CN112521566A - Preparation method of lignin-based flame-retardant phenolic foam - Google Patents
Preparation method of lignin-based flame-retardant phenolic foam Download PDFInfo
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- CN112521566A CN112521566A CN202011089672.6A CN202011089672A CN112521566A CN 112521566 A CN112521566 A CN 112521566A CN 202011089672 A CN202011089672 A CN 202011089672A CN 112521566 A CN112521566 A CN 112521566A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/14—Modified phenol-aldehyde condensates
Abstract
The invention discloses a preparation method of lignin-based flame-retardant phenolic foam. The method comprises the steps of partially replacing phenol with lignin-based benzophenone, adding paraformaldehyde in batches under the action of multi-component composite catalysis, after the o-para position of phenolic hydroxyl in the lignin-based benzophenone participates in addition reaction for a certain time, increasing the reaction temperature to carry out polycondensation reaction, adding an aldehyde-binding agent when the viscosity meets the requirement, cooling and discharging to obtain the lignin-based intrinsic flame-retardant resol resin with a lignin-based benzophenone structure in a molecular structure. The resin is added with a surfactant and a foaming agent and is rapidly and uniformly stirred, then the self-made curing agent is added, the mixture is uniformly stirred to reach a milky state, and the milky state is rapidly poured into a preheated mold and is placed into an oven for foaming. The oxygen index of the obtained lignin-based intrinsic flame-retardant foam is obviously increased, and the invention promotes high-valued and fine utilization of lignin.
Description
Technical Field
The invention belongs to the technical field of intrinsic flame-retardant composite materials, and can be used in the field of phenolic foam.
Background
At present, organic foam heat insulation materials which are dominant in the market, such as polystyrene foam, polyvinyl chloride foam, polyurethane foam and the like, have low heat-resistant temperature, emit a large amount of heat after combustion, generate a large amount of smoke gas, cause environmental pollution and become one of main factors causing casualties in fire. Phenolic foam is a new type of foam developed in recent years, and is named as the king of thermal insulation materials by the list of all foams with good flame resistance, low smoke, stable high-temperature performance, heat insulation, sound insulation, easy molding and processing and better durability. Phenolic foams, however, suffer from "smoldering" problems, requiring further improvements in their flame retardancy.
Flame retardance means that materials can hinder the chain reaction by absorbing free radicals generated by combustion during combustion, and the materials are usually not combusted or are not easily combusted when meeting flame and are extinguished soon after leaving the flame. There are two methods for improving the flame retardancy of materials: flame retardants and intrinsic flame retardancy. The flame retardant is divided into two major types of additive type and reactive type, the additive type flame retardant mainly comprises phosphate ester, halogen-containing phosphate ester, halogenated hydrocarbon, antimony oxide, aluminum hydroxide and the like, the use is convenient, the applicability is strong, but the performance of the product is influenced when the addition amount is generally 10-30%. The reactive flame retardant is a monomer containing a flame retardant element, has little influence on the performance of the product, and is commonly a halogenated anhydride of polyester, tetrabromobisphenol A used for epoxy resin, phosphorus-containing polyol used for polyurethane and the like. The intrinsic flame retardance does not add a flame retardant, and has flame retardance by introducing a benzene ring or an aromatic heterocycle. The intrinsic flame-retardant fiber such as meta-aramid, polysulfonamide, polyimide and polyphenylene sulfide is introduced into the structure, and mass production is realized in China, but the intrinsic flame-retardant phenolic foam has not been reported in China. Lignin is a natural phenolic compound, contains a large number of benzene ring structures, the oxygen index is not obviously improved in the preparation of foam plastic products by replacing phenol, a benzene ring in the lignin structure is utilized, one side of the benzene ring is connected with another benzene ring through carbonyl to form a benzophenone structure (see patent 201911240777.4), and the intrinsic flame retardant purpose is achieved by increasing the content of the benzene ring. The application of this patent can promote the high-valued and meticulous utilization of lignin, opens up phenolic foam fire-retardant new approach.
Disclosure of Invention
The technical problem to be solved is as follows: in order to solve the problem of 'smoldering' of the phenolic foam and develop more application fields of the phenolic foam, the invention provides a preparation method of the lignin-based intrinsic flame-retardant phenolic foam, and the flame retardance of the prepared foam is obviously improved.
A preparation method of lignin basic characteristic flame-retardant phenolic foam comprises the following steps: melting phenol and a measured multi-element composite catalyst, adding lignin-based benzophenone for replacing the phenol after uniformly stirring, reacting for 2-3h at 70-75 ℃, heating to 90-95 ℃, continuing to react for 0.5-1h, adding an aldehyde-binding agent, cooling and discharging to obtain lignin-based intrinsic flame-retardant resol resin with a lignin-benzophenone structure in a molecular structure, adding a surfactant and a foaming agent into the resin, rapidly and uniformly stirring, adding a compound curing agent, rapidly pouring the mixture into a preheated mold after uniformly stirring to achieve a milky white state, and placing the mixture into an oven for foaming.
The multi-element composite catalyst is obtained by compounding inorganic salt which is hydrolyzed to be alkaline and amine substances, and the pH value of a reaction system is adjusted to be 7-8.5.
The inorganic salt which is alkaline in hydrolysis is any one of sodium carbonate, sodium bicarbonate and sodium sulfite, the amine substance is any one of ammonia water, diethylamine, triethylamine, diethylenetriamine, triethylene tetramine and tetraethylene pentamine, and the mass ratio of the inorganic salt and the amine substance which are alkaline in hydrolysis is 1: 1-5.
The mass percentage of the multi-element composite catalyst in the lignin is 3-8%.
The molar ratio of phenol to paraformaldehyde is 1.5-2.0.
The mass percentage of the lignin-based benzophenone replacing the phenol is 10-40%.
The compound curing agent is p-toluenesulfonic acid: small molecule polyols: phosphoric acid: phenolsulfonic acid ═ 15-10:6-4:5-4:4-1 (mass ratio).
The surfactant is added according to the mass ratio of DC-193 to Tween 80-5-4: 6-8.
The lignin-based intrinsic flame-retardant resol phenolic resin comprises a surfactant, a foaming agent and a curing agent, wherein the ratio of the foaming agent to the curing agent is 100:4-6:6-8: 10-15.
The temperature of the oven for foaming is 70-85 ℃, and the curing time is 10-30 min.
Advantageous effects
1. The invention is different from other methods for improving the flame retardance of phenolic foam, utilizes abundant lignin resources in China, utilizes a large number of benzene rings contained in lignin, and forms a benzophenone structure by a chemical method, so that the flame retardance of the foam is obviously improved.
2. The lignin-based benzophenone structure not only improves the flame retardant property of the foam, but also can replace part of phenol to participate in the reaction because the phenolic hydroxyl does not participate in the reaction, thereby reducing the cost. The lignin in the invention has the effect of 'one dose and multiple effects'.
Drawings
Fig. 1 is a combustion comparison diagram.
Detailed Description
The lignin-based benzophenone used in the present invention can be prepared as described in patent application No. 201911240777.4.
Example 1
(1) Melting 360g of phenol, adding 90g of lignin-based benzophenone (20% substituted phenol), adding 15g of water, fully and uniformly stirring, adding 3% of catalyst (accounting for the mass percent of the phenol), compounding the catalyst by sodium carbonate and ammonia water (in a mass ratio of 1:5), controlling the pH of the system to be 7.5, adding 220g of paraformaldehyde in four batches (in a phenolic aldehyde molar ratio of 1:1.7), reacting at 70 ℃ for 2 hours, reacting at 90 ℃ for 40 minutes, adding 20g of melamine, cooling and discharging to obtain the black resol.
(2) 100g of black resol, 6g of surfactant (DC-193: Tween 80: 5:6) and 6g of foaming agent n-pentane are added, high-speed blending is carried out for 20s, 10g of curing agent (p-toluenesulfonic acid: small-molecular polyol: phosphoric acid: phenolsulfonic acid: 15:6:5:1 (mass ratio) is added, the mixture is milk-white and then is quickly poured into a preheated mold, the mixture is cured for 15min in an oven at 70 ℃, and the mixture is cured for one week at room temperature, and the oxygen index is tested.
Example 2
(1) Melting 360g of phenol, adding 101.5g of lignin-based benzophenone (22% substituted phenol), adding 15g of water, fully stirring uniformly, adding 3.5% of catalyst (accounting for the mass percent of the phenol), compounding sodium bicarbonate and diethylamine (the mass ratio is 1:4), adjusting the pH value of the system to 8, adding 223g of paraformaldehyde into the mixture in four batches (the molar ratio of the formaldehyde to the phenol is 1.7), reacting at 70 ℃ for 2 hours, reacting at 90 ℃ for 40 minutes, adding 21g of melamine, cooling and discharging to obtain the black resol.
(2) 100g of black resol, 4g of surfactant (DC-193: Tween 80: 5:7) and 7g of foaming agent n-pentane are added, high-speed blending is carried out for 20s, 12g of curing agent (p-toluenesulfonic acid: small-molecular polyol: phosphoric acid: phenolsulfonic acid: 10:5:4:1 (mass ratio) is added, the mixture is milk-white and then is quickly poured into a preheated mold, the mixture is cured for 20min in an oven at 75 ℃, and the mixture is cured for one week at room temperature, and the oxygen index is tested.
Example 3
(1) Melting 360g of phenol, adding 40g of lignin-based benzophenone (10% substituted phenol), adding 15g of water, fully and uniformly stirring, adding 3.5% of catalyst (accounting for the mass percent of the phenol), compounding the catalyst by sodium sulfite and diethylenetriamine (the mass ratio is 1:4), controlling the pH of the system to be 8, adding 218.5g of paraformaldehyde into the system in four batches (the molar ratio of the formaldehyde to the phenol is 1.8), reacting for 2 hours at 70 ℃, reacting for 40 minutes at 90 ℃, adding 21g of melamine, cooling and discharging to obtain the black resol.
(2) 100g of black resol, 5g of surfactant (DC-193: Tween 80: 3:7) and 7g of foaming agent n-pentane are added, high-speed blending is carried out for 20s, 12g of curing agent (p-toluenesulfonic acid: small-molecular polyol: phosphoric acid: phenolsulfonic acid: 10:5:4:1 (mass ratio) is added, the mixture is milk-white and then is quickly poured into a preheated mold, the mixture is cured for 15min in an oven at 80 ℃, and the mixture is cured for one week at room temperature, and the oxygen index is tested.
Example 4
(1) Melting 360g of phenol, adding 120g of lignin-based benzophenone (25% substituted phenol), adding 15g of water, fully and uniformly stirring, adding 6% of catalyst (accounting for the mass percent of the phenol), compounding the catalyst by sodium sulfite and triethylene tetramine (the mass ratio is 1:4), adding 241.5g of paraformaldehyde into the mixture in four batches, reacting at 70 ℃ for 2 hours, reacting at 90 ℃ for 40 minutes, adding 21g of melamine, cooling and discharging to obtain the black resol.
(2) 100g of black resol, 5g of surfactant (DC-193: Tween 80: 5:7) and 8g of foaming agent n-pentane are added, high-speed blending is carried out for 20s, 14g of curing agent (p-toluenesulfonic acid: small-molecular polyol: phosphoric acid: phenolsulfonic acid: 12:5:4:3 (mass ratio)) is added, the mixture is milk-white and then is quickly poured into a preheated mold, the mixture is cured for 20min in an oven at 80 ℃, and the mixture is cured for one week at room temperature, and the oxygen index is tested.
Example 5
(1) Melting 360g of phenol, adding 120g of lignin-based benzophenone (30% substituted phenol), adding 20g of water, fully and uniformly stirring, adding 8% of catalyst (accounting for the mass percent of the phenol), compounding sodium sulfite and tetraethylenepentamine (in a mass ratio of 1:5), adding 279g of paraformaldehyde into the mixture in four batches (in a phenolic aldehyde molar ratio of 2.0), reacting at 70 ℃ for 2 hours, reacting at 90 ℃ for 40 minutes, adding 25g of melamine, cooling and discharging to obtain the black resol.
(2) 100g of black resol, 6g of surfactant (DC-193: Tween 80: 5:7) and 8g of foaming agent n-pentane are added, high-speed blending is carried out for 20s, 15g of curing agent (p-toluenesulfonic acid: small-molecular polyol: phosphoric acid: phenolsulfonic acid: 15:6:4:3 (mass ratio)) is added, the mixture is milk-white and then is quickly poured into a preheated mold, the mixture is cured for 30min in an oven at 85 ℃, and the mixture is cured for one week at room temperature, and the oxygen index is tested.
Comparative example
(1) Melting 360g of phenol, adding 90g of degraded lignin (refer to patent 201911240777.4 (application number), 20% of the degraded lignin replaces phenol), adding 15g of water, fully stirring uniformly, adding 3% of catalyst (accounting for the mass percent of phenol), wherein the catalyst is sodium carbonate and ammonia water (the mass ratio is 1:5), the pH value of the system is 7.5, adding 220g of paraformaldehyde into the system in four batches (the molar ratio of phenol aldehyde is 1:1.7), reacting at 70 ℃ for 2 hours, reacting at 90 ℃ for 40min, adding 20g of melamine, cooling and discharging to obtain the black resol.
(2) 100g of black resol, 6g of surfactant (DC-193: Tween 80: 5:6) and 6g of foaming agent n-pentane are added, high-speed blending is carried out for 20s, 10g of curing agent (p-toluenesulfonic acid: small-molecular polyol: phosphoric acid: phenolsulfonic acid: 15:6:5:1 (mass ratio) is added, the mixture is milk-white and then is quickly poured into a preheated mold, the mixture is cured for 15min in an oven at 70 ℃, and the mixture is cured for one week at room temperature, and the oxygen index is tested.
EXAMPLES oxygen index COMPARATIVE TABLE
| Examples | Oxygen index/% |
| 1 | 46.8 |
| 2 | 48.2 |
| 3 | 42.6 |
| 4 | 51.8 |
| 5 | 55.6 |
| Comparative example | 37.8 |
Note: density ranges for foams prepared in examples 1-5 and comparative examples: 50-55kg/m3
As can be seen from the comparison table, the flame retardance of the foam is obviously improved with the increase of the mass percentage of the lignin-based benzophenone replacing the phenol, and when the replacing amount is 30%, the oxygen index of example 5 is improved by 47% compared with that of the control example (the lignin is degraded to replace the phenol by 20%). Example 1 (lignin-based benzophenone substituted for phenol 20%) had an oxygen index increase of 23.8% over the control. Further, as shown in fig. 1, the comparative example burns a lot, and example 5 is almost non-combustible, so that the phenolic foam containing the benzophenone structure has a remarkable flame retardant effect.
Claims (10)
1. A preparation method of lignin basic characteristic flame-retardant phenolic foam is characterized by comprising the following steps: melting phenol and a measured multi-element composite catalyst, adding lignin-based benzophenone for replacing the phenol after uniformly stirring, reacting for 2-3h at 70-75 ℃, heating to 90-95 ℃, continuing to react for 0.5-1h, adding an aldehyde-binding agent, cooling and discharging to obtain lignin-based intrinsic flame-retardant resol resin with a lignin-benzophenone structure in a molecular structure, adding a surfactant and a foaming agent into the resin, rapidly and uniformly stirring, adding a compound curing agent, rapidly pouring the mixture into a preheated mold after uniformly stirring to achieve a milky white state, and placing the mixture into an oven for foaming.
2. The preparation method of the lignin-based inherently flame-retardant phenolic foam as claimed in claim 1, which is characterized in that: the multi-element composite catalyst is obtained by compounding inorganic salt which is hydrolyzed to be alkaline and amine substances, and the pH value of a reaction system is adjusted to be 7-8.5.
3. The method for preparing lignin-based inherently flame-retardant phenolic foam according to claim 1, wherein: the inorganic salt which is alkaline in hydrolysis is any one of sodium carbonate, sodium bicarbonate and sodium sulfite, the amine substance is any one of ammonia water, diethylamine, triethylamine, diethylenetriamine, triethylene tetramine and tetraethylene pentamine, and the mass ratio of the inorganic salt and the amine substance which are alkaline in hydrolysis is 1: 1-5.
4. The method for preparing lignin-based inherently flame-retardant phenolic foam according to claim 1, wherein: the mass percentage of the multi-element composite catalyst in the lignin is 3-8%.
5. The method for preparing lignin-based inherently flame-retardant phenolic foam according to claim 1, wherein: the molar ratio of phenol to paraformaldehyde is 1.5-2.0.
6. The method for preparing lignin-based inherently flame-retardant phenolic foam according to claim 1, wherein: the mass percentage of the lignin-based benzophenone replacing the phenol is 10-40%.
7. The method for preparing lignin-based inherently flame-retardant phenolic foam according to claim 1, wherein: the compound curing agent is p-toluenesulfonic acid: small molecule polyols: phosphoric acid: phenolsulfonic acid ═ 15-10:6-4:5-4:4-1 (mass ratio).
8. The method for preparing lignin-based inherently flame-retardant phenolic foam according to claim 1, wherein: the surfactant is added according to the mass ratio of DC-193 to Tween 80-5-4: 6-8.
9. The method for preparing lignin-based inherently flame-retardant phenolic foam according to claim 1, wherein: the lignin-based intrinsic flame-retardant resol phenolic resin comprises a surfactant, a foaming agent and a curing agent, wherein the ratio of the foaming agent to the curing agent is 100:4-6:6-8: 10-15.
10. The method for preparing lignin-based inherently flame-retardant phenolic foam according to claim 1, wherein: the temperature of the oven for foaming is 70-85 ℃, and the curing time is 10-30 min.
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| JPS62186226A (en) * | 1986-02-12 | 1987-08-14 | Mitsui Toatsu Chem Inc | Orienting agent for liquid crystal panel |
| CN102504477A (en) * | 2011-10-18 | 2012-06-20 | 中国林业科学研究院林产化学工业研究所 | Lignin-modified phenolic foam and preparation method thereof |
| CN103613728A (en) * | 2013-12-13 | 2014-03-05 | 中国林业科学研究院林产化学工业研究所 | Preparation method of lignin phenolic foams |
| CN110240685A (en) * | 2018-10-11 | 2019-09-17 | 中国林业科学研究院林产化学工业研究所 | A kind of high activity lignin modification resol and its preparation method and application |
| CN111205437A (en) * | 2020-02-26 | 2020-05-29 | 中国林业科学研究院林产化学工业研究所 | Preparation method of biological basic characteristic type flame-retardant epoxy resin |
-
2020
- 2020-10-13 CN CN202011089672.6A patent/CN112521566A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62186226A (en) * | 1986-02-12 | 1987-08-14 | Mitsui Toatsu Chem Inc | Orienting agent for liquid crystal panel |
| CN102504477A (en) * | 2011-10-18 | 2012-06-20 | 中国林业科学研究院林产化学工业研究所 | Lignin-modified phenolic foam and preparation method thereof |
| CN103613728A (en) * | 2013-12-13 | 2014-03-05 | 中国林业科学研究院林产化学工业研究所 | Preparation method of lignin phenolic foams |
| CN110240685A (en) * | 2018-10-11 | 2019-09-17 | 中国林业科学研究院林产化学工业研究所 | A kind of high activity lignin modification resol and its preparation method and application |
| CN111205437A (en) * | 2020-02-26 | 2020-05-29 | 中国林业科学研究院林产化学工业研究所 | Preparation method of biological basic characteristic type flame-retardant epoxy resin |
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| Title |
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| 王积涛等: "《有机化学》", 31 December 2009, 南开大学出版社 * |
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Application publication date: 20210319 |