CN106810701B - Poly (hydroxyethyl methacrylate) modified phenolic foam and preparation method thereof - Google Patents
Poly (hydroxyethyl methacrylate) modified phenolic foam and preparation method thereof Download PDFInfo
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- CN106810701B CN106810701B CN201611250867.8A CN201611250867A CN106810701B CN 106810701 B CN106810701 B CN 106810701B CN 201611250867 A CN201611250867 A CN 201611250867A CN 106810701 B CN106810701 B CN 106810701B
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- phenolic foam
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000006260 foam Substances 0.000 title claims abstract description 47
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 18
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 17
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 13
- 239000005011 phenolic resin Substances 0.000 claims abstract description 13
- 239000004088 foaming agent Substances 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000005187 foaming Methods 0.000 claims abstract description 9
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims abstract description 9
- 229920000053 polysorbate 80 Polymers 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- -1 aldehyde compounds Chemical class 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 150000002989 phenols Chemical class 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 7
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 claims description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 claims description 2
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 claims description 2
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 2
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 2
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940044654 phenolsulfonic acid Drugs 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 claims description 2
- 239000004604 Blowing Agent Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 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 abstract description 7
- 239000003063 flame retardant Substances 0.000 abstract description 7
- 238000009413 insulation Methods 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006266 etherification reaction Methods 0.000 abstract description 3
- 229920000578 graft copolymer Polymers 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 abstract description 3
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000002585 base Substances 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920002866 paraformaldehyde Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- NWQCVVREYYCLTJ-UHFFFAOYSA-N 3-(3-anilino-4-oxo-5H-pyrazolo[4,3-c]pyridin-1-yl)oxane-4-carbonitrile Chemical compound O=c1[nH]ccc2n(nc(Nc3ccccc3)c12)C1COCCC1C#N NWQCVVREYYCLTJ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
-
- 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
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The invention discloses polyhydroxyethyl methacrylate modified phenolic foam and a preparation method thereof, relates to phenolic foam and a preparation method thereof, and relates to polyhydroxyethyl methacrylate modified phenolic foam; in the foaming stage, a surfactant, a foaming agent and a curing agent are applied, wherein the surfactant is tween-80; the foaming agent is n-pentane; the curing agent is p-toluenesulfonic acid; the product prepared by the invention mainly uses the hydroxyl of the polyhydroxyethyl methacrylate to generate etherification reaction with the hydroxymethyl of the phenolic resin to generate ether bond, and then the ether bond forms a graft copolymer with longer side group, so that the toughness of the material is greatly improved under the condition of good flame retardant property, and the compressive strength is obviously improved, thus the product is suitable for the external wall heat insulation construction with higher requirements.
Description
Technical Field
The invention relates to phenolic foam and a preparation method thereof, in particular to polyhydroxyethyl methacrylate modified phenolic foam and a preparation method thereof.
Background
The phenolic foam plastic is a novel flame-retardant, fireproof and low-smoke heat-insulating material, and is closed-cell rigid foam plastic prepared by adding a flame retardant, a smoke inhibitor, a foaming agent, a curing agent and other auxiliary agents into phenolic resin. The phenolic foam can meet the requirements of heat insulation and fire prevention simultaneously as a heat insulation material, and can be used for public buildings as a material for sealing and controlling fire, so that the double hazards of safety and health brought by the pollution of dust and fine fibers of organic and combustible materials and inorganic materials can be fundamentally avoided. However, the phenolic foam has some defects of mechanical properties, such as lower compression performance, poorer toughness and the like.
Chinese patent CN105802124A is a toughened phenolic resin, which is prepared from formaldehyde, phenol, hexamethylenetetramine, methacrylic acid, melamine and a toughening agent 3- (4-oxo-3- (phenylamino) -4, 5-dihydro-1H-pyrazolo [4, 3-c ] pyridin-1-yl) tetrahydro-2H-pyran-4-carbonitrile, and the proposal only greatly improves the toughness of the phenolic resin, but does not improve the compressive strength, which is not preferable for thermal insulation materials. Therefore, for the phenolic foam thermal insulation material, under the condition of good flame retardant property, the compressive strength is improved while the toughness is improved.
Disclosure of Invention
The invention aims to provide polyhydroxyethyl methacrylate modified phenolic foam and a preparation method thereof, wherein hydroxyl of polyhydroxyethyl methacrylate is subjected to etherification reaction with hydroxymethyl of phenolic resin to generate an ether bond, so that a graft copolymer with longer side groups is formed, the toughness of the material is greatly improved under the condition of good flame retardant property, and meanwhile, the compressive strength is also obviously improved, so that the polyhydroxyethyl methacrylate modified phenolic foam is suitable for the heat insulation construction of the outer wall with higher requirements.
The purpose of the invention is realized by the following technical scheme:
the polyhydroxyethyl methacrylate modified phenolic foam is synthesized by the following structural reaction;
the phenolic foam consists of a resin synthesis stage and a resin foaming stage, and comprises the following specific steps:
in the resin synthesis stage, the components by weight are as follows:
100 parts of phenolic compound;
30-70 parts of aldehyde compounds;
10-60 parts of a catalyst;
5-30 parts of polyhydroxyethyl methacrylate (modifier);
in the resin foaming stage, the components by weight are as follows:
100 parts of phenolic resin;
5-30 parts of a surfactant;
5-30 parts of a foaming agent;
5-30 parts of a curing agent.
The polyhydroxyethyl methacrylate modified phenolic foam is characterized in that the phenolic compound is one or more selected from phenol, cresol, xylenol, nonylphenol, bisphenol A, resorcinol, propylphenol, ethylphenol and cardanol, and phenol is preferred.
The aldehyde compound is selected from one or more of formaldehyde, acetaldehyde, butyraldehyde, polyformaldehyde and furfural, and formaldehyde is preferably selected.
The catalyst of the polyhydroxyethyl polymethacrylate modified phenolic foam is one or more of strong alkali substances such as sodium hydroxide, potassium hydroxide and the like, and sodium hydroxide is preferably selected.
In the polyhydroxyethyl polymethacrylate modified phenolic foam, the surfactant is at least one of tween-80 and silicone oil, and tween-80 is preferably selected.
The foaming agent is at least one of n-pentane and isopentane, and n-pentane is preferably selected.
The curing agent of the polyhydroxyethyl polymethacrylate modified phenolic foam is one or more of p-toluenesulfonic acid, xylene sulfonic acid, phenol sulfonic acid and benzene sulfonic acid, and p-toluenesulfonic acid is preferably selected.
8. A preparation method of polyhydroxyethyl methacrylate modified phenolic foam comprises the following steps:
(1) weighing phenolic compounds, catalysts, modifiers and the like, placing the phenolic compounds, the catalysts, the modifiers and the like in a reaction kettle at the temperature of 60-80 ℃, then adding aldehyde compounds, and heating the mixture to 80-100 ℃ for reaction; after the reaction is finished, carrying out reduced pressure distillation, and adjusting the pH value to obtain the polyhydroxyethyl methacrylate expandable phenolic resin;
(2) placing the modified phenolic resin into a container for later use, weighing the surfactant and the foaming agent in sequence, adding the surfactant and the foaming agent into the container, quickly stirring for 1-3 minutes, pouring the weighed curing agent into the container, stirring for 10-20 seconds, pouring the stirred liquid into a mold, placing the mold into an oven at 60-80 ℃ for foaming and molding, and taking out and demolding the mold after foaming and molding are completed to obtain the polyhydroxyethyl methacrylate modified phenolic foam.
The invention has the advantages and effects that:
the invention introduces a polyhydroxyethyl methacrylate modified phenolic foam, mainly utilizes hydroxyl of polyhydroxyethyl methacrylate and hydroxymethyl of phenolic resin to generate etherification reaction to generate an ether bond, thereby forming a graft copolymer with longer side groups, greatly improving the toughness of the material under the condition of good flame retardant property, obviously improving the compressive strength, and being suitable for the outer wall heat insulation construction with higher requirements.
Detailed Description
The present invention will be described in detail with reference to examples.
The present invention will be described with reference to examples, but the present invention is not limited to these examples.
Example 1
1) Adding 100g of phenol, 10g of polyhydroxyethyl methacrylate and 3g of saturated sodium hydroxide solution into a reaction kettle, adding 35g of solid paraformaldehyde in batches at the water bath temperature of 60 ℃, controlling the water bath temperature to be finished after half an hour, continuously reacting for half an hour, raising the temperature to 90 ℃, continuously reacting for 70min, then keeping the vacuum degree in a reaction device at 650MPa for reduced pressure distillation, controlling the material temperature at about 48 ℃ in the distillation process, stopping distillation until the distilled water reaches a certain requirement, adding acetic acid to adjust the pH value of a product to about 7, and obtaining the phenolic basic resin.
2) Mixing phenolic aldehyde base resin, tween-80, n-pentane and p-toluenesulfonic acid according to the proportion of 100: 12: 10: 12, stirring quickly for 3min, transferring the mixed materials into a die, reacting at 70 ℃ for 10 min, demoulding to obtain a phenolic foam product, and detecting the index of the synthesized product.
Example 2
1) Adding 100g of phenol, 15g of polyhydroxyethyl methacrylate and 3g of saturated sodium hydroxide solution into a reaction kettle, adding 35g of solid paraformaldehyde in batches at the water bath temperature of 60 ℃, controlling the water bath temperature to be finished after half an hour, continuously reacting for half an hour, raising the temperature to 90 ℃, continuously reacting for 70min, then keeping the vacuum degree in a reaction device at 650MPa for reduced pressure distillation, controlling the material temperature at about 48 ℃ in the distillation process, stopping distillation until the distilled water reaches a certain requirement, adding acetic acid to adjust the pH value of a product to about 7, and obtaining the phenolic basic resin.
2) Mixing phenolic aldehyde base resin, tween-80, n-pentane and p-toluenesulfonic acid according to the proportion of 100: 12: 10: 12, stirring quickly for 3min, transferring the mixed materials into a die, reacting at 70 ℃ for 10 min, demoulding to obtain a phenolic foam product, and detecting the index of the synthesized product.
Example 3
1) Adding 100g of phenol, 20g of polyhydroxyethyl methacrylate and 3g of saturated sodium hydroxide solution into a reaction kettle, adding 35g of solid paraformaldehyde in batches at the water bath temperature of 60 ℃, controlling the water bath temperature to be finished after half an hour, continuously reacting for half an hour, raising the temperature to 90 ℃, continuously reacting for 70min, then keeping the vacuum degree in a reaction device at 650MPa for reduced pressure distillation, controlling the material temperature at about 48 ℃ in the distillation process, stopping distillation until the distilled water reaches a certain requirement, adding acetic acid to adjust the pH value of a product to about 7, and obtaining the phenolic basic resin.
2) Mixing phenolic aldehyde base resin, tween-80, n-pentane and p-toluenesulfonic acid according to the proportion of 100: 12: 10: 12, stirring quickly for 3min, transferring the mixed materials into a die, reacting at 70 ℃ for 10 min, demoulding to obtain a phenolic foam product, and detecting the index of the synthesized product.
Example 4
1) Adding 100g of phenol, 25g of polyhydroxyethyl methacrylate and 3g of saturated sodium hydroxide solution into a reaction kettle, adding 35g of solid paraformaldehyde in batches at the water bath temperature of 60 ℃, controlling the water bath temperature to be finished after half an hour, continuously reacting for half an hour, raising the temperature to 90 ℃, continuously reacting for 70min, then keeping the vacuum degree in a reaction device at 650MPa for reduced pressure distillation, controlling the material temperature at about 48 ℃ in the distillation process, stopping distillation until the distilled water reaches a certain requirement, adding acetic acid to adjust the pH value of a product to about 7, and obtaining the phenolic basic resin.
2) Mixing phenolic aldehyde base resin, tween-80, n-pentane and p-toluenesulfonic acid according to the proportion of 100: 12: 10: 12, stirring quickly for 3min, transferring the mixed materials into a die, reacting at 70 ℃ for 10 min, demoulding to obtain a phenolic foam product, and detecting the index of the synthesized product.
Base contrast
1) Adding 100g of phenol and 3g of sodium hydroxide saturated solution into a reaction kettle, adding 35g of solid paraformaldehyde in batches at the water bath temperature of 60 ℃, controlling the water bath temperature to be added for half an hour, continuously reacting for half an hour, raising the temperature to 90 ℃, continuously reacting for 70min, then keeping the vacuum degree in a reaction device at 650MPa for reduced pressure distillation, controlling the material temperature at about 48 ℃ in the distillation process, stopping distillation until the distilled water reaches a certain requirement, and adding acetic acid to adjust the pH value of a product to about 7 to obtain the phenolic base resin.
2) Mixing phenolic aldehyde base resin, tween-80, n-pentane and p-toluenesulfonic acid according to the proportion of 100: 12: 10: 12, stirring quickly for 3min, transferring the mixed materials into a die, reacting at 70 ℃ for 10 min, demoulding to obtain a phenolic foam product, and detecting the index of the synthesized product.
The performance pairs for the modified phenolic foam products prepared in examples 1 to 4 of the present invention versus the unmodified phenolic foam products are as follows:
| compressive strength/MPa | Bending deformation/mm | Oxygen index% | |
| Example 1 | 0.32 | 14.24 | 31.43 |
| Example 2 | 0.43 | 18.46 | 32.59 |
| Example 3 | 0.51 | 21.21 | 33.72 |
| Example 4 | 0.64 | 24.33 | 33.98 |
| Base contrast | 0.14 | 6.27 | 29.78 |
It can be seen from the above table that with the increase of the modifier of polyhydroxyethyl methacrylate, the bending deformation degree of the modified phenolic foam is increased continuously, and as a longer flexible chain is introduced into the phenolic resin, the rigid molecular structure of the phenolic resin is changed fundamentally, so that the toughness of the foam product is improved, and the brittleness is reduced. Meanwhile, the compressive strength is obviously increased by introducing the polyhydroxyethyl methacrylate, and the compressive strength of the phenolic foam is obviously increased mainly because the polyhydroxyethyl methacrylate participates in the reaction, the closed cell rate of the foam is improved, and the compression resistance is increased. Therefore, the modified phenolic foam has improved toughness and compressive strength under the condition of good and unchanged flame retardant property, and is suitable for the heat insulation construction of external walls with higher requirements.
The present invention is further illustrated by the following specific examples, which are only exemplary and not intended to limit the scope of the present invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made on the technical solution of the present invention and the embodiments thereof without departing from the spirit and scope of the present invention, and these shall fall within the scope of the present invention. The scope of the invention is to be determined by the claims appended hereto.
Claims (8)
1. The polyhydroxyethyl methacrylate modified phenolic foam is characterized in that the phenolic foam is synthesized into a structural reaction as follows;
the phenolic foam consists of a resin synthesis stage and a resin foaming stage, and comprises the following specific steps:
in the resin synthesis stage, the components by weight are as follows:
100 parts of phenolic compound;
30-70 parts of aldehyde compounds;
10-60 parts of a catalyst;
the modifier is 5-30 parts of polyhydroxyethyl methacrylate;
in the resin foaming stage, the components by weight are as follows:
100 parts of phenolic resin;
5-30 parts of a surfactant;
5-30 parts of a foaming agent;
5-30 parts of a curing agent.
2. The foam of claim 1, wherein the phenolic compound is selected from one or more of phenol, cresol, xylenol, nonylphenol, bisphenol A, resorcinol, propylphenol, ethylphenol and cardanol.
3. The polyhydroxyethylmethacrylate-modified phenolic foam according to claim 1, wherein the aldehyde compound is selected from one or more of formaldehyde, acetaldehyde, butyraldehyde, polyoxymethylene and furfural.
4. The polyhydroxyethylmethacrylate modified phenolic foam according to claim 1, wherein the catalyst is one or more of sodium hydroxide and potassium hydroxide.
5. The polyhydroxyethylmethacrylate modified phenolic foam according to claim 1, wherein the surfactant is at least one of tween-80 and silicone oil.
6. The polyhydroxyethylmethacrylate-modified phenolic foam according to claim 1, wherein the blowing agent is at least one of n-pentane and isopentane.
7. The polyhydroxyethylmethacrylate modified phenolic foam according to claim 1, wherein the curing agent is one or more of p-toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid and benzenesulfonic acid.
8. The polyhydroxyethylmethacrylate modified phenolic foam according to claim 1, wherein the preparation method of the polyhydroxyethylmethacrylate modified phenolic foam comprises the following steps:
(1) weighing phenolic compounds, catalysts and modifiers, placing the phenolic compounds, the catalysts and the modifiers in a reaction kettle at the temperature of 60-80 ℃, then adding aldehyde compounds, and heating the mixture to 80-100 ℃ for reaction; after the reaction is finished, carrying out reduced pressure distillation, and adjusting the pH value to obtain the polyhydroxyethyl methacrylate expandable phenolic resin;
(2) putting the polyhydroxyethyl methacrylate expandable phenolic resin into a container for later use, weighing the surfactant and the foaming agent in sequence, adding the weighed surfactant and the foaming agent into the container, quickly stirring for 1-3 minutes, pouring the weighed curing agent into the container, stirring for 10-20 seconds, then pouring the stirred liquid into a mold, putting the mold into an oven at 60-80 ℃ for foaming and molding, and taking out and demolding the mold after foaming and molding are finished to obtain the polyhydroxyethyl methacrylate modified phenolic foam.
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| CN106810701B true CN106810701B (en) | 2020-05-19 |
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| SU883103A1 (en) * | 1979-10-19 | 1981-11-23 | Научно-Исследовательский Институт Прикладных Физических Проблем Им.А.Н.Севченко При Белорусском Ордена Трудового Красного Знамени Государственном Университете Им. В.И.Ленина | Method of producing ureaformaldehyde porous plastic material |
| CN102492091A (en) * | 2011-12-07 | 2012-06-13 | 上海久安水质稳定剂厂 | Special modifier for phenolic foam foaming and manufacturing method thereof |
| CN102492167A (en) * | 2011-12-16 | 2012-06-13 | 上海久安水质稳定剂厂 | Secondary utilization method for phenol formaldehyde foam waste |
| WO2014059674A1 (en) * | 2012-10-19 | 2014-04-24 | 江苏博特新材料有限公司 | Water reducer intermediate, preparation method therefor, and water reducer prepared by using the same |
| KR101533297B1 (en) * | 2015-01-08 | 2015-07-02 | 청원화학 주식회사 | Flame Retardant FRP Panel Composition Using Eco Friendly Basalt Fiber and Phenol Resin and Reinforcement of Concrete Structure Using Thereof |
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2016
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| SU883103A1 (en) * | 1979-10-19 | 1981-11-23 | Научно-Исследовательский Институт Прикладных Физических Проблем Им.А.Н.Севченко При Белорусском Ордена Трудового Красного Знамени Государственном Университете Им. В.И.Ленина | Method of producing ureaformaldehyde porous plastic material |
| CN102492091A (en) * | 2011-12-07 | 2012-06-13 | 上海久安水质稳定剂厂 | Special modifier for phenolic foam foaming and manufacturing method thereof |
| CN102492167A (en) * | 2011-12-16 | 2012-06-13 | 上海久安水质稳定剂厂 | Secondary utilization method for phenol formaldehyde foam waste |
| WO2014059674A1 (en) * | 2012-10-19 | 2014-04-24 | 江苏博特新材料有限公司 | Water reducer intermediate, preparation method therefor, and water reducer prepared by using the same |
| KR101533297B1 (en) * | 2015-01-08 | 2015-07-02 | 청원화학 주식회사 | Flame Retardant FRP Panel Composition Using Eco Friendly Basalt Fiber and Phenol Resin and Reinforcement of Concrete Structure Using Thereof |
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Application publication date: 20170609 Assignee: SHENYANG XINFEIYU RUBBER PRODUCTS CO.,LTD. Assignor: SHENYANG University OF CHEMICAL TECHNOLOGY Contract record no.: X2023210000283 Denomination of invention: Polyhydroxyethyl methacrylate modified phenolic foam and its preparation method Granted publication date: 20200519 License type: Common License Record date: 20231205 |