CN112341495A - Rosinyl silicon-phosphorus synergistic flame retardant, preparation method thereof and polyurethane foam prepared from rosinyl silicon-phosphorus synergistic flame retardant - Google Patents
Rosinyl silicon-phosphorus synergistic flame retardant, preparation method thereof and polyurethane foam prepared from rosinyl silicon-phosphorus synergistic flame retardant Download PDFInfo
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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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- 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
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
Abstract
The invention discloses a rosinyl silicon phosphorus synergistic flame retardant, which has a structural formula as follows:
and the like. According to the invention, through the chemical reaction of rosin and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, the organic combination of silicon and phosphorus elements is realized, and the prepared flame retardant has higher thermal stability and flame retardance under the action of a synergistic mechanism; the introduction of the rosinyl silicon phosphorus synergistic flame retardant enhances the stability and the flame retardant performance of the rigid foam polyurethane, and simultaneously enhances the mechanical performance of the rigid foam polyurethane to meet the requirement of constructionThe application requirements in the fields of building insulation boards, box body packaging and the like are met, the using amount is small, polyurethane is introduced in a chemical combination mode, no flame retardant overflows, and the flame retardant stability is good.
Description
Technical Field
The invention relates to a rosinyl silicon phosphorus synergistic flame retardant, a preparation method thereof and polyurethane foam prepared from the same, and belongs to the field of flame retardant materials.
Background
Polyurethane foam is one of important high molecular polymers, and is widely applied to the fields of pipelines, building heat preservation and box transportation due to excellent heat preservation performance, higher compressive strength and stronger solvent resistance. However, the hard polyurethane foam brings convenience to people and has some hidden dangers, the hard polyurethane foam is extremely easy to burn in the air due to the fact that a molecular chain segment contains a large amount of carbon and hydrogen elements, and has the characteristic of flammability.
At present, flame retardant products for modifying the flame retardant property of polyurethane foam mainly comprise phosphorus flame retardants, nitrogen flame retardants and silicon flame retardants, but have the following problems: 1) the flame retardant performance is improved to a limited extent; 2) the addition amount of the flame retardant is large; 3) leading to the reduction of the mechanical property of the material; 4) poor compatibility with the matrix material, uneven distribution of the flame retardant, and over time, spillage of the flame retardant out of the material occurs. Therefore, research is needed to prepare a multi-element synergistic flame-retardant rigid polyurethane foam.
Disclosure of Invention
In order to simultaneously enhance the flame retardant property and the mechanical property of the existing polyurethane foam and avoid the phenomenon of fire retardant overflow, the invention provides a rosinyl silicon phosphorus synergistic fire retardant, a preparation method thereof and a polyurethane foam prepared by the same.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a rosinyl silicon phosphorus synergistic flame retardant has a structural formula as follows:
the raw material components of the rosinyl silicon phosphorus synergistic flame retardant comprise: 10-20 parts of rosin, 20-40 parts of triethoxy (3-epoxypropyloxypropyl) silane, 6-10 parts of triethylamine, 500 parts of dichloromethane 200-ion-substituted resin, 500 parts of anhydrous ethanol 300-ion-substituted resin, 5-15 parts of carbon tetrachloride, 40-100 parts of sodium chloride, 20-40 parts of hydrochloric acid, 3-10 parts of anhydrous sodium sulfate and 5-20 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, wherein the parts are in parts by mass.
The silicon-phosphorus synergistic flame retardant can be used as a raw material for preparing polyurethane foam.
The rosin is dehydroabietic acid, tetrahydroabietic acid, abietic acid, acrylpimaric acid or fumylpimaric acid.
The preparation method of the rosinyl silicon-phosphorus synergistic flame retardant comprises the following steps:
(1) reacting triethoxy (3-epoxypropyloxypropyl) silane with pine to prepare rosin-based organosilicon polyol;
(2) reacting the rosinyl organic silicon polyol obtained in the step (1), triethylamine and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in an ice bath, washing and drying to obtain the rosinyl silicon-phosphorus synergistic flame retardant.
In order to further ensure the product performance, the preparation method of the rosinyl silicon phosphorus synergistic flame retardant comprises the following steps:
(1) dissolving triethoxy (3-epoxypropyloxypropyl) silane and rosin in a three-neck flask filled with absolute ethyl alcohol, reacting for 5-7 h under the protection of nitrogen at the temperature of 80-90 ℃, and removing the absolute ethyl alcohol by rotary evaporation to obtain rosin-based organic silicon polyol;
(2) dissolving the rosin-based organic silicon polyol obtained in the step (1), triethylamine and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) in dichloromethane at room temperature, cooling the solution to minus 10 ℃ to minus 5 ℃ in an ice bath, dropwise adding carbon tetrachloride into the solution, keeping the temperature of the solution at 0-10 ℃, and reacting for 12-15 hours after dropwise adding;
(3) and (3) washing the material obtained in the step (2) by using a saturated sodium chloride solution of 1M hydrochloric acid, and drying to obtain the rosinyl silicon phosphorus synergistic flame retardant.
In order to further ensure the product quality, in the step (3), the drying is carried out for 4-6 h by using anhydrous sodium sulfate, then the solvent is removed by rotary evaporation, and then the drying is carried out for 24-30 h in an oven at the temperature of 75-85 ℃. The drying degree of the product and the purity of the material can be better ensured, and the applicant finds through research and development practice that if rotary evaporation and drying are directly carried out, crystal water cannot be effectively removed.
A rosinyl silicon phosphorus synergistic flame-retardant polyurethane foam comprises a component A and a component B, wherein the component A comprises the following raw material components: 100 parts of polyol, 2-3 parts of foam stabilizer, 1-2 parts of foaming agent, 0.1-0.3 part of catalyst and 5-20 parts of rosinyl silicon phosphorus synergistic flame retardant as described in claim 1 or 2, wherein the polyol is polyether polyol and/or polyester polyol; the component B is polyisocyanate, and the mass ratio of the component A to the component B is 1: 0.8-1.2, wherein the parts are parts by mass.
In order to improve the stability and mechanical property of the polyurethane foam material, the foam homogenizing agent is GT-320 hard foam silicone oil, the foaming agent is water, the catalyst is N, N-Dimethylcyclohexylamine (DMCHA), and the polyisocyanate is at least one of xylene diisocyanate, toluene diisocyanate or polymethylene polyphenyl polyisocyanate.
The preparation method of the rosinyl silicon-phosphorus synergistic flame-retardant polyurethane foam is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly mixing polyol, a foam stabilizer, a foaming agent, a catalyst and a rosinyl silicon phosphorus synergistic flame retardant to prepare a component A;
(2) and (3) stirring the component A and the component B for 10-20 seconds under the condition of high-speed stirring, quickly pouring into a mold, standing at 80-90 ℃ for 22-26 hours to finish curing, and obtaining the rosinyl silicon-phosphorus synergistic flame-retardant polyurethane foam after curing.
In order to improve and ensure the uniformity of material mixing and the quality of the obtained polyurethane foam, the rotating speed of high-speed stirring in the step (2) is 2000-2500 r/min.
The rosin-based silicon-phosphorus synergistic flame retardant is prepared by reacting rosin-based organic silicon polyol with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), and then is added into the component A of the hard foam polyurethane, and the flame retardant is uniformly distributed in a high-speed stirring manner to prepare the hard foam polyurethane material with long flame retardant time-effect and excellent mechanical property, and the flame retardance of the polyurethane foam material is further improved by utilizing the synergistic action mechanism of silicon and phosphorus elements.
The prior art is referred to in the art for techniques not mentioned in the present invention.
Compared with the prior art, the invention has the following beneficial effects:
1. the organic combination of silicon-phosphorus elements is realized through the chemical reaction of rosin and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the prepared flame retardant has higher thermal stability and flame retardance under the action of a synergistic mechanism.
2. The introduction of the rosin-based silicon-phosphorus synergistic flame retardant enhances the stability and the flame retardant performance of the rigid foam polyurethane, simultaneously enhances the mechanical performance of the rigid foam polyurethane, meets the application requirements in the fields of building insulation boards, box body packaging and the like, has small dosage, introduces the polyurethane in a chemical combination mode, has no phenomenon of overflowing of the flame retardant, and has good flame retardant stability.
Drawings
FIG. 1 is an infrared spectrum of fumaropimaric acid modified silicon phosphorus synergistic flame retardant obtained in example 1.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
Weighing 15 parts by weight of fumaropimaric acid and 30 parts by weight of triethoxy (3-epoxypropyloxypropyl) silane (KH-561) in a three-neck flask, adding 300 parts by weight of absolute ethanol solvent, heating to 90 ℃ under the conditions of nitrogen protection and condensation reflux, reacting for 6 hours, and then performing rotary evaporation to remove ethanol to obtain light yellow viscous fumaropimaric acid modified organosilicon polyol (FASO). 30 parts by weight of fumaropimaric acid-modified silicone polyol was weighed out and dissolved in 210 parts by weight of methylene chloride in a three-necked flask, 5.1 parts by weight of DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and 2.7 parts by weight of triethylamine were weighed out and dissolved in 30 parts by weight of methylene chloride, and the solution was added to the three-necked flask. Under the condition of ice bath, the temperature of the system is reduced to be between 10 ℃ below zero and 5 ℃ below zero, 3.7 parts by weight of carbon tetrachloride is dripped, and meanwhile, the temperature of the system is kept to be not more than 10 ℃. After the dropwise addition, the reaction was carried out at room temperature for 16 hours. And after the reaction is finished, washing the obtained product for three times by using a saturated sodium chloride solution of 1M hydrochloric acid, adding 5 parts by weight of anhydrous sodium sulfate into the washed solution to remove water for 4 hours, then removing the solvent by rotary evaporation, and drying the obtained product in an oven at the temperature of 80 ℃ for 24 hours to obtain the yellow viscous fumaropimaric acid modified silicophosphate synergistic Flame Retardant (FR). Weighing 12.2 parts by weight of fumaropimaric acid modified silicon phosphorus synergistic flame retardant, 100 parts by weight of polyether polyol (ZS4110, Jiangsu clock mountain chemical Co., Ltd.), 3 parts by weight of GT-320, 1.5 parts by weight of water and 0.2 part by weight of N, N-Dimethylcyclohexylamine (DMCHA), and uniformly mixing to obtain a component A. 132 parts by weight of a polyisocyanate (PM-200, Vanhua chemical group Co., Ltd.) was weighed out and named as component B. Stirring the component A and the component B at the rotating speed of 2000r/min for 15s, pouring into a mold, and curing at 80 ℃ for 24h to obtain the product.
The formula of the fumaropimaric acid modified silicon-phosphorus synergistic flame retardant is shown in table 1, the formula of the polyurethane foam is shown in table 2, and the performance test is shown in table 3.
As shown in figure 1, the IR spectrum of the rosinyl silicon phosphorus synergistic flame retardant is identified as follows:
1688cm-1the absorption peak of-COOH in fumaropimaric acid disappears after the reaction with triethoxy (3-epoxypropyloxypropyl) silane is completed, and the absorption peak of-COOH is at 3318cm-1the-OH absorption peak in the rosin-based organic silicon polyol is shown and is 957cm-1Si-OEt absorption peaks appear, and the results show that the rosin-based organosilicon polyol is successfully prepared.
2384cm-1Is the absorption peak of P-H bond in DOPO, 1225cm-1Is the characteristic absorption peak of the phosphaphenanthrene ring in DOPO. 2384cm in IR spectrum of rosinyl silicon phosphorus synergistic flame retardant-1Disappearance of absorption peak, and 1225cm-1The retention of absorption peak indicates that the rosin-based silicon-phosphorus synergistic flame retardant is successfully prepared. Fumaropimaric acid modified silicon-phosphorus synergistic flame retardant structural formulaThe following were used:
example 2
Weighing 15 parts by weight of fumaropimaric acid and 30 parts by weight of triethoxy (3-epoxypropyloxypropyl) silane (KH-561) in a three-neck flask, adding 300 parts by weight of absolute ethanol solvent, heating to 90 ℃ under the conditions of nitrogen protection and condensation reflux, reacting for 6 hours, and then performing rotary evaporation to remove ethanol to obtain light yellow viscous fumaropimaric acid modified organosilicon polyol (FASO). 30 parts by weight of fumaropimaric acid-modified silicone polyol was weighed out and dissolved in 210 parts by weight of methylene chloride in a three-necked flask, 5.1 parts by weight of DOPO and 2.7 parts by weight of triethylamine were weighed out and dissolved in 30 parts by weight of methylene chloride, and the solution was added to the three-necked flask. Under the condition of ice bath, the temperature of the system is reduced to be between 10 ℃ below zero and 5 ℃ below zero, 3.7 parts by weight of carbon tetrachloride is dripped, and meanwhile, the temperature of the system is kept to be not more than 10 ℃. After the dropwise addition, the reaction was carried out at room temperature for 16 hours. And after the reaction is finished, washing the obtained product for three times by using a saturated sodium chloride solution of 1M hydrochloric acid, adding 5 parts by weight of anhydrous sodium sulfate into the washed solution to remove water for 4 hours, then removing the solvent by rotary evaporation, and drying the obtained product in an oven at the temperature of 80 ℃ for 24 hours to obtain the yellow viscous fumaropimaric acid modified silicophosphate synergistic Flame Retardant (FR). 25.8 parts by weight of fumaropimaric acid modified silicon phosphorus synergistic flame retardant, 100 parts by weight of polyether polyol (ZS4110, Jiangsu clock mountain chemical Co., Ltd.), 3 parts by weight of GT-320, 1.5 parts by weight of water and 0.2 part by weight of N, N-Dimethylcyclohexylamine (DMCHA) are weighed and mixed uniformly to prepare a component A. 132 parts by weight of a polyisocyanate (PM-200, Vanhua chemical group Co., Ltd.) was weighed out and named as component B. Stirring the component A and the component B at the rotating speed of 2000r/min for 15s, pouring into a mold, and curing at 80 ℃ for 24h to obtain the product.
The formula of the fumaropimaric acid modified silicon-phosphorus synergistic flame retardant is shown in table 1, the formula of the polyurethane foam is shown in table 2, and the performance test is shown in table 3.
Example 3
Weighing 15 parts by weight of fumaropimaric acid and 30 parts by weight of triethoxy (3-epoxypropyloxypropyl) silane (KH-561) in a three-neck flask, adding 300 parts by weight of absolute ethanol solvent, heating to 90 ℃ under the conditions of nitrogen protection and condensation reflux, reacting for 6 hours, and then performing rotary evaporation to remove ethanol to obtain light yellow viscous fumaropimaric acid modified organosilicon polyol (FASO). 30 parts by weight of fumaropimaric acid-modified silicone polyol was weighed out and dissolved in 210 parts by weight of methylene chloride in a three-necked flask, 5.1 parts by weight of DOPO and 2.7 parts by weight of triethylamine were weighed out and dissolved in 30 parts by weight of methylene chloride, and the solution was added to the three-necked flask. Under the condition of ice bath, the temperature of the system is reduced to be between 10 ℃ below zero and 5 ℃ below zero, 3.7 parts by weight of carbon tetrachloride is dripped, and meanwhile, the temperature of the system is kept to be not more than 10 ℃. After the dropwise addition, the reaction was carried out at room temperature for 16 hours. And after the reaction is finished, washing the obtained product for three times by using a saturated sodium chloride solution of 1M hydrochloric acid, adding 5 parts by weight of anhydrous sodium sulfate into the washed solution to remove water for 4 hours, then removing the solvent by rotary evaporation, and drying the obtained product in an oven at the temperature of 80 ℃ for 24 hours to obtain the yellow viscous fumaropimaric acid modified silicophosphate synergistic Flame Retardant (FR). 41.1 parts by weight of fumaropimaric acid modified silicon phosphorus synergistic flame retardant, 100 parts by weight of polyether polyol (ZS4110, Jiangsu clock mountain chemical Co., Ltd.), 3 parts by weight of GT-320, 1.5 parts by weight of water and 0.2 part by weight of N, N-Dimethylcyclohexylamine (DMCHA) are weighed and mixed uniformly to prepare a component A. 132 parts by weight of a polyisocyanate (PM-200, Vanhua chemical group Co., Ltd.) was weighed out and named as component B. Stirring the component A and the component B at the rotating speed of 2000r/min for 15s, pouring into a mold, and curing at 80 ℃ for 24h to obtain the product.
The formula of the fumaropimaric acid modified silicon-phosphorus synergistic flame retardant is shown in table 1, the formula of the polyurethane foam is shown in table 2, and the performance test is shown in table 3.
Example 4
Weighing 15 parts by weight of fumaropimaric acid and 30 parts by weight of triethoxy (3-epoxypropyloxypropyl) silane (KH-561) in a three-neck flask, adding 300 parts by weight of absolute ethanol solvent, heating to 90 ℃ under the conditions of nitrogen protection and condensation reflux, reacting for 6 hours, and then performing rotary evaporation to remove ethanol to obtain light yellow viscous fumaropimaric acid modified organosilicon polyol (FASO). 30 parts by weight of fumaropimaric acid-modified silicone polyol was weighed out and dissolved in 210 parts by weight of methylene chloride in a three-necked flask, 5.1 parts by weight of DOPO and 2.7 parts by weight of triethylamine were weighed out and dissolved in 30 parts by weight of methylene chloride, and the solution was added to the three-necked flask. Under the condition of ice bath, the temperature of the system is reduced to be between 10 ℃ below zero and 5 ℃ below zero, 3.7 parts by weight of carbon tetrachloride is dripped, and meanwhile, the temperature of the system is kept to be not more than 10 ℃. After the dropwise addition, the reaction was carried out at room temperature for 16 hours. And after the reaction is finished, washing the obtained product for three times by using a saturated sodium chloride solution of 1M hydrochloric acid, adding 5 parts by weight of anhydrous sodium sulfate into the washed solution to remove water for 4 hours, then removing the solvent by rotary evaporation, and drying the obtained product in an oven at the temperature of 80 ℃ for 24 hours to obtain the yellow viscous fumaropimaric acid modified silicophosphate synergistic Flame Retardant (FR). 58.2 parts by weight of fumaropimaric acid modified silicon phosphorus synergistic flame retardant, 100 parts by weight of polyether polyol (ZS4110, Jiangsu clock mountain chemical Co., Ltd.), 3 parts by weight of GT-320, 1.5 parts by weight of water and 0.2 part by weight of N, N-Dimethylcyclohexylamine (DMCHA) are weighed and mixed uniformly to prepare a component A. 132 parts by weight of a polyisocyanate (PM-200, Vanhua chemical group Co., Ltd.) was weighed out and named as component B. Stirring the component A and the component B at the rotating speed of 2000r/min for 15s, pouring into a mold, and curing at 80 ℃ for 24h to obtain the product.
The formula of the fumaropimaric acid modified silicon-phosphorus synergistic flame retardant is shown in table 1, the formula of the polyurethane foam is shown in table 2, and the performance test is shown in table 3.
Example 5
Weighing 15 parts by weight of dehydroabietic acid and 30 parts by weight of triethoxy (3-epoxypropyloxypropyl) silane (KH-561) in a three-neck flask, adding 300 parts by weight of an absolute ethanol solvent, heating to 90 ℃ under the conditions of nitrogen protection and condensation reflux, reacting for 6 hours, and then performing rotary evaporation to remove ethanol to obtain light yellow viscous dehydroabietic acid modified organic silicon polyol. 30 parts by weight of dehydroabietic acid-modified silicone polyol was weighed out and dissolved in 210 parts by weight of methylene chloride in a three-necked flask, 5.1 parts by weight of DOPO and 2.7 parts by weight of triethylamine were weighed out and dissolved in 30 parts by weight of methylene chloride, and the solution was added to the above three-necked flask. Under the condition of ice bath, the temperature of the system is reduced to be between 10 ℃ below zero and 5 ℃ below zero, 3.7 parts by weight of carbon tetrachloride is dripped, and meanwhile, the temperature of the system is kept to be not more than 10 ℃. After the dropwise addition, the reaction was carried out at room temperature for 16 hours. And after the reaction is finished, washing the mixture for three times by using a saturated sodium chloride solution of 1M hydrochloric acid, adding 5 parts by weight of anhydrous sodium sulfate into the washed solution to remove water for 4 hours, then removing the solvent by rotary evaporation, and drying the mixture in an oven at the temperature of 80 ℃ for 24 hours to obtain the yellow viscous dehydroabietic acid modified silicon-phosphorus synergistic flame retardant. 58.2 parts by weight of dehydroabietic acid modified silicon-phosphorus synergistic flame retardant, 100 parts by weight of polyether polyol (ZS4110, Jiangsu clock hill chemical Co., Ltd.), 3 parts by weight of GT-320, 1.5 parts by weight of water and 0.2 part by weight of N, N-Dimethylcyclohexylamine (DMCHA) were weighed and mixed uniformly to obtain component A. 132 parts by weight of a polyisocyanate (PM-200, Vanhua chemical group Co., Ltd.) was weighed out and named as component B. Stirring the component A and the component B at the rotating speed of 2000r/min for 15s, pouring into a mold, and curing at 80 ℃ for 24h to obtain the product.
The formula of the dehydroabietic acid modified silicon-phosphorus synergistic flame retardant is shown in table 1, the formula of the polyurethane foam is shown in table 2, and the performance test is shown in table 3.
The infrared spectrograms before and after the comparison and the modification show that the dehydroabietic acid carboxyl reacts with epoxy silane, and meanwhile, the phosphaphenanthrene ring of DOPO is grafted on the dehydroabietic acid modified organic silicon polyol, so that the preparation success of the dehydroabietic acid modified organic silicon polyol is proved. The structural formula of the dehydroabietic acid modified silicon-phosphorus synergistic flame retardant is as follows:
example 6
Weighing 15 parts by weight of tetrahydroabietic acid and 30 parts by weight of triethoxy (3-epoxypropyloxypropyl) silane (KH-561) in a three-neck flask, adding 300 parts by weight of absolute ethanol solvent, heating to 90 ℃ under the conditions of nitrogen protection and condensation reflux, reacting for 6 hours, and then performing rotary evaporation to remove ethanol to obtain pale yellow viscous tetrahydroabietic acid modified organic silicon polyol. 30 parts by weight of a tetrahydroabietic acid-modified silicone polyol was weighed out and dissolved in 210 parts by weight of methylene chloride in a three-necked flask, 5.1 parts by weight of DOPO and 2.7 parts by weight of triethylamine were weighed out and dissolved in 30 parts by weight of methylene chloride, and the solution was added to the above three-necked flask. Under the condition of ice bath, the temperature of the system is reduced to be between 10 ℃ below zero and 5 ℃ below zero, 3.7 parts by weight of carbon tetrachloride is dripped, and meanwhile, the temperature of the system is kept to be not more than 10 ℃. After the dropwise addition, the reaction was carried out at room temperature for 16 hours. And after the reaction is finished, washing the mixture for three times by using a saturated sodium chloride solution of 1M hydrochloric acid, adding 5 parts by weight of anhydrous sodium sulfate into the washed solution to remove water for 4 hours, then removing the solvent by rotary evaporation, and drying the mixture in an oven at the temperature of 80 ℃ for 24 hours to obtain the yellow viscous tetrahydroabietic acid modified silicon-phosphorus synergistic Flame Retardant (FR). 58.2 parts by weight of the pine tetrahydroabietic acid modified silicon-phosphorus synergistic flame retardant, 100 parts by weight of polyether polyol (ZS4110, Jiangsu clock mountain chemical Co., Ltd.), 3 parts by weight of GT-320, 1.5 parts by weight of water and 0.2 part by weight of N, N-Dimethylcyclohexylamine (DMCHA) are weighed and mixed uniformly to prepare a component A. 132 parts by weight of a polyisocyanate (PM-200, Vanhua chemical group Co., Ltd.) was weighed out and named as component B. Stirring the component A and the component B at the rotating speed of 2000r/min for 15s, pouring into a mold, and curing at 80 ℃ for 24h to obtain the product.
The formula of the tetrahydroabietic acid modified silicon-phosphorus synergistic flame retardant is shown in table 1, the formula of the polyurethane foam is shown in table 2, and the performance test is shown in table 3.
The infrared spectrograms before and after the comparison and the modification show that the carboxyl of the tetrahydroabietic acid reacts with the epoxy silane, and meanwhile, the phosphaphenanthrene ring of the DOPO is grafted on the tetrahydroabietic acid modified organic silicon polyol, so that the preparation success of the tetrahydroabietic acid modified organic silicon polyol is proved. The structural formula of the tetrahydroabietic acid modified silicon-phosphorus synergistic flame retardant is as follows:
example 7
Weighing 15 parts by weight of abietic acid and 30 parts by weight of triethoxy (3-epoxypropyloxypropyl) silane (KH-561) in a three-neck flask, adding 300 parts by weight of absolute ethanol solvent, heating to 90 ℃ under the conditions of nitrogen protection and condensation reflux, reacting for 6 hours, and then performing rotary evaporation to remove ethanol to obtain light yellow viscous abietic acid modified organosilicon polyol (FASO). 30 parts by weight of abietic acid-modified silicone polyol was weighed out and dissolved in 210 parts by weight of methylene chloride in a three-necked flask, 5.1 parts by weight of DOPO and 2.7 parts by weight of triethylamine were weighed out and dissolved in 30 parts by weight of methylene chloride, and the solution was added to the above three-necked flask. Under the condition of ice bath, the temperature of the system is reduced to be between 10 ℃ below zero and 5 ℃ below zero, 3.7 parts by weight of carbon tetrachloride is dripped, and meanwhile, the temperature of the system is kept to be not more than 10 ℃. After the dropwise addition, the reaction was carried out at room temperature for 16 hours. And after the reaction is finished, washing the mixture for three times by using a saturated sodium chloride solution of 1M hydrochloric acid, adding 5 parts by weight of anhydrous sodium sulfate into the washed solution to remove water for 4 hours, then removing the solvent by rotary evaporation, and drying the mixture in an oven at the temperature of 80 ℃ for 24 hours to obtain the yellow viscous abietic acid modified silicon-phosphorus synergistic Flame Retardant (FR). 58.2 parts by weight of abietic acid modified silicon-phosphorus synergistic flame retardant, 100 parts by weight of polyether polyol (ZS4110, Jiangsu clock hill chemical Co., Ltd.), 3 parts by weight of GT-320, 1.5 parts by weight of water and 0.2 part by weight of N, N-Dimethylcyclohexylamine (DMCHA) were weighed and mixed uniformly to prepare component A. 132 parts by weight of a polyisocyanate (PM-200, Vanhua chemical group Co., Ltd.) was weighed out and named as component B. Stirring the component A and the component B at the rotating speed of 2000r/min for 15s, pouring into a mold, and curing at 80 ℃ for 24h to obtain the product.
The formula of the abietic acid modified silicon-phosphorus synergistic flame retardant is shown in table 1, the formula of the polyurethane foam is shown in table 2, and the performance test is shown in table 3.
The infrared spectrograms before and after the modification are compared to find that the abietic acid carboxyl reacts with epoxy silane, and meanwhile, a phosphaphenanthrene ring of DOPO is grafted on the abietic acid modified organic silicon polyol, so that the success in preparing the abietic acid modified organic silicon polyol is proved. The structural formula of the abietic acid modified silicon-phosphorus synergistic flame retardant is as follows:
example 8
Weighing 15 parts by weight of acrylpimaric acid and 30 parts by weight of triethoxy (3-epoxypropyloxypropyl) silane (KH-561) in a three-neck flask, adding 300 parts by weight of absolute ethanol solvent, heating to 90 ℃ under the conditions of nitrogen protection and condensation reflux, reacting for 6 hours, and then performing rotary evaporation to remove ethanol to obtain the light yellow viscous acrylpimaric acid modified organic silicon polyol. 30 parts by weight of an acrylpimaric acid-modified silicone polyol was weighed out and dissolved in 210 parts by weight of methylene chloride in a three-necked flask, 5.1 parts by weight of DOPO and 2.7 parts by weight of triethylamine were weighed out and dissolved in 30 parts by weight of methylene chloride, and the solution was added to the three-necked flask. Under the condition of ice bath, the temperature of the system is reduced to be between 10 ℃ below zero and 5 ℃ below zero, 3.7 parts by weight of carbon tetrachloride is dripped, and meanwhile, the temperature of the system is kept to be not more than 10 ℃. After the dropwise addition, the reaction was carried out at room temperature for 16 hours. And after the reaction is finished, washing the mixture for three times by using a saturated sodium chloride solution of 1M hydrochloric acid, adding 5 parts by weight of anhydrous sodium sulfate into the washed solution to remove water for 4 hours, then removing the solvent by rotary evaporation, and drying the mixture in an oven at the temperature of 80 ℃ for 24 hours to obtain the yellow viscous silicon phosphorus acrylpimarate synergistic Flame Retardant (FR). 58.2 parts by weight of the acrylic pimaric acid modified silicon-phosphorus synergistic flame retardant, 100 parts by weight of polyether polyol (ZS4110, Jiangsu clock hill chemical Co., Ltd.), 3 parts by weight of GT-320, 1.5 parts by weight of water and 0.2 part by weight of N, N-Dimethylcyclohexylamine (DMCHA) are weighed and mixed uniformly to prepare the component A. 132 parts by weight of a polyisocyanate (PM-200, Vanhua chemical group Co., Ltd.) was weighed out and named as component B. Stirring the component A and the component B at the rotating speed of 2000r/min for 15s, pouring into a mold, and curing at 80 ℃ for 24h to obtain the product. Tests show that the flame retardant property and the mechanical property of the samples of examples 1-8 are not attenuated after standing for 18 months at room temperature.
The formula of the acrylpimaric acid modified silicon-phosphorus synergistic flame retardant is shown in table 1, the formula of the polyurethane foam is shown in table 2, and the performance test is shown in table 3.
The infrared spectrograms before and after the modification are compared to find that the carboxyl of the acrylpimaric acid reacts with the epoxy silane, and meanwhile, the phosphaphenanthrene ring of the DOPO is grafted on the acrylpimaric acid modified organic silicon polyol, so that the preparation of the acrylpimaric acid modified organic silicon polyol is proved to be successful. The structural formula of the acrylpimaric acid modified silicon-phosphorus synergistic flame retardant is as follows:
comparative example 1
100 parts by weight of polyether polyol (ZS4110, chemical Co., Ltd., Jiangsu clock mountain), 3 parts by weight of GT-320, 1.5 parts by weight of water and 0.2 part by weight of N, N-Dimethylcyclohexylamine (DMCHA) were weighed and mixed uniformly to prepare component A. 132 parts by weight of a polyisocyanate (PM-200, Vanhua chemical group Co., Ltd.) was weighed out and named as component B. Stirring the component A and the component B at the rotating speed of 2000r/min for 15s, pouring into a mold, and curing at 80 ℃ for 24h to obtain the product.
Comparative example 2
Unlike example 4, there was no DOPO in the reactants.
Comparative example 3
Different from example 4, DOPO is used as the flame retardant.
The polyurethane foam formulations are shown in Table 2 and the performance tests are shown in Table 3.
TABLE 1 formulation of the rosinyl phosphorus synergistic flame retardant of examples 1-4 (parts by weight)
TABLE 2 polyurethane foam formulations (parts by weight) of examples 1-4 and comparative example 1
TABLE 3 Performance testing of examples 1-4 and comparative example 1
As can be seen from the table above, the increase of the rosinyl silicon phosphorus synergistic flame retardant not only improves the flame retardant performance, but also improves the pressure loss strength and stability.
Claims (10)
1. A rosinyl silicon-phosphorus synergistic flame retardant is characterized in that: the structural formula is as follows:
2. the rosinyl phosphorosilicate synergistic flame retardant of claim 1, wherein: the raw material components comprise: 10-20 parts of rosin, 20-40 parts of triethoxy (3-epoxypropyloxypropyl) silane, 6-10 parts of triethylamine, 500 parts of dichloromethane 200-ion-substituted resin, 500 parts of anhydrous ethanol 300-ion-substituted resin, 5-15 parts of carbon tetrachloride, 40-100 parts of sodium chloride, 20-40 parts of hydrochloric acid, 3-10 parts of anhydrous sodium sulfate and 5-20 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, wherein the parts are in parts by mass.
3. The rosinyl phosphorosilicate synergistic flame retardant of claim 2, wherein: the rosin is dehydroabietic acid, tetrahydroabietic acid, abietic acid, acrylpimaric acid or fumylpimaric acid.
4. The method for preparing the rosinyl silicon phosphorus synergistic flame retardant of any one of claims 1 to 3, characterized in that: the method comprises the following steps:
(1) reacting triethoxy (3-epoxypropyloxypropyl) silane with pine to prepare rosin-based organosilicon polyol;
(2) reacting the rosinyl organic silicon polyol obtained in the step (1), triethylamine and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in an ice bath, washing and drying to obtain the rosinyl silicon-phosphorus synergistic flame retardant.
5. The method for preparing the rosinyl silicon phosphorus synergistic flame retardant of claim 4, wherein the method comprises the following steps: the method comprises the following steps:
(1) dissolving triethoxy (3-epoxypropyloxypropyl) silane and rosin in a three-neck flask filled with absolute ethyl alcohol, reacting for 5-7 h under the protection of nitrogen at the temperature of 80-90 ℃, and removing the absolute ethyl alcohol by rotary evaporation to obtain rosin-based organic silicon polyol;
(2) dissolving the rosin-based organic silicon polyol, triethylamine and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide obtained in the step (1) in dichloromethane at room temperature, cooling the solution to minus 10 ℃ to minus 5 ℃ in an ice bath, dropwise adding carbon tetrachloride into the solution, keeping the temperature of the solution at 0-10 ℃, and reacting for 12-15 hours after dropwise adding;
(3) and (3) washing the material obtained in the step (2) by using a saturated sodium chloride solution of 1M hydrochloric acid, and drying to obtain the rosinyl silicon phosphorus synergistic flame retardant.
6. The method for preparing the rosinyl silicon phosphorus synergistic flame retardant of claim 5, wherein the method comprises the following steps: in the step (3), drying is carried out for 4-6 h by using anhydrous sodium sulfate, then drying is carried out for 24-30 h in an oven at 75-85 ℃ after the solvent is removed by rotary evaporation.
7. A rosinyl silicon phosphorus synergistic flame retardant polyurethane foam comprises a component A and a component B, and is characterized in that:
the raw material components of the component A comprise: 100 parts of polyol, 2-3 parts of foam stabilizer, 1-2 parts of foaming agent, 0.1-0.3 part of catalyst and 5-20 parts of rosinyl silicon phosphorus synergistic flame retardant as claimed in any one of claims 1-3, wherein the polyol is polyether polyol and/or polyester polyol;
the component B is polyisocyanate, and the mass ratio of the component A to the component B is 1: 0.8-1.2, wherein the parts are parts by weight.
8. The rosin-based silicone-phosphorous synergistic flame retardant polyurethane foam according to claim 7, wherein: the foam stabilizer is GT-320 hard foam silicone oil, the foaming agent is water, the catalyst is N, N-Dimethylcyclohexylamine (DMCHA), and the polyisocyanate is at least one of xylene diisocyanate, toluene diisocyanate or polymethylene polyphenyl polyisocyanate.
9. The method for preparing the rosinyl silicon phosphorus synergistic flame retardant polyurethane foam according to claim 7 or 8, wherein the method comprises the following steps: the method comprises the following steps:
(1) uniformly mixing polyol, a foam stabilizer, a foaming agent, a catalyst and a rosinyl silicon phosphorus synergistic flame retardant to prepare a component A;
(2) and (3) stirring the component A and the component B for 10-20 seconds under the condition of high-speed stirring, quickly pouring into a mold, standing at 80-90 ℃ for 22-26 hours to finish curing, and obtaining the rosinyl silicon-phosphorus synergistic flame-retardant polyurethane foam after curing.
10. The method of claim 8, wherein: the rotating speed of the high-speed stirring in the step (2) is 2000-2500 r/min.
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