CN109369699B - Reactive organosilicon flame retardant allyl silicic acid trisilacyl alcohol ester compound and preparation method thereof - Google Patents
Reactive organosilicon flame retardant allyl silicic acid trisilacyl alcohol ester compound and preparation method thereof Download PDFInfo
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- CN109369699B CN109369699B CN201811298987.4A CN201811298987A CN109369699B CN 109369699 B CN109369699 B CN 109369699B CN 201811298987 A CN201811298987 A CN 201811298987A CN 109369699 B CN109369699 B CN 109369699B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 60
- 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 54
- -1 alcohol ester compound Chemical class 0.000 title claims abstract description 39
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000005047 Allyltrichlorosilane Substances 0.000 claims abstract description 10
- HKFSBKQQYCMCKO-UHFFFAOYSA-N trichloro(prop-2-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CC=C HKFSBKQQYCMCKO-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- PUWSPTQNHGUGDZ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butane-1,3-diol Chemical compound CC(O)C(CO)(CO)CO PUWSPTQNHGUGDZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000010992 reflux Methods 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 12
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 12
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 8
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical group CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 16
- 239000011347 resin Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052710 silicon Inorganic materials 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004952 Polyamide Substances 0.000 abstract description 4
- 239000003822 epoxy resin Substances 0.000 abstract description 4
- 229920002647 polyamide Polymers 0.000 abstract description 4
- 229920000647 polyepoxide Polymers 0.000 abstract description 4
- 229920000728 polyester Polymers 0.000 abstract description 4
- 229920000098 polyolefin Polymers 0.000 abstract description 4
- 239000004814 polyurethane Substances 0.000 abstract description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 description 14
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006757 chemical reactions by type Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 229910003849 O-Si Inorganic materials 0.000 description 2
- 229910003872 O—Si Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- REFYUHMDDXHPQO-UHFFFAOYSA-N [Si].[Si].[Si].C1(=CC=CC=C1)O[Si](O)(O)O Chemical compound [Si].[Si].[Si].C1(=CC=CC=C1)O[Si](O)(O)O REFYUHMDDXHPQO-UHFFFAOYSA-N 0.000 description 1
- AWPXVGLPVPEEBH-UHFFFAOYSA-N [Si].[Si].[Si].[Si] Chemical compound [Si].[Si].[Si].[Si] AWPXVGLPVPEEBH-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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- 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 Table
- 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
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/549—Silicon-containing compounds containing silicon in a ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to a reactive organosilicon flame retardant allylThe structure of the silicic acid trisilacyl alcohol ester compound is shown as the following formula:
Description
Technical Field
The invention relates to a reactive organosilicon flame retardant allyl silicic acid trisilacyl alcohol ester compound and a preparation method thereof, in particular to a reactive organosilicon flame retardant allyl tris { 1-methyl-1-sila-2, 6, 7-trioxabicyclo [2, 2, 2] octyl- (4) -methyleneoxy } silane compound and a preparation method thereof, wherein the compound is suitable for serving as a flame retardant for materials such as unsaturated resin, styrene, acrylate, polyester, polyamide, polyurethane, epoxy resin, polyolefin and the like.
Background
The wide application of flammable synthetic polymer materials drives the rapid development of the flame retardant industry; along with the continuous improvement of living standard and the continuous enhancement of consciousness of safety and environmental protection of people, higher requirements are made on a flame retardant, the flame retardant efficiency is required, meanwhile, the safety, non-toxicity and environmental protection performance are better emphasized, the research and application of the organic silicon flame retardant cater to the social requirements, and particularly, the cage-shaped organic silicon derivative serving as the flame retardant has good thermal stability and good char formation property and has the function of preventing molten drops from causing secondary combustion, so that the cage-shaped organic silicon derivative becomes a popular research topic of the flame retardant which is halogen-free, environment-friendly, low-toxicity, high-temperature-resistant and efficient at present.
In addition, the flame retardants used in the current polymer materials are additive flame retardants and reactive flame retardants. Because of more or less incompatibility between the additive flame retardant and the polymer matrix, the additive flame retardant can escape, decompose and the like during processing, and the performance of the material is influenced. The reactive flame retardant is prepared by directly introducing flame retardant elements into a main chain or a side chain of a polymer in a copolymerization or grafting mode, so that the effect of improving the flame retardance can be achieved, the defect that an additive flame retardant migrates or volatilizes from the surface of the polymer can be overcome, the influence on the physical and chemical properties of the polymer is small, and the development prospect is good.
The invention discloses a reactive organosilicon flame retardant allyl silicic acid trisilicon alcohol ester compound and a preparation method thereof. The invention takes pentaerythritol methylsilicate and allyl trichlorosilane or allyl trimethoxy silane as raw materials, prepares the reaction type cage-shaped silicon compound by a one-step method, has simple process, less equipment investment, convenient operation and low cost, and is easy to convert into industrial production; the flame retardant has the advantages of high silicon content, high flame-retardant efficiency, good char formation, symmetrical structure, good compatibility with materials, no toxic gas generated in the combustion process and the like. In particular, the molecule has active allyl group which can be polymerized with the material to generate the bulk flame-retardant polymer material, and the flame retardant does not migrate and does not deteriorate the physical properties of the material due to the addition of the flame retardant, so the flame retardant has very good application and development prospects.
Disclosure of Invention
One of the purposes of the invention is to provide a reactive organosilicon flame retardant allyl silicic acid trisilicon caged alcohol ester compound which has the advantages of high silicon content, symmetrical structure, moderate polarity, good compatibility with materials, capability of being used as a reactive flame retardant, capability of being used as an additive flame retardant, no toxic or harmful gas generation in the combustion process and the like; the flame retardant is suitable for being used as a flame retardant for unsaturated resin, styrene, acrylate, polyester, polyamide, polyurethane, epoxy resin, polyvinyl alcohol, polyolefin and other materials, and can overcome the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a reactive organosilicon flame retardant allyl silicic acid trisilacyl alcohol ester compound is characterized in that the structure of the compound is shown as the following formula:
the invention also aims to provide a preparation method of the reactive organosilicon flame retardant allyl silicic acid trisilacyl alcohol ester compound, which has the advantages of simple process, easy large-scale production, cheap and easily-obtained raw materials, low equipment investment and low cost.
The method comprises the following steps:
adding an organic solvent and methyl pentaerythritol silicate into a reactor which is provided with a stirrer, a thermometer and a reflux condenser and is connected with a drying and hydrogen chloride absorption device, heating to 60 ℃, starting to dropwise add allyl trichlorosilane under the protection of nitrogen, heating to 120-150 ℃, carrying out heat preservation reaction for 11-15h after finishing dripping, adjusting the pH to 6.5-8 by using an acid-binding agent, cooling to 25 ℃, filtering, washing a filter cake by using cold water with the volume of 2 times milliliter of the theoretical mass gram of the product, and drying to obtain white solid allyl silicic acid trisilicon ester.
The method can also comprise the following steps:
adding pentaerythritol methylsilicate, organic solvent and allyltrimethoxysilane into a reactor provided with a stirrer, a thermometer and a fractionating device, heating to 100 ℃, starting reflux, gradually heating to 120-150 ℃ in reflux, keeping the temperature for reaction for 14-18h, controlling the temperature at the top of the tower to be not higher than 65 ℃ in the whole process, leading the separated methanol to reach the theoretical amount, stopping the reaction, cooling to 25 ℃, filtering, washing a filter cake with 60 ml of cold water, and drying to obtain white solid allylsilicic acid trisilicon alcohol ester
The organic solvent is ethylene glycol diethyl ether, tetrachloroethane, diethylene glycol dimethyl ether or anisole, and the volume milliliter number of the organic solvent is 3 to 5 times of the mass number of the pentaerythritol methylsilicate.
The acid-binding agent is triethylamine, pyridine or N, N-dimethylaniline.
The methyl pentaerythrityl silicate is 1-methyl-1-sila-2, 6, 7-trioxa-4-hydroxymethyl bicyclo [2, 2, 2] octane, and the structure of the methyl pentaerythrityl silicate is shown as the following formula:
the reaction type organosilicon flame retardant allyl silicic acid trisilicon cage alcohol ester compound is a white solid, and the decomposition temperature is as follows: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The product is obtainedThe flame retardant has a ratio of 85.2-92.6%, and is suitable for use as a flame retardant for materials such as unsaturated resins, styrene, acrylates, polyesters, polyamides, polyurethanes, epoxy resins, polyolefins, and the like. The preparation principle of the phenyl silicic acid trisilicon caged alcohol ester compound serving as the organic silicon flame-retardant charring agent is as follows:
compared with the prior art, the invention has the beneficial effects that:
the organic silicon flame retardant allyl silicic acid trisilicon alcohol ester belongs to a multi-cage polysilicone compound, and has the advantages of high silicon content, high flame retardant efficiency, good symmetry of cage ring structure, stable product, high decomposition temperature and good processing performance; can be used as a reaction type flame retardant and an additive type flame retardant, and has wide application range.
The organic silicon flame retardant allyl silicic acid trisilicon caged alcohol ester compound has good char forming property, belongs to a high-efficiency environment-friendly flame retardant char forming agent, and has better char forming and melting and dripping prevention functions.
The preparation method of the organosilicon flame retardant allyl silicic acid trisilicon alcohol ester compound has the advantages of one-step reaction, simple process, less equipment investment, convenient operation, low cost and easy large-scale conversion and production.
Drawings
The following figures are presented to further illustrate the structure and performance characteristics of the product.
FIG. 1 is an infrared spectrum of trisilacagol allylsilicate; FIG. 1 shows, 3000cm-1is-CH ═ CH2A stretching vibration peak of the key; 2872cm-1Is the stretching vibration peak of the C-H bond; 1442cm-1Is the peak of bending vibration of the C-H bond; 1034cm-1Is the stretching vibration peak of the Si-O-C bond; 878cm-1Is the bending vibration peak of the Si-O-C bond; 754cm-1Is the stretching vibration peak of the Si-C bond; 1074.7cm-1Is the stretching vibration peak of the-C-O bond.
FIG. 2 is a nuclear magnetic spectrum of trisilacagyl allylsilicate; FIG. 2 shows the use of deuterated DMSO asIs a solvent, 0.10-0.12 is CH3-methyl hydrogen peak on Si; 1.0-1.06 is C-CH2Exocyclic methylene hydrogen peak on O-Si; 1.08-1.25 is Si-CH2-CH＝CH2The upper silicon-bonded methylene hydrogen peak; 3.5-3.6 is C-CH2A methylene peak in the ring on O-Si; 3.6-4.0 is Si-OCH2CH＝CH2Hydrogen peak on the olefinic bond; 2.5 is H in DMSO solvent2Hydrogen peak in O.
FIG. 3 is a differential thermogram of trisilacyl allylsilicate; FIG. 3 shows that weight loss begins when the temperature rises to around 355 ℃; when the temperature is heated to 380 ℃, the weight loss rate of the product reaches 50 percent; after the final temperature reached 800 ℃, there was still 21% residue, indicating that the synthesized product has good thermal stability properties.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The technical solution of the present invention is further described below with reference to the specific embodiments.
Example 1 in a 250ml three-neck flask equipped with a stirrer, a thermometer, a reflux condenser and a drying tube and a hydrogen chloride absorption device connected at the upper port, 0.15mol (26.40g) of pentaerythritol methylsilicate and 130ml of ethylene glycol diethyl ether are added, under the protection of nitrogen, the temperature is raised to 60 ℃, 0.05mol (8.78g) of allyl trichlorosilane is started to be dripped, after dripping is finished, the reflux is gradually raised to 120 ℃, the temperature is kept for reaction for 11h, the pH value is adjusted to 6.5-8 by a triethylamine acid-binding agent, the reaction is cooled to 25 ℃, the reaction solution is filtered, washed by 70ml of cold water and dried, and white solid allyl caged alcohol silicate is obtained, the decomposition temperature: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 85.3%.
Example 2 in a 250ml three-neck flask equipped with a stirrer, a thermometer, a reflux condenser and a drying tube and a hydrogen chloride absorption device connected at the upper port, 0.155mol (27.28g) of pentaerythritol methylsilicate and 100ml of tetrachloroethane were added, under the protection of nitrogen, the temperature was raised to 60 ℃, 0.05mol (8.78g) of allyl trichlorosilane was started to be added dropwise, after the dropwise addition, the reflux was gradually raised to 130 ℃, the reaction was carried out for 12 hours, the pH was adjusted to 6.5-8 with a pyridine acid-binding agent, the reaction was cooled to 25 ℃, the reaction solution was filtered, washed with 70ml of cold water and dried to obtain white solid allyl trisilicate alcohol ester, the decomposition temperature of which was 6.5-8Degree: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 89.2%.
Example 3 in a 250ml three-neck flask equipped with a stirrer, a thermometer, a reflux condenser and a drying tube and a hydrogen chloride absorption device connected at the upper port, 0.16mol (28.40g) of methyl pentaerythritol silicate and 100ml of diethylene glycol dimethyl ether are added, under the protection of nitrogen, the temperature is raised to 60 ℃, 0.05mol (8.78g) of allyl trichlorosilane is started to be dripped, after dripping is finished, the reflux is gradually raised to 140 ℃, the temperature is kept for reaction for 13h, the pH value is adjusted to 6.5-8 by a triethylamine acid-binding agent, the reaction is cooled to 25 ℃, and the reaction solution is filtered, washed by 70ml of cold water and dried to obtain white solid allyl trisilicon ester, the decomposition temperature of the white solid is: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 92.2%.
Example 4 in a 250ml three-neck flask equipped with a stirrer, a thermometer, a reflux condenser and connected with a drying tube and a hydrogen chloride absorption device at the upper port, 0.165mol (29.04g) of methyl pentaerythritol silicate and 110ml of anisole are added, under the protection of nitrogen, the reflux is gradually heated to 60 ℃, 0.05mol (8.78g) of allyl trichlorosilane is started to be dripped, after the dripping is finished, the temperature is raised to 150 ℃, the reaction is kept for 13h, the pH value is adjusted to 6.5-8 by triethylamine acid-binding agent, the reaction is cooled to 25 ℃, the reaction solution is filtered, washed by 70ml of cold water and dried, and white solid allyl trisilicon alcohol ester is obtained, the decomposition temperature: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 92.1%.
Example 5 in a 250ml three-neck flask equipped with a stirrer, a thermometer, a reflux condenser and a drying tube and a hydrogen chloride absorption device connected to the upper port, 0.17mol (29.92g) of pentaerythritol methylsilicate and 90ml of tetrachloroethane were added, under the protection of nitrogen, the temperature was raised to 60 ℃, 0.05mol (8.78g) of allyl trichlorosilane was started to be added dropwise, after the dropwise addition, the reflux was gradually raised to 140 ℃, the reaction was maintained for 15 hours, the pH was adjusted to 6.5-8 with a pyridine acid-binding agent, the reaction was cooled to 25 ℃, the reaction solution was filtered, washed with 70ml of cold water and dried to obtain white solid allyl trisilicate alcohol ester, the decomposition temperature thereof: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 92.6%.
Example 6A reflux condenser tube with a stirrer, a thermometer and a condenser was usedAdding 0.16mol (28.40g) of methyl pentaerythritol silicate and 120ml of diethylene glycol dimethyl ether into a 250ml three-neck flask with an upper opening connected with a drying tube and a hydrogen chloride absorption device, heating to 60 ℃ under the protection of nitrogen, starting to dropwise add 0.05mol (8.78g) of allyl trichlorosilane, after dropwise adding, refluxing and gradually heating to 150 ℃, preserving heat for reaction for 13 hours, adjusting the pH to 6.5-8 by using a triethylamine acid-binding agent, cooling to 25 ℃, filtering, washing by using 70ml of cold water, and drying to obtain white solid allyl caged alcohol silicate, wherein the decomposition temperature is as follows: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 91.4%.
Example 7 in a 250ml three-neck flask equipped with a stirrer, a thermometer and a fractionating device, 0.15mol (26.40g) of methyl pentaerythritol silicate, 130ml of ethylene glycol diethyl ether and 0.05mol (8.10g) of allyl trimethoxy silane are added, the temperature is raised to 100 ℃, reflux is started, the reflux is gradually raised to 120 ℃, the temperature is kept for 14h, the temperature at the top of the column is controlled to be not higher than 65 ℃ in the whole process, the separated methanol reaches a theoretical amount, the reaction is stopped, the temperature is cooled to 25 ℃, the filtration is carried out, a filter cake is washed by 70ml of cold water and dried, and white solid allyl trisilicon alcohol silicate is obtained, the decomposition temperature is: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 85.2%.
Example 8 in a 250ml three-neck flask equipped with a stirrer, a thermometer and a fractionating device, 0.155mol (27.28g) of pentaerythritol methylsilicate, 100ml of tetrachloroethane and 0.05mol (8.10g) of allyltrimethoxysilane are added, the temperature is raised to 100 ℃, reflux is started, the temperature is gradually raised to 130 ℃, the temperature is kept for 15h, the temperature at the top of the column is controlled to be not higher than 65 ℃ in the whole process, the separated methanol reaches the theoretical amount, the reaction is stopped, the temperature is cooled to 25 ℃, the filtration is carried out, a filter cake is washed by 70ml of cold water and dried, and white solid allylsilicic acid trisilicon alcohol ester is obtained, the decomposition temperature is: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 88.0%.
Example 9A 250ml three-necked flask equipped with a stirrer, a thermometer and a fractionating device was charged with 0.16mol (28.40g) of pentaerythritol methylsilicate, 100ml of diethylene glycol dimethyl ether and 0.05mol (8.10g) of allyltrimethoxysilane, heated to 100 ℃ to initiate reflux,and (3) refluxing, gradually raising the temperature to 140 ℃, carrying out heat preservation reaction for 16h, controlling the temperature at the top of the tower to be not higher than 65 ℃ in the whole process, enabling the separated methanol to reach the theoretical amount, stopping the reaction, cooling to 25 ℃, filtering, washing a filter cake with 70ml of cold water, and drying to obtain white solid allyl silicic acid trisilicon alcohol ester, wherein the decomposition temperature is as follows: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 91.2%.
Example 10 in a 250ml three-neck flask equipped with a stirrer, a thermometer and a fractionating device, 0.165mol (29.04g) of pentaerythritol methylsilicate, 110ml of anisole and 0.05mol (8.10g) of allyltrimethoxysilane are added, the temperature is raised to 100 ℃, reflux is started, the temperature is gradually raised to 150 ℃ in reflux, the temperature is kept for 16h, the temperature at the top of the column is controlled to be not higher than 65 ℃ in the whole process, the separated methanol reaches theoretical amount, the reaction is stopped, the temperature is cooled to 25 ℃, the filtration is carried out, a filter cake is washed by 70ml of cold water and dried, and white solid trisilicon ester of allylsilicate is obtained, the decomposition temperature is: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 92.1%.
Example 11 in a 250ml three-neck flask equipped with a stirrer, a thermometer and a fractionating device, 0.17mol (29.29g) of methyl pentaerythritol silicate, 90ml of tetrachloroethane and 0.05mol (8.10g) of allyltrimethoxysilane are added, the temperature is raised to 100 ℃, reflux is started, the temperature is gradually raised to 140 ℃ in reflux, the temperature is kept for 18h, the temperature at the top of the column is controlled to be not higher than 65 ℃ in the whole process, the separated methanol reaches the theoretical amount, the reaction is stopped, the temperature is cooled to 25 ℃, the filtration is carried out, a filter cake is washed by 70ml of cold water and dried, and white solid allylsilicic acid trisilicon alcohol ester is obtained, the decomposition temperature is: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 92.2%.
Example 12 to a 250ml three-neck flask equipped with a stirrer, a thermometer and a fractionating device, 0.16mol (28.40g) of pentaerythritol methylsilicate, 120ml of diethylene glycol dimethyl ether and 0.05mol (8.10g) of allyltrimethoxysilane were added, the temperature was raised to 100 ℃ to start reflux, the reflux was gradually raised to 150 ℃ to carry out a heat preservation reaction for 16 hours, the temperature at the top of the column was controlled to be not higher than 65 ℃ in the whole process, the separated methanol was theoretically stopped, the reaction was cooled to 25 ℃, the reaction was stopped, the filtrate was filtered, and 70ml of a filter cake was cooledWashing with water, and drying to obtain white solid allyl silicic acid trisilicon alcohol ester, wherein the decomposition temperature is as follows: 350 + -5 deg.C, density (25 deg.C): 1.384g/cm3The yield was 91.1%.
TABLE 1 preparation examples Main Process parameters
The inventor also applies the prepared product allyl silicic acid trisilicon alcohol ester to 191 unsaturated resin, uniformly mixes the allyl silicic acid trisilicon alcohol ester with the 191 unsaturated resin, methyl ethyl ketone peroxide and cobalt naphthenate according to the proportion in the following table, pours the mixture into a mold paved with glass fiber cloth to prepare a flame-retardant resin sample strip with the length of 15cm, the width of 0.7cm and the thickness of 0.3cm, and tests the flame-retardant performance, wherein the experimental result is shown in table 2.
TABLE 2 oxygen index test results for trisilicon allyl silicate ester in unsaturated resins
From table 2, when the flame retardant additive is not added, the limit oxygen index of the unsaturated resin is 18 percent and the unsaturated resin is combusted when meeting fire, and when the allyl silicon trisilicon alcohol silicate is added to reach 14 percent of the mass of the 191 unsaturated resin system, the limit oxygen index of the flame retardant resin sample strip can reach more than 27 percent of the flame retardant level; when the addition amount of the flame retardant reaches 20% of the mass of the 191 unsaturated resin, the LOI reaches more than 29%, and when the addition amount of the flame retardant reaches 25% of the mass of the 191 unsaturated resin, the LOI reaches more than 31%, the synthesized product contains active groups and is copolymerized with the unsaturated resin to form a body flame-retardant structure, so that the glass fiber reinforced plastic material with excellent performance is obtained, and the allyl silicon trisilicon caged alcohol ester has good flame-retardant performance when being applied to the unsaturated resin.
Claims (5)
1. A reactive organosilicon flame retardant allyl silicic acid trisilacyl alcohol ester compound is characterized in that the structure of the compound is as follows:
2. the method for preparing the reactive organosilicon flame retardant trisilicon allyl silicate alcohol ester compound as claimed in claim 1, wherein the method comprises:
adding an organic solvent and methyl pentaerythritol silicate into a reactor which is provided with a stirrer, a thermometer and a reflux condenser and is connected with a hydrogen chloride absorption device, heating to 60 ℃, starting to dropwise add allyl trichlorosilane under the protection of nitrogen, heating to 120-150 ℃, carrying out heat preservation reaction for 11-15h, adjusting the pH to 6.5-8 by using an acid-binding agent, cooling to 25 ℃, filtering, washing a filter cake by using cold water with the theoretical mass gram of the product of 2 times volume milliliter, and drying to obtain white solid allyl silicic acid trisilicon ester; the methyl pentaerythrityl silicate is 1-methyl-1-sila-2, 6, 7-trioxa-4-hydroxymethyl bicyclo [2, 2, 2] octane, and the structure of the methyl pentaerythrityl silicate is shown as the following formula:
3. the method for preparing the reactive organosilicon flame retardant trisilicon allyl silicate alcohol ester compound as claimed in claim 1, wherein the method comprises:
adding pentaerythritol methylsilicate, organic solvent and allyltrimethoxysilane into a reactor provided with a stirrer, a thermometer and a fractionating device, heating to 100 ℃, starting reflux, gradually heating to 120-150 ℃ in reflux, keeping the temperature for reaction for 14-18h, controlling the temperature at the top of the tower to be not higher than 65 ℃ in the whole process, leading the separated methanol to reach the theoretical amount, stopping the reaction, cooling to 25 ℃, filtering, washing a filter cake with 60 ml of cold water, and drying to obtain white solid allylsilicic acid trisilicon ester.
4. A process for preparing a reactive organosilicon flame retardant trisilicon allyl silicate alcohol ester compound as claimed in claim 2 or 3, wherein:
the organic solvent is ethylene glycol diethyl ether, tetrachloroethane, diethylene glycol dimethyl ether or anisole, and the volume milliliter number of the organic solvent is 3 to 5 times of the mass gram number of the pentaerythritol methylsilicate.
5. The method for preparing a reactive organosilicon flame retardant trisilicon allyl silicate alcohol ester compound as claimed in claim 2, wherein:
the acid-binding agent is triethylamine, pyridine or N, N-dimethylaniline.
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