drying a product to obtain the copper hydroxystannate-loaded graphene oxide, wherein fig. 3 is a transmission electron microscope image of the copper hydroxystannate-loaded graphene oxide.
The preparation method of the reinforced toughened flame-retardant rigid polyvinyl chloride foam material comprises the following specific steps: 100 parts of PVC resin powder, 70 parts of polyphenyl polymethylene polyisocyanate, 25 parts of methyl hexahydrophthalic anhydride, 3 parts of azodiisobutyronitrile, 1 part of azodicarbonamide, 2.5 parts of barium-zinc stearate composite stabilizer and 1 part of prepared copper hydroxystannate-loaded graphene oxide are weighed. After uniformly stirring and mixing, adding the mixture into a mold, carrying out crosslinking and curing for 0.5h at 170 ℃ and 15MPa to obtain pre-foamed foam, cooling and demolding, continuously foaming the pre-foamed foam for 0.5h under 100 ℃ of water vapor, and drying to obtain the copper hydroxystannate-loaded graphene oxide reinforced and toughened rigid polyvinyl chloride foam material, wherein the performance test results are shown in Table 1.
Example 2
The preparation of copper hydroxystannate-loaded graphene oxide in this embodiment is the same as that in embodiment 1, and is different from that in embodiment 1 in that: 100 parts of PVC resin powder, 60 parts of polyphenyl polymethylene polyisocyanate, 30 parts of methyl hexahydrophthalic anhydride, 4 parts of azodiisobutyronitrile, 2 parts of azodicarbonamide, 3 parts of barium-zinc stearate composite stabilizer and 2 parts of prepared copper hydroxystannate-loaded graphene oxide are weighed. After uniformly stirring and mixing, adding the mixture into a mold, carrying out crosslinking and curing for 1.0h at 175 ℃ and 15MPa to obtain pre-foamed foam, cooling and demolding, continuously foaming the pre-foamed foam for 0.5h under 100 ℃ of water vapor, and drying to obtain the copper hydroxystannate-loaded graphene oxide reinforced and toughened rigid polyvinyl chloride foam material, wherein the performance test results are shown in Table 1.
Example 3
The preparation of copper hydroxystannate-loaded graphene oxide in this embodiment is the same as that in embodiment 1, and is different from that in embodiment 1 in that: 100 parts of PVC resin powder, 80 parts of polyphenyl polymethylene polyisocyanate, 20 parts of methyl hexahydrophthalic anhydride, 2.5 parts of azodiisobutyronitrile, 2 parts of azodicarbonamide, 2 parts of barium-zinc stearate composite stabilizer and 4 parts of prepared copper hydroxystannate-loaded graphene oxide are weighed. Stirring and mixing uniformly, adding the mixture into a mold, carrying out crosslinking and curing for 0.5h at 180 ℃ and 15MPa to obtain pre-foamed foam, cooling and demolding, continuously foaming the pre-foamed foam for 1.0h under 100 ℃ of water vapor, and drying to obtain the copper hydroxystannate-loaded graphene oxide reinforced and toughened rigid polyvinyl chloride foam material, wherein the performance test results are shown in Table 1.
Example 4
The preparation of copper hydroxystannate-loaded graphene oxide in this embodiment is the same as that in embodiment 1, and is different from that in embodiment 1 in that: 100 parts of PVC resin powder, 65 parts of polyphenyl polymethylene polyisocyanate, 25 parts of methyl hexahydrophthalic anhydride, 3 parts of azodiisobutyronitrile, 2 parts of azodicarbonamide, 2 parts of barium-zinc stearate composite stabilizer and 6 parts of prepared copper hydroxystannate-loaded graphene oxide are weighed. After uniformly stirring and mixing, adding the mixture into a mold, carrying out crosslinking and curing for 0.5h at 170 ℃ and 15MPa to obtain pre-foamed foam, cooling and demolding, continuously foaming the pre-foamed foam for 2.0h under 100 ℃ of water vapor, and drying to obtain the copper hydroxystannate-loaded graphene oxide reinforced and toughened rigid polyvinyl chloride foam material, wherein the performance test results are shown in Table 1.
Example 5
The preparation method of the zinc hydroxystannate-loaded graphene oxide comprises the following steps:
graphene oxide was synthesized by a modified Hummers method, the preparation method being the same as in example 1. Carrying out ultrasonic treatment on 170ml of graphene oxide aqueous solution for 1h, adding the solution into a reaction container with stirring, reacting for 1h, stirring and dissolving 2.88g of zinc sulfate heptahydrate in 100ml of deionized water, adding the solution into the reaction container, stirring and dissolving 10.67g of sodium stannate trihydrate in 100ml of deionized water, adding the solution into the reaction container, reacting for 24h under stirring, filtering, washing and drying a product to obtain zinc hydroxystannate-loaded graphene oxide, wherein fig. 2 is a transmission electron microscope image of the zinc hydroxystannate-loaded graphene oxide.
100 parts of PVC resin powder, 70 parts of polyphenyl polymethylene polyisocyanate, 25 parts of methyl hexahydrophthalic anhydride, 3 parts of azodiisobutyronitrile, 1 part of azodicarbonamide, 2.5 parts of barium-zinc stearate composite stabilizer and 4 parts of prepared zinc hydroxystannate-loaded graphene oxide are weighed. After uniformly stirring and mixing, adding the mixture into a mold, carrying out crosslinking and curing for 1.0h at 170 ℃ and 15MPa to obtain pre-foamed foam, cooling and demolding, continuously foaming the pre-foamed foam for 0.5h under 100 ℃ of water vapor, and drying to obtain the zinc hydroxystannate-loaded graphene oxide reinforced and toughened rigid polyvinyl chloride foam material, wherein the performance test results are shown in Table 1.
Example 6
The preparation method of the hydroxyl cobalt stannate-loaded graphene oxide comprises the following steps:
graphene oxide was synthesized by a modified Hummers method, the preparation method being the same as in example 1.
The preparation method comprises the following steps of carrying out ultrasonic treatment on 170ml of graphene oxide aqueous solution for 1h, adding the obtained product into a reaction container with a stirrer for reaction for 1h, stirring and dissolving 2.38g of cobalt chloride hexahydrate in 100ml of deionized water, adding the obtained product into the reaction container, stirring and dissolving 10.67g of sodium stannate trihydrate in 100ml of deionized water, adding the obtained product into the reaction container, reacting for 24h under stirring, and then filtering, washing and drying a product to obtain cobalt hydroxystannate-loaded graphene oxide, wherein a picture 1 is a transmission electron microscope picture of the cobalt hydroxystannate-loaded graphene oxide.
100 parts of PVC resin powder, 70 parts of polyphenyl polymethylene polyisocyanate, 25 parts of methyl hexahydrophthalic anhydride, 3 parts of azodiisobutyronitrile, 1 part of azodicarbonamide, 2.5 parts of barium-zinc stearate composite stabilizer and 4 parts of prepared cobalt hydroxystannate-loaded graphene oxide are weighed. After uniformly stirring and mixing, adding the mixture into a mold, carrying out crosslinking and curing for 0.5h at 170 ℃ and 15MPa to obtain pre-foamed foam, cooling and demolding, continuously foaming the pre-foamed foam for 0.5h under 100 ℃ of water vapor, and drying to obtain the cobalt hydroxystannate-loaded graphene oxide reinforced and toughened rigid polyvinyl chloride foam material, wherein the performance test results are shown in Table 1.
Comparative example 1
Compared with the embodiment 6, 100 parts of PVC resin powder, 70 parts of polyphenyl polymethylene polyisocyanate, 25 parts of methyl hexahydrophthalic anhydride, 3 parts of azobisisobutyronitrile, 1 part of azodicarbonamide and 2.5 parts of barium zinc stearate composite stabilizer are weighed without adding a flame retardant toughening agent. Stirring and mixing uniformly, adding into a mould, carrying out crosslinking and curing for 0.5h at 170 ℃ and 15MPa to obtain pre-foamed foam, cooling, demoulding, continuously foaming the pre-foamed foam for 0.5h under 100 ℃ water vapor, and drying to obtain the rigid polyvinyl chloride foam, wherein the performance test results are shown in Table 1.
Comparative example 2
Compared with the example 6, the cobalt hydroxystannate-loaded graphene oxide is replaced by the common graphite oxide, the rest is the same as that of the example 6, the rigid polyvinyl chloride foam is prepared by drying, and the performance test results are shown in the table 1.
The performance test method of the rigid polyvinyl chloride foam material comprises the following steps:
1. oxygen index LOI: the test is carried out according to GB reinforcing and toughening T2406, and the sample bar size is 10mm multiplied by 6.5mm multiplied by 3 mm.
2. Vertical burning class: the test was carried out according to standard GB reinforcing and toughening T2408, the sample size being 127mm by 13mm by 3 mm.
3. Testing total smoke release amount: the test was carried out according to ISO5660 standard, the specimen dimensions being 100mm by 3 mm.
4. And (3) testing mechanical properties: the compressive strength is tested according to the regulation of GB reinforcing and toughening T20974-2014(GB reinforcing and toughening T8813-2008), and the size of a test sample is 50mm multiplied by 50 mm; the bending strength is tested according to GB reinforcing and toughening T20974-2014(GB reinforcing and toughening T8812.1-2007) standard, and the size of a test sample is 120mm multiplied by 25mm multiplied by 20 mm.
As can be seen from table 1, after the hydroxyl stannic acid metal salt loaded graphene oxide flame retardant is added into the rigid polyvinyl chloride foam material, the oxygen index (LOI) is obviously improved, and the higher the oxygen index is, the better the flame retardant performance is; the vertical burn level maintains the V0 rating. Compared with the rigid polyvinyl chloride foam material without the flame retardant (comparative example 1), the rigid polyvinyl chloride foam material with the hydroxyl stannic acid metal salt loaded with the graphene oxide (example 6) has a greatly reduced total smoke release amount during combustion; compared with the rigid polyvinyl chloride foam material added with the common graphite oxide (comparative example 2), the rigid polyvinyl chloride foam material added with the hydroxyl stannic acid metal salt loaded graphene oxide (example 6) has greatly reduced total smoke release amount during combustion, and in addition, the mechanical property of the rigid polyvinyl chloride foam material added with the hydroxyl stannic acid metal salt loaded graphene oxide is also improved.
TABLE 1 summary of properties of rigid polyvinyl chloride foams obtained in examples and comparative examples
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The reinforced toughened flame-retardant rigid polyvinyl chloride foam material is characterized by comprising the following raw materials in parts by weight: 100 parts of PVC resin, 60-80 parts of isocyanate, 20-30 parts of anhydride, 2-6 parts of initiator, 1-3 parts of foaming agent, 2-5 parts of stabilizer and 1-6 parts of flame retardant toughening agent, wherein the flame retardant toughening agent is hydroxyl stannic acid metal salt loaded graphene oxide.
2. The reinforced and toughened flame-retardant rigid polyvinyl chloride foam material as claimed in claim 1, wherein said PVC resin is PVC paste resin, and K value is 70-80.
3. The reinforced and toughened flame retardant rigid polyvinyl chloride foam material as claimed in claim 1, wherein said isocyanate is selected from any one of toluene diisocyanate, diphenylmethane diisocyanate or polyphenyl polymethylene polyisocyanate.
4. The reinforced and toughened flame-retardant rigid polyvinyl chloride foam material as claimed in claim 1, wherein said acid anhydride is selected from any one of phthalic anhydride, tetrahydrophthalic anhydride or methylhexahydrophthalic anhydride.
5. The reinforced and toughened flame-retardant rigid polyvinyl chloride foam material as claimed in claim 1, wherein said initiator is azobisisobutyronitrile.
6. The reinforced and toughened flame-retardant rigid polyvinyl chloride foam material as claimed in claim 1, wherein said blowing agent is azodicarbonamide.
7. The reinforced and toughened flame-retardant rigid polyvinyl chloride foam material as claimed in claim 1, wherein said stabilizer is one or more selected from barium stearate, zinc stearate or calcium stearate.
8. The reinforced and toughened flame retardant rigid polyvinyl chloride foam material as claimed in any one of claims 1 to 7, wherein the flame retardant toughening agent is selected from one or more of copper hydroxystannate-loaded graphene oxide, cobalt hydroxystannate-loaded graphene oxide, zinc hydroxystannate-loaded graphene oxide, strontium hydroxystannate-loaded graphene oxide or barium hydroxystannate-loaded graphene oxide.
9. The reinforced and toughened flame-retardant rigid polyvinyl chloride foam material as claimed in claim 8, wherein the hydroxyl stannic acid metal salt loaded graphene oxide flame retardant is prepared by the following method:
(1) graphene oxide was synthesized by a modified Hummers method: mixing graphite with NaNO3Adding H in ice water bath2SO4After low-temperature intercalation oxidation, potassium permanganate is added, then stirring is carried out, and H is added2SO4The solution is reacted and then H is added2O2Carrying out reaction; adding water to continue reacting, then, centrifugally washing the obtained graphene oxide by using HCl and water until sulfate ions in the graphene oxide are cleaned, drying, and then, dispersing the graphene oxide in a deionized water solution to obtain a graphene oxide aqueous solution;
(2) carrying out ultrasonic treatment on the graphene oxide aqueous solution, adding water into metal salt, fully stirring and dissolving, and adding the obtained solution and the graphene oxide aqueous solution into a reaction container for reaction;
(3) adding water into stannate trihydrate, stirring and dissolving, wherein the molar ratio of the stannate trihydrate to the metal salt is 1: 1, the ratio of the addition amount of water to the use amount of stannate trihydrate is 20-50ml/g), adding an aqueous solution of stannate trihydrate into a reaction container, reacting at room temperature, filtering, washing and drying a product to obtain the hydroxyl stannate metal salt loaded graphene oxide.
10. The preparation method of the reinforced and toughened flame-retardant rigid polyvinyl chloride foam material as claimed in claim 1, which is characterized by comprising the following steps: weighing polyvinyl chloride resin, isocyanate, anhydride, an initiator, a foaming agent, a stabilizer and a flame retardant toughening agent according to a ratio, stirring and mixing uniformly, adding into a mold, crosslinking and curing for 0.5-1h under the conditions that the temperature of the mold is 170-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010999336.9A CN112126172A (en) | 2020-09-22 | 2020-09-22 | Reinforced toughened flame-retardant rigid polyvinyl chloride foam material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010999336.9A CN112126172A (en) | 2020-09-22 | 2020-09-22 | Reinforced toughened flame-retardant rigid polyvinyl chloride foam material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112126172A true CN112126172A (en) | 2020-12-25 |
Family
ID=73841986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010999336.9A Pending CN112126172A (en) | 2020-09-22 | 2020-09-22 | Reinforced toughened flame-retardant rigid polyvinyl chloride foam material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112126172A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104893248A (en) * | 2015-05-27 | 2015-09-09 | 河北大学 | Preparation method and application of inorganic hybrid smoke-suppression flame retardant |
| CN106009036A (en) * | 2016-07-04 | 2016-10-12 | 沈阳化工大学 | Preparation method for nanometer composite flame retardant |
| WO2017053554A1 (en) * | 2015-09-22 | 2017-03-30 | Nature Tech Llc | Hybrid fire-retarded cellulose materials |
| CN109054235A (en) * | 2018-07-12 | 2018-12-21 | 洛阳科博思新材料科技有限公司 | A kind of New Rigid crosslinked polyvinyl chloride structural foam material and preparation method thereof |
-
2020
- 2020-09-22 CN CN202010999336.9A patent/CN112126172A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104893248A (en) * | 2015-05-27 | 2015-09-09 | 河北大学 | Preparation method and application of inorganic hybrid smoke-suppression flame retardant |
| WO2017053554A1 (en) * | 2015-09-22 | 2017-03-30 | Nature Tech Llc | Hybrid fire-retarded cellulose materials |
| CN106009036A (en) * | 2016-07-04 | 2016-10-12 | 沈阳化工大学 | Preparation method for nanometer composite flame retardant |
| CN109054235A (en) * | 2018-07-12 | 2018-12-21 | 洛阳科博思新材料科技有限公司 | A kind of New Rigid crosslinked polyvinyl chloride structural foam material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4330634A (en) | Foam composites | |
| JP2008535982A (en) | Process for improving the thermal insulation capacity of foamed vinyl aromatic polymers and the products so obtained | |
| US3050476A (en) | Method of making a self extinguishing expandable polymer of styrene by bromination | |
| JP2002521543A (en) | Method for producing expandable styrene polymer containing graphite particles | |
| KR20140011911A (en) | Compositions including polytetrafluoroethylene and processes for the preparation thereof | |
| CN113337054B (en) | High-strength heat-resistant PVC (polyvinyl chloride) foamed sheet and preparation method thereof | |
| JP7336532B2 (en) | Semi-rigid cyanurotriamide foamed plastic and its production method | |
| EP3087125B1 (en) | Combination of a mineral component with carbon black and its use for decreasing the thermal conductivity of vinyl aromatic polymer | |
| CN104194031B (en) | A kind of preparation method of the expandable polystyrene granule containing fire retardant | |
| CN112126172A (en) | Reinforced toughened flame-retardant rigid polyvinyl chloride foam material and preparation method thereof | |
| CN106380731A (en) | PVC film for wallpaper and preparation method thereof | |
| CN107337750B (en) | A kind of expandable poly-styrene and preparation method thereof | |
| JP4007738B2 (en) | Expandable thermoplastic copolymer particles | |
| WO2014111628A2 (en) | Method of producing polystyrene beads having low moisture content | |
| CN108250666B (en) | Amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material and preparation method thereof | |
| CN106995565A (en) | A kind of preparation method of the sol-gel modified poly styrene composite material of fire-retardant phosphotidic | |
| KR100884817B1 (en) | Method for producing expandable polystyrene beads | |
| CN108409931A (en) | A kind of preparation method of polyurethane thermal insulation wallboard for building | |
| KR0122425B1 (en) | Method for manufacturing polystyrene bead foam | |
| JPS61171705A (en) | Production of styrene resin beads | |
| KR101772544B1 (en) | Surface modified expandable polystyrene beads having excellent bonding and a method of manufacturing the same | |
| CN117186278A (en) | Method for preparing environment-friendly flame-retardant expandable polystyrene | |
| WO2006080783A1 (en) | Colored expandable polystyrene resin having high strength, method for producing thereof, and expandable molded product using the same | |
| JPH0234976B2 (en) | ||
| KR820000799B1 (en) | Process for preparing of bublle sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201225 |