CN108250666B - Amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material and preparation method thereof - Google Patents
Amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material and preparation method thereof Download PDFInfo
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- CN108250666B CN108250666B CN201810047464.6A CN201810047464A CN108250666B CN 108250666 B CN108250666 B CN 108250666B CN 201810047464 A CN201810047464 A CN 201810047464A CN 108250666 B CN108250666 B CN 108250666B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 50
- -1 Amino trimethylene phosphonate Chemical compound 0.000 title claims abstract description 34
- 239000006261 foam material Substances 0.000 title claims abstract description 34
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003063 flame retardant Substances 0.000 claims abstract description 31
- 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 claims abstract description 30
- 239000012745 toughening agent Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000004088 foaming agent Substances 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- 229920003987 resole Polymers 0.000 claims abstract description 13
- 238000005187 foaming Methods 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 9
- CMQAMENQCKNUPB-UHFFFAOYSA-N NC1CCOP(=O)O1 Chemical compound NC1CCOP(=O)O1 CMQAMENQCKNUPB-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- ZLQHCZRLKFRCNH-UHFFFAOYSA-N P1(OC(CCO1)N)=O.[Mg] Chemical compound P1(OC(CCO1)N)=O.[Mg] ZLQHCZRLKFRCNH-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 239000004604 Blowing Agent Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 3
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 8
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 7
- 229920000053 polysorbate 80 Polymers 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical group C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 206010000369 Accident Diseases 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011489 building insulation material Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- 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
- C08J9/12—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 physical blowing agent
- C08J9/14—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 physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- 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
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
Abstract
The invention belongs to the technical field of materials, and particularly relates to an amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material and a preparation method thereof. The specific preparation method comprises the following steps: after 100 parts of resol, 8-10 parts of curing agent, 6-12 parts of foaming agent, 4-6 parts of surfactant and 1-5 parts of amino trimethylene phosphonate loaded graphene oxide flame retardant toughening agent are quickly and uniformly stirred, adding a mold to close the mold, and carrying out foaming and curing at 70-90 ℃ for 40-80 min, thereby obtaining the amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material. The phenolic foam material prepared by the invention has the characteristics of higher strength, good flame retardant property and low pulverization rate.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material and a preparation method thereof.
Background
Polymer foams, such as Polystyrene (PS) foams and Polyurethane (PU) foams, are widely used in building insulation materials due to their advantages of excellent insulation, good mechanical properties, excellent weatherability, easy molding processability, etc. However, both PS foam and PU foam are very flammable materials, and fire accidents caused by their fires frequently occur, resulting in significant casualties and property damage. Although the phenolic foam material has the advantages of good heat insulation effect, excellent flame resistance, good flame penetration resistance, low smoke and low toxicity during combustion and the like, the phenolic foam material also has the defects of high hardness, high brittleness and easy pulverization, and the application field of the phenolic foam material is greatly limited, so the phenolic foam material has important theoretical significance and application value in toughening and modifying the phenolic foam material.
It is reported that [ j. appl.polym.sci., 2013, 128, 2720-2728 ], polymer toughening agents commonly used for phenolic foam materials, such as polyurethane prepolymers, flexible epoxy resins, polyethylene glycol, and the like, can improve the toughness of the phenolic foam materials, but generally reduce the flame retardant properties of the phenolic foam materials due to their flammability. Graphene Oxide (GO) has a unique layered structure, a large specific surface area and excellent electrical, optical and mechanical properties, and is widely applied to polymer materials to improve the thermal stability, mechanical properties and flame retardant properties [ J. mater. chem. A, 2015, 3, 9826-. According to the report of the literature [ J. Mater. chem. A, 2015, 3, 9826-.
Therefore, the invention prepares the reinforced, toughened and flame-retardant phenolic foam material on the surface of the graphene oxide loaded with the amino trimethylene phosphonate serving as the flame retardant.
Disclosure of Invention
The invention aims to provide an amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material and a preparation method thereof.
The invention provides an amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material, which consists of resol, a flame retardant toughening agent, a surfactant, a curing agent and a foaming agent, and comprises the following components in parts by weight: 100 parts of resol, 1-5 parts of flame-retardant toughening agent, 4-6 parts of surfactant, 8-10 parts of curing agent and 6-12 parts of foaming agent.
In the invention, the surfactant is tween-80.
In the invention, the curing agent is a mixed solution compounded by phosphoric acid, water and toluene-4-sulfonic acid, and the volume ratio of the water, the toluene-4-sulfonic acid and the phosphoric acid is 2:2: 1.
In the invention, the foaming agent is n-pentane.
In the invention, the flame retardant toughening agent is any one of graphene oxide loaded by magnesium aminotrimethylene phosphonate, graphene oxide loaded by zinc aminotrimethylene phosphonate, graphene oxide loaded by calcium aminotrimethylene phosphonate or graphene oxide loaded by iron aminotrimethylene phosphonate. Preferred is aminotrimethylene magnesium phosphonate supported graphene oxide.
The invention provides a preparation method of an amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material, which comprises the following specific steps:
uniformly mixing the resol phenolic resin, the amino trimethylene phosphonate loaded graphene oxide flame-retardant toughening agent, the surfactant, the curing agent and the foaming agent under the stirring condition, adding the mixture into a mould, foaming and curing at 70-90 ℃, and controlling the curing time to be 40-80 minutes to prepare the amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material.
In the invention, the curing temperature is 80-90 ℃, and the curing time is 60 minutes.
The preparation method of the amino trimethylene phosphonate loaded graphene oxide flame retardant toughening agent comprises the following specific steps:
(1) preparing a graphene oxide aqueous solution:
(1.1) uniformly mixing natural graphite and sodium nitrate, keeping the formed mixed reaction system in an ice-water bath, and slowly adding concentrated sulfuric acid and continuously stirring for 2 hours;
(1.2) under an ice-water bath, adding an oxidant potassium permanganate into the mixed solution finally obtained in the step, raising the temperature of the formed mixed reaction system to 35 ℃, and stirring for 2 hours under heat preservation;
(1.3) raising the temperature of the mixed reaction system finally obtained in the step (1.2) to 60 ℃, slowly adding 5% dilute sulfuric acid, and stirring for 2 hours under heat preservation;
(1.4) raising the temperature of the mixed reaction system finally obtained in the step (1.3) to 90 ℃, slowly adding 20ml of hydrogen peroxide, keeping the temperature and stirring for 1 hour, and finally adding 1L of distilled water to continue to react for 1 hour, wherein the system is golden yellow;
(1.5) separating solid matters from the mixed reaction system finally obtained in the step (1.4), washing and drying to obtain graphene oxide;
(2) preparation of a precursor solution of aminotrimethylene phosphonate:
dissolving 0.3-10 g of metal chloride in 25ml of deionized water, and slowly adding 10-40 ml of 50% amino trimethylene phosphonic acid to obtain the solution;
(3) and (3) adding the precursor solution of the amino trimethylene phosphonate obtained in the step (2) into 90-120 ml of graphene oxide aqueous solution with the concentration of 3mg/ml obtained in the step (1), uniformly mixing, stirring and reacting for 24-30 h at 90-110 ℃, centrifuging, washing and drying to obtain the amino trimethylene phosphonate loaded graphene oxide flame retardant.
In the invention, the metal chloride in the step (2) is any one of magnesium chloride, zinc chloride, calcium chloride or ferric chloride.
The invention has the beneficial effects that: the amino trimethylene phosphonate loaded graphene oxide flame retardant toughening agent synthesized by the invention has good thermal stability and flame retardant performance, and further has double effects of flame retardance and toughening. Aiming at the defects of high brittleness and easy powder falling of the phenolic foam material, the invention maintains the excellent flame retardant property of the phenolic foam material while enhancing and toughening.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1:
the preparation method of the nano amino trimethylene magnesium phosphonate loaded graphene oxide (Mg-AMP/GO) flame retardant comprises the following steps: the graphene oxide is synthesized by a Hummers method, namely 2 g of graphite and 2 g of NaNO3Adding into a three-necked flask, and slowly adding 80 ml of 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 H2SO4200 ml 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 with 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 (3 mg/ml).
1 g of magnesium chloride (MgCl)2·6H2O) is dissolved in 6 ml of deionized water, 15 ml of 50 percent amino trimethylene phosphonic acid is slowly added to prepare precursor solution of amino trimethylene magnesium phosphonate, 90 ml of graphene oxide solution with the concentration of 3mg/ml is added, then stirring and refluxing are carried out for 24 h at 100 ℃, and washing is carried outAnd drying to obtain the nano amino trimethylene magnesium phosphonate loaded graphene oxide flame retardant toughening agent.
Weighing 100 parts of resol, respectively stirring 5 parts of tween-80 surfactant, 1 part of flame retardant toughening agent, 9 parts of mixed acid curing agent (water: toluene-4-sulfonic acid: phosphoric acid =2:2: 1) and 8 parts of n-pentane foaming agent uniformly, pouring into a mold, and foaming at 80 ℃ for 1h to obtain the aminotrimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material.
Example 2:
weighing 100 parts of resol, respectively stirring 5 parts of tween-80 surfactant, 2 parts of flame retardant toughening agent, 9 parts of mixed acid curing agent (water: toluene-4-sulfonic acid: phosphoric acid =2:2: 1) and 8 parts of n-pentane foaming agent uniformly, pouring into a mold, and foaming at 80 ℃ for 1h to obtain the aminotrimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material. The flame retardant toughener is prepared as in example 1.
Example 3:
weighing 100 parts of resol, respectively stirring 5 parts of tween-80 surfactant, 3 parts of flame retardant toughening agent, 9 parts of mixed acid curing agent (water: toluene-4-sulfonic acid: phosphoric acid =2:2: 1) and 8 parts of n-pentane foaming agent uniformly, pouring into a mold, and foaming at 80 ℃ for 1h to obtain the aminotrimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material. The flame retardant toughener is prepared as in example 1.
Example 4:
weighing 100 parts of resol, respectively stirring 5 parts of tween-80 surfactant, 4 parts of flame retardant toughening agent, 9 parts of mixed acid curing agent (water: toluene-4-sulfonic acid: phosphoric acid =2:2: 1) and 8 parts of n-pentane foaming agent uniformly, pouring into a mold, and foaming at 80 ℃ for 1h to obtain the aminotrimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material. The flame retardant toughener is prepared as in example 1.
Example 5:
weighing 100 parts of resol, respectively stirring 5 parts of tween-80 surfactant, 5 parts of flame retardant toughening agent, 9 parts of mixed acid curing agent (water: toluene-4-sulfonic acid: phosphoric acid =2:2: 1) and 8 parts of n-pentane foaming agent uniformly, pouring into a mold, and foaming at 80 ℃ for 1h to obtain the aminotrimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material. The flame retardant toughener is prepared as in example 1.
Comparative example 1:
weighing 100 parts of resol, respectively stirring 5 parts of tween-80 surfactant, 9 parts of mixed acid curing agent (water: toluene-4-sulfonic acid: phosphoric acid =2:2: 1) and 8 parts of n-pentane foaming agent uniformly, pouring into a mold, and foaming at 80 ℃ for 1h to obtain a phenolic foam material control sample. The phenolic foam test results are as follows:
TABLE 1 amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material performance
Claims (6)
1. The amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material is characterized by comprising a resol resin, a flame retardant toughening agent, a surfactant, a curing agent and a foaming agent in parts by weight: 100 parts of resol, 1-5 parts of flame-retardant toughening agent, 4-6 parts of surfactant, 8-10 parts of curing agent and 6-12 parts of foaming agent; the flame retardant toughening agent is any one of graphene oxide loaded by magnesium aminotrimethylene phosphonate, graphene oxide loaded by zinc aminotrimethylene phosphonate, graphene oxide loaded by calcium aminotrimethylene phosphonate or graphene oxide loaded by iron aminotrimethylene phosphonate.
2. The amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material as claimed in claim 1, wherein the curing agent is a mixed solution compounded by phosphoric acid, water and toluene-4-sulfonic acid.
3. The aminotrimethylene phosphonate supported graphene oxide reinforced and toughened phenolic foam material of claim 1, wherein the blowing agent is n-pentane.
4. The amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material of claim 1, wherein the flame retardant toughening agent is amino trimethylene magnesium phosphonate loaded graphene oxide.
5. The preparation method of the amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material as claimed in claim 1, is characterized by comprising the following specific steps:
uniformly mixing the resol phenolic resin, the amino trimethylene phosphonate loaded graphene oxide flame-retardant toughening agent, the surfactant, the curing agent and the foaming agent under the stirring condition, adding the mixture into a mould, foaming and curing at 70-90 ℃, and controlling the curing time to be 40-80 minutes to prepare the amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material.
6. The method according to claim 5, wherein the curing temperature is 80 ℃ to 90 ℃ and the curing time is 60 minutes.
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| CN201810047464.6A CN108250666B (en) | 2018-01-18 | 2018-01-18 | Amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material and preparation method thereof |
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| CN201810047464.6A CN108250666B (en) | 2018-01-18 | 2018-01-18 | Amino trimethylene phosphonate loaded graphene oxide reinforced and toughened phenolic foam material and preparation method thereof |
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|---|---|---|---|---|
| GB2421728B (en) * | 2004-12-23 | 2010-09-08 | Kingspan Holdings | A phenolic foam |
| CN102746613A (en) * | 2012-07-05 | 2012-10-24 | 同济大学 | Preparation method for phosphate ester flame retardant toughening phenolic foam material |
| CN105175984B (en) * | 2015-07-22 | 2017-05-31 | 同济大学 | A kind of preparation method of activeness and quietness flame-proof phenolic foam |
| CN105694107B (en) * | 2016-01-26 | 2018-12-18 | 同济大学 | A kind of preparation method of nanometer of alpha zirconium phosphate load graphene oxide fire retardant |
| CN106009490B (en) * | 2016-07-08 | 2018-06-19 | 江南大学 | A kind of phenolic resin foam of heterogeneous nucleation agent toughening modifying and preparation method thereof |
| CN106632468B (en) * | 2016-11-22 | 2019-08-06 | 同济大学 | The preparation method of aminotrimethylenephosphonic acid metal salt fire retardant |
-
2018
- 2018-01-18 CN CN201810047464.6A patent/CN108250666B/en not_active Expired - Fee Related
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