CN116874869A - Flame-retardant polystyrene heat-insulating plate and preparation process thereof - Google Patents
Flame-retardant polystyrene heat-insulating plate and preparation process thereof Download PDFInfo
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- CN116874869A CN116874869A CN202311032740.9A CN202311032740A CN116874869A CN 116874869 A CN116874869 A CN 116874869A CN 202311032740 A CN202311032740 A CN 202311032740A CN 116874869 A CN116874869 A CN 116874869A
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- flame
- retardant
- cyclodextrin
- naphthalene
- histidine
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 85
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 30
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 64
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical group O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 51
- -1 naphthalene-histidine Chemical compound 0.000 claims abstract description 38
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000003094 microcapsule Substances 0.000 claims abstract description 24
- 239000011324 bead Substances 0.000 claims abstract description 22
- 229920006248 expandable polystyrene Polymers 0.000 claims abstract description 22
- YASRHLDAFCMIPB-UHFFFAOYSA-N (1-oxo-2,6,7-trioxa-1$l^{5}-phosphabicyclo[2.2.2]octan-4-yl)methanol Chemical compound C1OP2(=O)OCC1(CO)CO2 YASRHLDAFCMIPB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000009413 insulation Methods 0.000 claims abstract description 13
- 229920001807 Urea-formaldehyde Polymers 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000005187 foaming Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000001116 FEMA 4028 Substances 0.000 claims description 15
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 15
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 15
- 229960004853 betadex Drugs 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 7
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 7
- IQDQMRZGMILNMQ-UHFFFAOYSA-N naphthalene-2,6-dicarbaldehyde Chemical compound C1=C(C=O)C=CC2=CC(C=O)=CC=C21 IQDQMRZGMILNMQ-UHFFFAOYSA-N 0.000 claims description 7
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical class OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 3
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 230000000694 effects Effects 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000007723 die pressing method Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229920006327 polystyrene foam Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
- C08B37/0015—Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes
-
- 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
- C08J2325/00—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 an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/16—Cyclodextrin; Derivatives thereof
-
- 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
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2461/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic and acyclic or carbocyclic compounds
-
- 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
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of flame-retardant materials, and discloses a flame-retardant polystyrene heat-insulating board and a preparation process thereof, wherein naphthalene-histidine crosslinked cyclodextrin forms a microcapsule structure with a space crosslinked network structure, so that the embedding amount of 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide can be increased, and a cyclodextrin microcapsule flame retardant is obtained. And (3) compounding the flame-retardant coating liquid with melamine modified urea resin to form flame-retardant coating liquid, and foaming, blending and die pressing the flame-retardant coating liquid with expandable polystyrene beads to obtain the flame-retardant polystyrene heat-insulating board. The naphthalene-histidine crosslinked cyclodextrin and 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide form an intumescent flame retardant system, so that the limiting oxygen index and the char formation effect of the polystyrene heat insulation board during combustion are improved, the combustion heat release rate is reduced, the flame retardant effect of the board is improved, and the polystyrene board has better application in the fields of fire protection, flame retardance and the like.
Description
Technical Field
The invention relates to the technical field of flame-retardant materials, in particular to a flame-retardant polystyrene heat-insulating board and a preparation process thereof.
Background
The polystyrene foam board has the advantages of light weight, low cost, small heat conductivity, good heat preservation performance, good electrical insulation performance and the like, is a building material with excellent comprehensive performance, and is widely used in the fields of building, heat preservation, packaging, daily necessities and the like, but the polystyrene foam board has the problems of easy combustion, toxic smoke release and the like, and is unfavorable for the application in the fields of fire protection, flame retardance and the like, so that the novel halogen-free environment-friendly flame retardant, such as an intumescent flame retardant, a silicon flame retardant, a bio-based flame retardant and the like, needs to be developed.
Beta-cyclodextrin is a nontoxic and environment-friendly natural macromolecule, has the characteristics of high char formation, hydrophobic inside a cavity and hydrophilic outside the cavity, so that the beta-cyclodextrin can only embed various organic compounds, has wide application prospects in the aspects of microcapsules, flame retardants, drug separation and enrichment, drug slow release and the like, is an effective method for improving the embedding amount of the characteristic compounds, and can expand the practical application of the beta-cyclodextrin in the aspects of flame retardants, high polymer materials and the like.
Disclosure of Invention
The invention solves the technical problems that: the cyclodextrin microcapsule flame retardant is prepared, and the flame retardant property of the polystyrene heat-insulating board is enhanced.
The technical scheme of the invention is as follows:
the preparation process of the flame-retardant polystyrene heat-insulating plate comprises 75-90 parts by weight of expandable polystyrene beads and 10-25 parts by weight of melamine modified urea resin flame-retardant coating liquid; the preparation process comprises the following steps:
s1, adding melamine modified urea-formaldehyde resin and cyclodextrin microcapsule flame retardant into a stirrer, uniformly mixing, and uniformly stirring to obtain melamine modified urea-formaldehyde resin flame-retardant coating liquid;
s2, pre-foaming the expandable polystyrene beads in a steam system at 100 ℃ for 3-6min, curing the expandable polystyrene beads at room temperature for 18-24h, uniformly mixing the expandable polystyrene beads with melamine modified urea resin flame-retardant coating liquid in a stirrer, and molding the materials in a press vulcanizer to obtain the flame-retardant polystyrene heat-insulation board.
Further, in the step S1, the stirring speed is controlled to be 80-150r/min, and the stirring time is controlled to be 5-10min; and S2, controlling the stirring speed to be 200-300r/min and the stirring time to be 30-60min.
Further, the temperature is controlled to be 100-120 ℃ and the pressure is controlled to be 7-10MPa during the molding in the step S2, and the time is 3-5min.
Further, the preparation process of the cyclodextrin microcapsule flame retardant comprises the following steps:
(1) Adding naphthalene-2, 6-dicarboxaldehyde and histidine into ethanol, dropwise adding glacial acetic acid, refluxing at 70-80deg.C for 2-5 hr, concentrating to remove ethanol, adding water and dichloromethane, extracting, concentrating organic phase, washing with petroleum ether, and drying to obtain naphthalene-2, 6-histidine intermediate.
(2) Adding beta-cyclodextrin, naphthalene-2, 6-histidine intermediate, N-hydroxysuccinimide and dicyclohexylcarbodiimide into dimethyl sulfoxide, reacting for 24-48h at 35-50 ℃, filtering, washing with ethanol, and drying to obtain naphthalene-histidine cross-linked cyclodextrin.
(3) Adding naphthalene-histidine cross-linked cyclodextrin, 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide into waterAnd (3) carrying out ultrasonic vibration for 0.5-1h, then stirring for 12-24h, filtering, washing with ethanol, and drying to obtain the cyclodextrin microcapsule flame retardant.
Further, the ratio of each reactant in the (1) is as follows: naphthalene-2, 6-dicarboxaldehyde histidine glacial acetic acid=1 g (1.7-2.5 g) (0.1-0.18) mL.
Further, the ratio of each reactant in the step (2) is beta-cyclodextrin, naphthalene-2, 6-histidine intermediate, N-hydroxysuccinimide and dicyclohexylcarbodiimide=1 g (0.8-2.5 g) (0.3-1 g) and (0.7-2.2 g).
Further, the ratio of each reactant in the step (3) is naphthalene-histidine cross-linked cyclodextrin, namely 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide=1 g (0.5-1.5 g).
The beneficial technical effects of the invention are as follows: naphthalene-2, 6-histidine intermediate is used as a cross-linking agent, two carboxyl groups of the intermediate are utilized to carry out esterification cross-linking reaction with hydroxyl groups of beta-cyclodextrin to obtain naphthalene-histidine cross-linked cyclodextrin, the cross-linked cyclodextrin forms a microcapsule structure with a space cross-linked network structure, the specific surface area is larger, embedding sites are more, and oxygen atoms in imidazole N-H bonds and ester groups of the cyclodextrin can carry out hydrogen bond interaction with hydroxyl groups of 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, so that the embedding amount is increased, and the cyclodextrin microcapsule flame retardant is obtained. And (3) compounding the flame-retardant coating liquid with melamine modified urea resin to form flame-retardant coating liquid, and foaming, blending and die pressing the flame-retardant coating liquid with expandable polystyrene beads to obtain the flame-retardant polystyrene heat-insulating board.
The naphthalene-histidine crosslinked cyclodextrin contains a rigid naphthalene ring structure with high carbon content, so that the char formation of the cyclodextrin during combustion can be improved, an intumescent flame-retardant system is formed by an imidazole structure and 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, the limiting oxygen index and the char formation effect of the polystyrene heat-insulating board during combustion are improved, the combustion heat release rate is reduced, the flame-retardant effect of the board is improved, and the polystyrene board has better application in the fields of fire protection, flame retardance and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) To 50mL of ethanol, 4g of naphthalene-2, 6-dicarboxaldehyde and 8.5g of histidine were added dropwise with 0.6mL of glacial acetic acid, refluxed at 70℃for 4 hours, concentrated to remove ethanol, added with water and dichloromethane, extracted, the organic phase concentrated, washed with petroleum ether and dried to obtain naphthalene-2, 6-histidine intermediate.
(2) 5g of beta-cyclodextrin, 4g of naphthalene-2, 6-histidine intermediate, 1.5g of N-hydroxysuccinimide and 3.5g of dicyclohexylcarbodiimide are added into 100mL of dimethyl sulfoxide for reaction for 36h at 40 ℃, and then the naphthalene-histidine cross-linked cyclodextrin is obtained after suction filtration, ethanol washing and drying.
(3) To 200mL of water were added 5g of naphthalene-histidine cross-linked cyclodextrin, 2.5g of 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxideAnd (3) carrying out ultrasonic vibration for 0.5h, then stirring for 24h, filtering, washing with ethanol, and drying to obtain the cyclodextrin microcapsule flame retardant.
(4) Adding the melamine modified urea-formaldehyde resin and the cyclodextrin microcapsule flame retardant into a stirrer, uniformly mixing, controlling the stirring speed to be 80r/min, and stirring for 8min to obtain melamine modified urea-formaldehyde resin flame-retardant coating liquid;
(5) Pre-foaming 90 parts by weight of expandable polystyrene beads in a steam system at 100 ℃ for 4min, curing the expandable polystyrene beads at room temperature for 24h, uniformly mixing the expandable polystyrene beads with 10 parts of melamine modified urea resin flame-retardant coating liquid in a stirrer, controlling the stirring speed to be 250r/min and the stirring time to be 60min, molding the materials in a flat vulcanizing machine, controlling the temperature to be 100 ℃, controlling the pressure to be 8MPa and the time to be 4min, and obtaining the flame-retardant polystyrene heat-insulating board.
Example 2
(1) To 80mL of ethanol, 4g of naphthalene-2, 6-dicarboxaldehyde and 6.8g of histidine were added dropwise with 0.72mL of glacial acetic acid, refluxed at 80℃for 5 hours, concentrated to remove ethanol, added with water and dichloromethane, extracted, the organic phase concentrated, washed with petroleum ether and dried to obtain naphthalene-2, 6-histidine intermediate.
(2) To 150mL of dimethyl sulfoxide, 5g of beta-cyclodextrin, 8g of naphthalene-2, 6-histidine intermediate, 3.5g of N-hydroxysuccinimide and 7g of dicyclohexylcarbodiimide were added, and the mixture was reacted at 35℃for 48 hours, filtered with suction, washed with ethanol and dried to obtain naphthalene-histidine crosslinked cyclodextrin.
(3) 5g of naphthalene-histidine cross-linked cyclodextrin and 5g of 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide are added into 200mL of water, ultrasonic vibration is carried out for 0.5h, then stirring is carried out for 24h, filtering, ethanol washing and drying are carried out, and the cyclodextrin microcapsule flame retardant is obtained.
(4) Adding the melamine modified urea-formaldehyde resin and the cyclodextrin microcapsule flame retardant into a stirrer, uniformly mixing, controlling the stirring speed to be 100r/min, and stirring for 8min to obtain melamine modified urea-formaldehyde resin flame-retardant coating liquid;
(5) Pre-foaming 85 parts by weight of expandable polystyrene beads in a steam system at 100 ℃ for 4min, curing the expandable polystyrene beads at room temperature for 24h, uniformly mixing the expandable polystyrene beads with 15 parts of melamine modified urea resin flame-retardant coating liquid in a stirrer, controlling the stirring speed to be 250r/min and the stirring time to be 60min, molding the materials in a flat vulcanizing machine, controlling the temperature to be 120 ℃ and the pressure to be 8MPa and the time to be 4min, and obtaining the flame-retardant polystyrene heat-insulating board.
Example 3
(1) To 80mL of ethanol, 4g of naphthalene-2, 6-dicarboxaldehyde and 10g of histidine were added, 0.6mL of glacial acetic acid was added dropwise, reflux was performed at 70℃for 5h, ethanol was removed by concentration, water and dichloromethane were added, extraction was performed, the organic phase was concentrated, petroleum ether was washed, and drying was performed to obtain a naphthalene-2, 6-histidine intermediate.
(2) 5g of beta-cyclodextrin, 12.5g of naphthalene-2, 6-histidine intermediate, 5g of N-hydroxysuccinimide and 11g of dicyclohexylcarbodiimide are added into 200mL of dimethyl sulfoxide for reaction for 24 hours at 50 ℃, and then the naphthalene-histidine cross-linked cyclodextrin is obtained after suction filtration, ethanol washing and drying.
(3) 5g of naphthalene-histidine cross-linked cyclodextrin and 7.5g of 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide are added into 200mL of water, ultrasonic vibration is carried out for 0.5h, then stirring is carried out for 24h, filtering, ethanol washing and drying are carried out, and the cyclodextrin microcapsule flame retardant is obtained.
(4) Adding the melamine modified urea-formaldehyde resin and the cyclodextrin microcapsule flame retardant into a stirrer, uniformly mixing, controlling the stirring speed to be 100r/min, and stirring for 8min to obtain melamine modified urea-formaldehyde resin flame-retardant coating liquid;
(5) Pre-foaming 75 parts by weight of expandable polystyrene beads in a steam system at 100 ℃ for 4min, curing the expandable polystyrene beads at room temperature for 24h, uniformly mixing the expandable polystyrene beads with 25 parts of melamine modified urea resin flame-retardant coating liquid in a stirrer, controlling the stirring speed to be 250r/min and the stirring time to be 60min, molding the materials in a flat vulcanizing machine, controlling the temperature to be 100 ℃, controlling the pressure to be 8MPa and the time to be 4min, and obtaining the flame-retardant polystyrene heat-insulating board.
Comparative example 1: the difference from example 1 is that no cyclodextrin microcapsule flame retardant is added.
Comparative example 2: the difference from example 1 is that beta-cyclodextrin is used instead of cyclodextrin microcapsule flame retardant.
Comparative example 3: the difference from example 1 is that naphthalene-histidine cross-linked cyclodextrin is used instead of cyclodextrin microcapsule flame retardant.
Comparative example 4: the difference from example 1 is that 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide is used instead of cyclodextrin microcapsule flame retardant.
Comparative example 5:
(1) To 200mL of water was added 5g of beta-cyclodextrin, 2.5g of 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxideAnd (3) carrying out ultrasonic vibration for 0.5h, then stirring for 24h, filtering, washing with ethanol, and drying to obtain the cyclodextrin flame retardant.
(2) Adding the melamine modified urea-formaldehyde resin and the cyclodextrin flame retardant into a stirrer, uniformly mixing, controlling the stirring speed to be 100r/min, and stirring for 8min to obtain melamine modified urea-formaldehyde resin flame-retardant coating liquid;
(3) Pre-foaming 90 parts by weight of expandable polystyrene beads in a steam system at 100 ℃ for 4min, curing the expandable polystyrene beads at room temperature for 24h, uniformly mixing the expandable polystyrene beads with 10 parts of melamine modified urea resin flame-retardant coating liquid in a stirrer, controlling the stirring speed to be 250r/min and the stirring time to be 60min, molding the materials in a flat vulcanizing machine, controlling the temperature to be 100 ℃, controlling the pressure to be 8MPa and the time to be 4min, and obtaining the flame-retardant polystyrene heat-insulating board.
The cyclodextrin microcapsule flame retardant prepared in step (3) of examples 1 to 3 and the cyclodextrin flame retardant prepared in step (1) of comparative example 5 were weighed (m), respectively, and the entrapment rate Q, q= (m-m) of 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide was calculated 0 )/m 0 ，m 0 Is naphthalene-histidine cross-linked cyclodextrin or beta-cyclodextrin (5 g).
As the dosage of 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide increases, the embedding amount of the naphthalene-histidine cross-linked cyclodextrin prepared in the examples 1-3 increases and then tends to be stable, reaching 0.378-0.722g/g. Whereas comparative example 5 had an entrapment amount of only 0.226g/g because naphthalene-histidine-crosslinked cyclodextrin had a space-crosslinked network structure, had a larger specific surface area, had more entrapment sites, and contained imidazole, ester functional groups, and could undergo hydrogen bond interactions with the hydroxyl groups of 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, thereby increasing the entrapment amount.
The flame retardant property of the polystyrene insulation board is tested by adopting an oxygen index tester and a cone calorimeter. The compressive strength was tested by a universal material tester.
Compared with comparative example 1, the usage amount of the melamine modified urea resin flame retardant coating liquid in the polystyrene heat insulation board of examples 1-3 is gradually increased, the limiting oxygen index and carbon residue of the polystyrene heat insulation board are larger and larger, the maximum oxygen index and carbon residue are 28.9 and 11.3 percent, the peak value of the heat release rate is smaller and smaller, and the minimum oxygen content is only 92.7kW/m 2 Has excellent flame retardant property. The cyclodextrin microcapsule flame retardant in the coating liquid contains rigid naphthalene ring and imidazole group, and forms an intumescent flame retardant system with the coated 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, so that the char forming effect and flame retardance of the board are obviously improved. Along with the gradual increase of the consumption of the melamine modified urea resin flame-retardant coating liquid, the compression strength of the plate can be reduced, so that the consumption of the coating liquid is not excessively large.
Comparative example 2 was added with only beta-cyclodextrin, comparative example 3 was added with only naphthalene-histidine cross-linked cyclodextrin, comparative example 4 was added with only 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, and no intumescent flame retardant system was formed, so that the char formation effect and flame retardance of polystyrene insulation boards were poor.
In comparative example 5, only cyclodextrin flame retardant is added, cyclodextrin does not form a space cross-linked network structure, and does not contain imidazole groups and ester groups, and hydrogen bond interaction cannot be formed between cyclodextrin and 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide, so that the coating amount is smaller, and the flame retardance of a plate can be improved, but the flame retardance effect is inferior to that of example 1.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The preparation process of the flame-retardant polystyrene heat-insulating plate is characterized in that the flame-retardant polystyrene heat-insulating plate comprises 75-90 parts by weight of expandable polystyrene beads and 10-25 parts by weight of melamine modified urea resin flame-retardant coating liquid; the preparation process comprises the following steps:
s1, adding melamine modified urea-formaldehyde resin and cyclodextrin microcapsule flame retardant into a stirrer, uniformly mixing, and uniformly stirring to obtain melamine modified urea-formaldehyde resin flame-retardant coating liquid;
s2, pre-foaming the expandable polystyrene beads in a water vapor system, curing the expandable polystyrene beads at room temperature, uniformly mixing the expandable polystyrene beads with melamine modified urea resin flame-retardant coating liquid in a stirrer, and molding the materials in a plate vulcanizing machine to obtain the flame-retardant polystyrene heat-insulation board.
2. The process for preparing the flame-retardant polystyrene thermal insulation board according to claim 1, wherein the stirring speed is controlled to be 80-150r/min in the step S1, and the stirring time is controlled to be 5-10min; and S2, controlling the stirring speed to be 200-300r/min and the stirring time to be 30-60min.
3. The process for preparing the flame-retardant polystyrene thermal insulation board according to claim 1, wherein the temperature is controlled to be 100-120 ℃ and the pressure is controlled to be 7-10MPa during the molding in the step S2, and the time is 3-5min.
4. The process for preparing the flame-retardant polystyrene thermal insulation board according to claim 1, wherein the process for preparing the cyclodextrin microcapsule flame retardant is as follows:
(1) Adding naphthalene-2, 6-dicarboxaldehyde and histidine into ethanol, dropwise adding glacial acetic acid, refluxing at 70-80deg.C for 2-5 hr, concentrating to remove ethanol, adding water and dichloromethane, extracting, concentrating organic phase, washing with petroleum ether, and drying to obtain naphthalene-2, 6-histidine intermediate;
(2) Adding beta-cyclodextrin, naphthalene-2, 6-histidine intermediate, N-hydroxysuccinimide and dicyclohexylcarbodiimide into dimethyl sulfoxide, reacting for 24-48h at 35-50 ℃, filtering, washing with ethanol, and drying to obtain naphthalene-histidine cross-linked cyclodextrin;
(3) Adding naphthalene-histidine crosslinked cyclodextrin and 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide into water, carrying out ultrasonic vibration for 0.5-1h, then stirring for 12-24h, filtering, washing with ethanol, and drying to obtain the cyclodextrin microcapsule flame retardant.
5. The process for preparing a flame-retardant polystyrene thermal insulation board according to claim 1, wherein the ratio of each reactant in (1) is as follows: naphthalene-2, 6-dicarboxaldehyde histidine glacial acetic acid=1 g (1.7-2.5 g) (0.1-0.18) mL.
6. The process for preparing a flame-retardant polystyrene insulation board according to claim 1, wherein the proportion of each reactant in (2) is beta-cyclodextrin, naphthalene-2, 6-histidine intermediate, N-hydroxysuccinimide and dicyclohexylcarbodiimide=1 g (0.8-2.5) g (0.3-1) g (0.7-2.2) g.
7. The process for preparing a flame-retardant polystyrene insulation board according to claim 1, wherein the ratio of each reactant in (3) is naphthalene-histidine cross-linked cyclodextrin 2,6, 7-trioxa-1-phosphabicyclo (2.2.2) octane-4-methanol-1-oxide=1 g (0.5-1.5 g).
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