CN115403609A - Preparation method of tris [3- (trimethoxysilyl) propyl ] isocyanurate - Google Patents
Preparation method of tris [3- (trimethoxysilyl) propyl ] isocyanurate Download PDFInfo
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- CN115403609A CN115403609A CN202210496369.0A CN202210496369A CN115403609A CN 115403609 A CN115403609 A CN 115403609A CN 202210496369 A CN202210496369 A CN 202210496369A CN 115403609 A CN115403609 A CN 115403609A
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- propyl
- trimethoxysilyl
- tris
- isocyanurate
- reaction
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- QWOVEJBDMKHZQK-UHFFFAOYSA-N 1,3,5-tris(3-trimethoxysilylpropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CO[Si](OC)(OC)CCCN1C(=O)N(CCC[Si](OC)(OC)OC)C(=O)N(CCC[Si](OC)(OC)OC)C1=O QWOVEJBDMKHZQK-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000003063 flame retardant Substances 0.000 claims abstract description 32
- 229920002472 Starch Polymers 0.000 claims abstract description 31
- 235000019698 starch Nutrition 0.000 claims abstract description 31
- 239000008107 starch Substances 0.000 claims abstract description 31
- -1 dimethylsilane-phosphate Chemical compound 0.000 claims abstract description 30
- 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 28
- 229920001523 phosphate polymer Polymers 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 claims abstract description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 11
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 10
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003463 adsorbent Substances 0.000 claims description 8
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 9
- 238000004132 cross linking Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000000779 smoke Substances 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract 1
- 230000001629 suppression Effects 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000881 Modified starch Polymers 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 241001122767 Theaceae Species 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ABUPITQJZCZPNC-UHFFFAOYSA-N diethyl 2-hydroxyethyl phosphate Chemical compound CCOP(=O)(OCC)OCCO ABUPITQJZCZPNC-UHFFFAOYSA-N 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 2
- 229930182490 saponin Natural products 0.000 description 2
- 150000007949 saponins Chemical class 0.000 description 2
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 125000005371 silicon functional group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
Abstract
The invention relates to the technical field of silane coupling agents, and discloses a tris [3- (trimethoxysilyl) propyl ] isocyanurate, which is synthesized by taking 3-isocyanatopropyl trimethoxy silane as a precursor, has a simple preparation method, simple and convenient operation and mild reaction and is suitable for industrial production, and the tris [3- (trimethoxysilyl) propyl ] isocyanurate is taken as a crosslinking modifier, is hydrolyzed to generate active silicon hydroxyl which can be subjected to dehydration condensation with the hydroxyl of starch and the terminal hydroxyl of dimethylsilane-phosphate polymer, so that the tris [3- (trimethoxysilyl) propyl ] isocyanurate, the hydroxyl of starch and the terminal hydroxyl of dimethylsilane-phosphate polymer are crosslinked to obtain the silicon-containing starch-based intumescent flame retardant, and the silicon-containing starch-based intumescent flame retardant has excellent effects of smoke suppression, molten drop prevention and oxygen barrier.
Description
Technical Field
The invention relates to the technical field of silane coupling agents, in particular to tris [3- (trimethoxysilyl) propyl ] isocyanurate and a preparation method thereof.
Background
The silane coupling agent contains silicon functional groups and carbon functional groups simultaneously in molecules, is an excellent chemical modifier and treating agent for inorganic, organic and composite materials, and is widely applied to the fields of coatings, buildings, automobiles, electronics, aviation and the like. The silane hydrolyzed oligomer is one or more than two silane coupling agents which are obtained by a certain hydrolytic condensation process and has the characteristics of high viscosity, high functionality and 2-10 silane chain links, and has the characteristics of high crosslinking, high adhesion, high boiling point, low volatility, low VOC (volatile organic compound), low dosage and the like.
The silane coupling agent has wide application in the field of flame retardance, for example, in the document silane coupling agent modified tea saponin intumescent flame retardant and coating application, the silane coupling agent KH-550 is reported to modify the tea saponin composite intumescent flame retardant, and the silane coupling agent KH-550 is applied to the flame retardant coating, so that the flame retardance of the coating is obviously improved; the intumescent flame retardant integrates a carbon source, a phosphorus source and a nitrogen source, such as an ammonium polyphosphate type intumescent flame retardant, a starch-based intumescent flame retardant and the like, has good char forming property and excellent flame retardance, and for example, patent CN112063019B discloses that a starch derivative is used as the carbon source, is subjected to composite crosslinking with the starch derivative through high-temperature dry-heat reaction to form a compact coating layer on the surface of the ammonium polyphosphate, and the ammonium polyphosphate is modified by utilizing the high char forming effect of the starch and combining the crosslinking effect of phosphate rich in phosphorus, so that the prepared composite intumescent flame retardant has excellent water resistance and flame retardance efficiency.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the isocyanuric acid tris [3- (trimethoxysilyl) propyl ] ester and the preparation method thereof, and the isocyanuric acid tris [3- (trimethoxysilyl) propyl ] ester is applied to the intumescent flame retardant.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: tri [3- (trimethoxysilyl) propyl ] isocyanurate and application thereof.
Preferably, the isocyanuric acid tris [3- (trimethoxy silicon)Alkyl) propyl group]The ester has the formula C 21 H 45 N 3 O 12 Si 3 The structural formula is shown as formula (I):
preferably, the preparation method of the isocyanuric acid tris [3- (trimethoxysilyl) propyl ] comprises the following steps:
s1: adding 3-isocyanate propyl trimethoxy silane into a reaction bottle, adjusting the pH value of a reaction system, adding dibutyltin dilaurate in a nitrogen atmosphere, heating and stirring for reaction.
S2: cooling after reaction, adding polyacrylamide adsorbent and diatomite filter aid, uniformly stirring, and carrying out reduced pressure filtration to obtain the tris [3- (trimethoxysilyl) propyl ] isocyanurate.
Preferably, disodium hydrogen phosphate is added into the S1 to adjust the pH of the reaction system to 7-10.
Preferably, the reaction in S1 is stirred and reacted for 2 to 8 hours at the temperature of 125 to 145 ℃.
Preferably, the weight ratio of the 3-isocyanatopropyltrimethoxysilane to the dibutyltin dilaurate in the S1 is 100.
Preferably, the weight ratio of 15-40 dimethyldichlorosilane to bis (2-hydroxyethyl) diethyl phosphate and triethylamine to the reaction solvent is 100-280-360, the mixture is uniformly stirred and then heated to 40-75 ℃, the reaction is carried out for 6-18h, the mixture is cooled after the reaction, methanol is added for precipitation, and the mixture is filtered, washed by distilled water and acetone, so as to obtain the hydroxyl-terminated dimethylsilane-phosphate polymer.
S3: adding gelatinized starch into an ethanol water solution, then adding hydroxyl-terminated dimethylsilane-phosphate polymer and tris [3- (trimethoxysilyl) propyl ] isocyanurate, heating and stirring for reaction, cooling after reaction, filtering, washing with distilled water and acetone to obtain the silicon-containing starch-based intumescent flame retardant.
Preferably, the reaction solvent is any one of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran and 1,4-dioxane.
Preferably, the weight ratio of gelatinized starch, hydroxydimethylsilane-phosphate polymer and tris [3- (trimethoxysilyl) propyl ] isocyanurate in S3 is from 15 to 65.
Preferably, the reaction in S3 is stirred and reacted for 5 to 15 hours at the temperature of 60 to 90 ℃.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the tris [3- (trimethoxysilyl) propyl ] isocyanurate takes 3-isocyanatopropyl trimethoxy silane as a precursor to synthesize a novel silane coupling agent, namely tris [3- (trimethoxysilyl) propyl ] isocyanurate, and the preparation method is simple, simple and convenient to operate, mild in reaction and suitable for industrial production.
Dimethyl dichlorosilane and diethyl bis (2-hydroxyethyl) phosphate are used as polymerization monomers, the reaction ratio is controlled, hydroxyl-terminated dimethylsilane-phosphate polymer is prepared, then tris [3- (trimethoxysilyl) propyl ] isocyanurate is used as a crosslinking modifier, the contained trimethoxy silicon is hydrolyzed to generate active silicon hydroxyl which can be subjected to dehydration condensation with the hydroxyl of starch and the hydroxyl-terminated groups of the dimethylsilane-phosphate polymer, and the three are crosslinked to obtain the silicon-containing starch-based intumescent flame retardant.
Starch is used as a carbon source, phosphate is used as a phosphorus source, triazine isocyanurate is used as a nitrogen source to form an intumescent flame retardant system, a large amount of nitrogen-containing non-combustible gas and phosphoric acid derivatives are generated during combustion, a continuous and stable intumescent carbon layer can be formed, the flame retardant contains rich silicon flame retardant elements, and micro-nano silicon dioxide is generated in situ in the intumescent carbon layer during combustion, so that the intumescent flame retardant can play a role in supporting the carbon layer, enhancing the stability of a carbon barrier layer, playing a better role in inhibiting smoke, preventing molten drops and blocking oxygen, and is an intumescent flame retardant with excellent comprehensive performance.
Drawings
FIG. 1 is a reaction scheme for preparing tris [3- (trimethoxysilyl) propyl ] isocyanurate.
FIG. 2 is a FT-IR diagram of tris [3- (trimethoxysilyl) propyl ] isocyanurate.
FIG. 3 is a reaction mechanism diagram for preparing a siliceous starch-based intumescent flame retardant.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a tris [3- (trimethoxysilyl) propyl ] isocyanurate is applied to an intumescent flame retardant:
(1) Adding 3-isocyanatopropyl trimethoxy silane into a reaction bottle, then adding disodium hydrogen phosphate to adjust the pH value of a reaction system to be 7-10, adding dibutyltin dilaurate in a nitrogen atmosphere, controlling the weight ratio of the 3-isocyanatopropyl trimethoxy silane to the dibutyltin dilaurate to be 0.15-0.3, and stirring at 125-145 ℃ for reaction for 2-8h.
(2) Cooling after reaction, adding polyacrylamide adsorbent and diatomite filter aid, stirring uniformly, and filtering under reduced pressure to obtain the tris [3- (trimethoxysilyl) propyl ] isocyanurate.
(3) Adding dimethyldichlorosilane, diethyl bis (2-hydroxyethyl) phosphate and triethylamine in a weight ratio of 100-280-360.
(4) Adding gelatinized starch into an ethanol water solution, then adding a hydroxyl-terminated dimethylsilane-phosphate polymer and tris [3- (trimethoxysilyl) propyl ] isocyanurate, controlling the weight ratio of the gelatinized starch, the hydroxyl-terminated dimethylsilane-phosphate polymer and the tris [3- (trimethoxysilyl) propyl ] isocyanurate to be 15-30, heating to 60-90 ℃, stirring for reaction for 5-15h, cooling after reaction, filtering, washing with distilled water and acetone, and obtaining the silicon-containing starch-based intumescent flame retardant.
Example 1
(1) Adding 20g of 3-isocyanatopropyl trimethoxy silane into a reaction bottle, then adding disodium hydrogen phosphate to adjust the pH of the reaction system to 9, adding 0.035g of dibutyltin dilaurate in a nitrogen atmosphere, and stirring for reaction at 125 ℃ for 8 hours.
(2) Cooling after reaction, adding polyacrylamide adsorbent and diatomite filter aid, uniformly stirring, and carrying out reduced pressure filtration to obtain the tris [3- (trimethoxysilyl) propyl ] isocyanurate.
(3) Adding 5g of dimethyldichlorosilane, 15g of diethyl bis (2-hydroxyethyl) phosphate and 0.75g of triethylamine into 100mL of N, N-dimethylformamide under an ice bath, uniformly stirring, heating to 75 ℃, reacting for 18h, cooling after reaction, adding methanol for precipitation, filtering, washing with distilled water and acetone to obtain the hydroxyl-terminated dimethylsilane-phosphate polymer.
(4) Adding 10g of gelatinized starch into 150mL of ethanol aqueous solution, then adding 0.26g of hydroxyl-terminated dimethylsilane-phosphate polymer and 1.5g of tris [3- (trimethoxysilyl) propyl ] isocyanurate, heating to 90 ℃, stirring for reaction for 5 hours, cooling after reaction, filtering, washing with distilled water and acetone to obtain the silicon-containing starch-based intumescent flame retardant.
Example 2
(1) 100g of 3-isocyanatopropyltrimethoxysilane is added into a reaction bottle, then disodium hydrogen phosphate is added to adjust the pH of the reaction system to 10, 0.15g of dibutyltin dilaurate is added under the nitrogen atmosphere, and the mixture is stirred and reacted for 8 hours at 125 ℃.
(2) Cooling after reaction, adding polyacrylamide adsorbent and diatomite filter aid, stirring uniformly, and filtering under reduced pressure to obtain the tris [3- (trimethoxysilyl) propyl ] isocyanurate.
(3) Adding 5g of dimethyldichlorosilane, 16g of diethyl bis (2-hydroxyethyl) phosphate and 0.75g of triethylamine into 150mL of tetrahydrofuran under an ice bath, uniformly stirring, heating to 40 ℃, reacting for 18h, cooling after reaction, adding methanol for precipitation, filtering, washing with distilled water and acetone to obtain the hydroxyl-terminated dimethylsilane-phosphate polymer.
(4) Adding 10g of gelatinized starch into 300mL of ethanol aqueous solution, then adding 0.65g of hydroxyl-terminated dimethylsilane-phosphate polymer and 3g of tris [3- (trimethoxysilyl) propyl ] isocyanurate, heating to 65 ℃, stirring for reacting for 15h, cooling after reacting, filtering, washing with distilled water and acetone to obtain the silicon-containing starch-based intumescent flame retardant.
Example 3
(1) 20g of 3-isocyanatopropyltrimethoxysilane is added into a reaction bottle, then disodium hydrogen phosphate is added to adjust the pH of the reaction system to 7, 0.042g of dibutyltin dilaurate is added under the nitrogen atmosphere, and the reaction is stirred at 145 ℃ for 3 hours.
(2) Cooling after reaction, adding polyacrylamide adsorbent and diatomite filter aid, stirring uniformly, and filtering under reduced pressure to obtain the tris [3- (trimethoxysilyl) propyl ] isocyanurate.
(3) Under ice bath, 150mL of 1,4-dioxane is added with 5g of dimethyldichlorosilane, 17.2g of diethyl bis (2-hydroxyethyl) phosphate and 1.8g of triethylamine, the mixture is uniformly stirred and heated to 45 ℃, the reaction is carried out for 12 hours, after the reaction, the mixture is cooled and added with methanol for precipitation, and the mixture is filtered, distilled water and acetone are washed to obtain the hydroxyl-terminated dimethylsilane-phosphate polymer.
(4) Adding 10g of gelatinized starch into 150mL of ethanol aqueous solution, then adding 0.52g of hydroxyl-terminated dimethylsilane-phosphate polymer and 3.5g of tris [3- (trimethoxysilyl) propyl ] isocyanurate, heating to 80 ℃, stirring for reacting for 8h, cooling after reacting, filtering, washing with distilled water and acetone to obtain the silicon-containing starch-based intumescent flame retardant.
Example 4
(1) 300g of 3-isocyanatopropyltrimethoxysilane was added to a reaction flask, then disodium hydrogen phosphate was added to adjust the pH of the reaction system to 8.5, 0.5g of dibutyltin dilaurate was added under a nitrogen atmosphere, and the reaction was stirred at 135 ℃ for 3 hours.
(2) Cooling after reaction, adding polyacrylamide adsorbent and diatomite filter aid, stirring uniformly, and filtering under reduced pressure to obtain the tris [3- (trimethoxysilyl) propyl ] isocyanurate.
(3) Adding 5g of dimethyldichlorosilane, 15g of bis (2-hydroxyethyl) diethyl phosphate and 1.1g of triethylamine into 100mL of N, N-dimethylformamide in an ice bath, uniformly stirring, heating to 75 ℃, reacting for 6h, cooling after reaction, adding methanol for precipitation, filtering, washing with distilled water and acetone to obtain the hydroxyl-terminated dimethylsilane-phosphate polymer.
(4) Adding 10g of gelatinized starch into 300mL of ethanol aqueous solution, then adding 0.6g of hydroxyl-terminated dimethylsilane-phosphate polymer and 3g of tris [3- (trimethoxysilyl) propyl ] isocyanurate, heating to 80 ℃, stirring for reaction for 12h, cooling after reaction, filtering, washing with distilled water and acetone to obtain the silicon-containing starch-based intumescent flame retardant.
Example 5
(1) 300g of 3-isocyanatopropyltrimethoxysilane is added into a reaction bottle, then disodium hydrogen phosphate is added to adjust the pH value of the reaction system to be 8, 0.6g of dibutyltin dilaurate is added under the nitrogen atmosphere, and the mixture is stirred and reacted for 3 hours at the temperature of 140 ℃.
(2) Cooling after reaction, adding polyacrylamide adsorbent and diatomite filter aid, stirring uniformly, and filtering under reduced pressure to obtain the tris [3- (trimethoxysilyl) propyl ] isocyanurate.
(3) Adding 5g of dimethyldichlorosilane, 15.8g of diethyl bis (2-hydroxyethyl) phosphate and 0.85g of triethylamine into 100mL of N, N-dimethylacetamide under an ice bath, uniformly stirring, heating to 75 ℃, reacting for 6h, cooling after reaction, adding methanol for precipitation, filtering, and washing with distilled water and acetone to obtain the hydroxyl-terminated dimethylsilane-phosphate polymer.
(4) Adding 10g of gelatinized starch into 200mL of ethanol aqueous solution, then adding 0.38g of hydroxyl-terminated dimethylsilane-phosphate polymer and 2.2g of tris [3- (trimethoxysilyl) propyl ] isocyanurate, heating to 70 ℃, stirring, reacting for 12h, cooling after reaction, filtering, washing with distilled water and acetone to obtain the silicon-containing starch-based intumescent flame retardant.
And (3) placing the silicon-containing starch-based intumescent flame retardant into a TGA thermogravimetric analyzer, introducing nitrogen, controlling the heating rate to be 20 ℃/min and the maximum test temperature to be 800 ℃, and performing thermal performance analysis.
The initial decomposition temperature of the siliceous starch base expanding flame retardant reaches 288.5-319.0 ℃, and the residual carbon content reaches 56.4-73.5%.
Claims (9)
1. Isocyanuric acid tri [3- (trimethoxysilyl) propyl group]An ester characterized by: the tris [3- (trimethoxysilyl) propyl isocyanurate]The ester has the formula C 21 H 45 N 3 O 12 Si 3 The structural formula is shown as formula (I):
2. tris [3- (trimethoxysilyl) propyl ] isocyanurate according to claim 1, wherein: the preparation method of the isocyanuric acid tris [3- (trimethoxysilyl) propyl ] comprises the following steps:
s1: adding 3-isocyanate propyl trimethoxy silane into a reaction bottle, adjusting the pH value of a reaction system, adding dibutyltin dilaurate in a nitrogen atmosphere, heating and stirring for reaction;
s2: cooling after reaction, adding polyacrylamide adsorbent and diatomite filter aid, stirring uniformly, and filtering under reduced pressure to obtain the tris [3- (trimethoxysilyl) propyl ] isocyanurate.
3. Tris [3- (trimethoxysilyl) propyl ] isocyanurate according to claim 2, wherein: and adding disodium hydrogen phosphate into the S1 to adjust the pH of the reaction system to 7-10.
4. Tris [3- (trimethoxysilyl) propyl ] isocyanurate according to claim 2, wherein: the reaction in the S1 is stirred and reacted for 2 to 8 hours at the temperature of between 125 and 145 ℃.
5. Tris [3- (trimethoxysilyl) propyl ] isocyanurate according to claim 2, wherein: the weight ratio of the 3-isocyanatopropyl trimethoxy silane to the dibutyltin dilaurate in the S1 is 0.15-0.3.
6. Use of tris [3- (trimethoxysilyl) propyl ] isocyanurate as claimed in any one of claims 1 to 5 in intumescent flame retardants, characterized in that: adding 15-40 parts by weight of dimethyldichlorosilane, diethyl bis (2-hydroxyethyl) phosphate and triethylamine into a reaction solvent in an ice bath, uniformly stirring, heating to 40-75 ℃, reacting for 6-18h, cooling after reaction, adding methanol for precipitation, filtering, washing with distilled water and acetone to obtain a hydroxyl-terminated dimethylsilane-phosphate polymer;
s3: adding gelatinized starch into an ethanol water solution, then adding hydroxyl-terminated dimethylsilane-phosphate polymer and tris [3- (trimethoxysilyl) propyl ] isocyanurate, heating and stirring for reaction, cooling after reaction, filtering, washing with distilled water and acetone to obtain the silicon-containing starch-based intumescent flame retardant.
7. Use of tris [3- (trimethoxysilyl) propyl ] isocyanurate in accordance with claim 6 in intumescent flame retardants, characterized in that: the reaction solvent is any one of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran and 1,4-dioxane.
8. Use of tris [3- (trimethoxysilyl) propyl ] isocyanurate in accordance with claim 6 in intumescent flame retardants, characterized in that: the weight ratio of the gelatinized starch, the hydroxyl-terminated dimethylsilane-phosphate polymer and the tris [3- (trimethoxysilyl) propyl ] isocyanurate in S3 is (100).
9. Use of tris [3- (trimethoxysilyl) propyl ] isocyanurate in accordance with claim 6 in intumescent flame retardants, characterized in that: the reaction in the S3 is stirred and reacted for 5 to 15 hours at the temperature of between 60 and 90 ℃.
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| CN116948390A (en) * | 2023-09-21 | 2023-10-27 | 赢胜节能集团股份有限公司 | Composite heat-insulating material based on aluminum silicate fibers |
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| CN116948390B (en) * | 2023-09-21 | 2023-12-01 | 赢胜节能集团股份有限公司 | Composite heat-insulating material based on aluminum silicate fibers |
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