CN111635511A - Crosslinked polymer flame retardant and preparation method thereof - Google Patents
Crosslinked polymer flame retardant and preparation method thereof Download PDFInfo
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- CN111635511A CN111635511A CN202010575528.7A CN202010575528A CN111635511A CN 111635511 A CN111635511 A CN 111635511A CN 202010575528 A CN202010575528 A CN 202010575528A CN 111635511 A CN111635511 A CN 111635511A
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a cross-linked polymer flame retardant and a preparation method thereof, the preparation method of the flame retardant comprises the steps of firstly preparing chlorinated paraffin containing carboxyl by the reaction of chlorinated paraffin and p-hydroxybenzoic acid, then acylating the chlorinated paraffin containing carboxyl to obtain chlorinated paraffin containing acyl chloride, then carrying out esterification reaction with tris (2-hydroxyethyl) isocyanurate to obtain chlorinated paraffin containing hydroxyl isocyanurate modification, then reacting with tetrabromophthalic anhydride to form novel dibasic acid, and finally carrying out polycondensation with tris (2-hydroxyethyl) isocyanurate to form the polymer flame retardant.
Description
Technical Field
The invention relates to a cross-linked polymer flame retardant and a preparation method thereof, belonging to the field of plastic rubber flame retardants.
Background
With the development of national economy and the improvement of the living standard of people, polymer materials such as synthetic fibers, plastics, rubbers and the like are more and more widely applied to various fields such as transportation, building materials, electronic appliances, daily furniture, interior decoration and the like. However, these polymer materials are generally flammable and easily cause fire accidents, and in order to solve the problems of flame resistance and smoke suppression of synthetic materials and to ensure the safety of the synthetic materials, the most effective method is to add a flame retardant. The halogen flame retardant has less addition amount, low cost and good compatibility with synthetic materials, and does not change the original machining performance of the flame retardant product, so the halogen flame retardant is the organic flame retardant with the largest output and use amount at present. However, the halogen-based flame retardants are limited because of problems such as decomposition to generate hydrogen halide during combustion. With the increasing awareness of flame-retardant fire prevention worldwide, the development of highly effective halogen flame retardants to reduce the amount of hydrogen halide released during combustion and to reduce the influence on the machinability of materials is an important research direction.
The chlorinated paraffin is a traditional polyvinyl chloride auxiliary additive and has the characteristics of low volatility, flame retardance, good electrical insulation, low price and the like. But the flame retardant effect is general, and the flame retardant effect needs to be improved by compounding other flame retardants when in use, so that the wide application of the flame retardant is hindered. In addition, over time, chlorinated paraffins tend to migrate out of the polymer network, reducing the durability of the flame retardant.
Disclosure of Invention
Aiming at the defects of chlorinated paraffin in the prior art, the invention aims to provide a bromine-containing isocyanurate modified chlorinated paraffin flame retardant with high flame retardant efficiency. The product has stable physical and chemical properties, good heat resistance and good migration resistance, has the function of preventing charring and dropping, and can overcome the defects in the prior art.
The invention also aims to provide a method for preparing the bromine-containing isocyanurate modified chlorinated paraffin, which has the advantages of wide raw material source, simple operation and mild reaction conditions.
The invention provides a cross-linked polymer flame retardant which is characterized by having a structure shown in a formula (I):
wherein, in the formula (I), R1、R2Is a chlorinated paraffin chain segment.
The invention also provides a preparation method of the macromolecular flame retardant, which comprises the following steps:
step (1): preparation of chlorinated paraffins containing carboxyl groups
Dissolving chlorinated paraffin in butanone, adding a certain amount of p-hydroxybenzoic acid and potassium carbonate, and heating to react under the protection of nitrogen to obtain chlorinated paraffin containing carboxyl;
step (2): preparation of chlorinated paraffins containing acid chlorides
Adding the chlorinated paraffin containing carboxyl obtained in the step (1) into a reaction kettle, and dropwise adding excessive phosphorus trichloride into the reaction kettle to react to obtain chlorinated paraffin containing acyl chloride;
and (3): preparation of chlorinated paraffin modified by isocyanuric ester containing dihydroxy
Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of tris (2-hydroxyethyl) isocyanurate and triethylamine serving as an acid-binding agent for esterification reaction, wherein the molar ratio of the chlorinated paraffin containing acyl chloride to the tris (2-hydroxyethyl) isocyanurate is 1-1.2: 1, and reacting to obtain chlorinated paraffin containing dihydroxy isocyanurate modification;
and (4): preparation of brominated isocyanurate-modified chlorinated Paraffin dibasic acid
Adding the chlorinated paraffin containing the dihydroxy isocyanurate modification obtained in the step (3) and tetrabromophthalic anhydride into a reaction kettle, and reacting at the temperature of 60-80 ℃ for 3-7 h to obtain brominated isocyanurate modified chlorinated paraffin dibasic acid;
and (5): preparation of high molecular flame retardant
And (3) adding brominated isocyanurate modified chlorinated paraffin dibasic acid prepared in the step (4), tris (2-hydroxyethyl) isocyanurate and a proper amount of water-carrying agent toluene or cyclohexane into a reaction kettle, adding p-toluenesulfonic acid with the mass fraction being 1-5% of the total mass of reactants, heating to 150-220 ℃ under stirring, reacting for 3-6 h, and drying and crushing the product to obtain the high-molecular flame retardant.
The preparation method of the cross-linked polymer flame retardant further comprises the following preferable scheme:
in the preferable scheme, the chlorinated paraffin and the p-hydroxybenzoic acid in the step (1) react at the temperature of 55-80 ℃ for 10-30 h to prepare the chlorinated paraffin containing carboxyl.
In the preferable scheme, the chlorinated paraffin containing carboxyl in the step (2) reacts with excessive phosphorus trichloride at the temperature of 50-70 ℃ for 4-6 h to prepare chlorinated paraffin containing acyl chloride.
In a preferable scheme, the esterification reaction in the step (3) is carried out under the reaction condition that chlorinated paraffin containing acyl chloride is slowly dripped into the mixed solution of the tris (2-hydroxyethyl) isocyanurate and the acid-binding agent in an ice-water bath for reaction, and the reaction is continued in the ice-water bath for 2-4 hours after the dripping is finished.
In the preferable scheme, the reaction molar ratio of the chlorinated paraffin containing the dihydroxy isocyanurate modification to the tetrabromophthalic anhydride in the step (4) is 1: 2.
In a preferred scheme, in the step (5), the reaction molar ratio of the brominated isocyanurate-modified chlorinated paraffin dibasic acid to the carboxyl and hydroxyl in the tris (2-hydroxyethyl) isocyanurate is 1: 1.
The invention has the beneficial effects that: according to the invention, isocyanurate is used as a bridge chain for the first time to connect traditional chlorinated paraffin and tetrabromophthalic anhydride to synthesize a novel high-molecular flame retardant, three excellent flame-retardant elements of nitrogen, bromine and chlorine are simultaneously embedded into the branched chlorinated paraffin molecule, and the three elements generate synergistic interaction from different flame-retardant mechanisms in a synergistic manner, so that higher flame-retardant efficiency can be expressed; meanwhile, the molecule has a cross-linked structure, is insoluble and infusible, and has good migration resistance. The whole preparation process has the advantages of easily available raw materials, low cost, simple operation, high purity of the obtained product and high yield, and meets the requirements of industrial production.
Drawings
FIG. 1 is an infrared chart of a crosslinked polymeric flame retardant obtained in example 3.
FIG. 1: 2920cm-1And 2850cm-1Respectively represents the stretching vibration absorption peak of methylene and methyl, 1470cm-1And 1370cm-1The bending vibration absorption peak of methyl group. 1745cm-1Is the absorption peak of stretching vibration of C ═ O in the ester group, 1690cm-1And 1420cm-1Is the expansion vibration absorption peak of C ═ O in isocyanurate, 1150cm-1At the stretching vibration peak of the C-N single bond, 1230cm-1And 1050cm-1Is a characteristic absorption peak of the C-O-C ether bond of 715cm-1At the stretching vibration peak of the C-Cl bond of 560cm-1And (b) is a stretching vibration peak of the C-Br bond.
Detailed Description
The following examples are intended to further illustrate the content of the invention, but not to limit the scope of the invention.
Example 1
(1) Preparation of chlorinated paraffin 42 containing carboxyl group: dissolving 20g of chlorinated paraffin 42 in 200mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 30g of potassium carbonate, and reacting at 55 ℃ for 30h under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 42 containing carboxyl.
(2) Preparation of acid chloride-containing chlorinated paraffin 42: adding 70mol of chlorinated paraffin 42 containing carboxyl into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 70 ℃, reacting for 4 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 42 containing acyl chloride.
(3) Preparation of the chlorinated paraffin 42 modified by the isocyanate containing the dihydroxy: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding dichloromethane solution containing 103mol of chlorinated paraffin 42 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 2h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the chlorinated paraffin 42 containing the binary hydroxyl isocyanurate modification.
(4) Preparation of brominated isocyanurate modified chlorinated paraffin 42 dibasic acid: adding 100mol of carbon tetrachloride, 70mol of chlorinated paraffin 42 modified by dihydroxy isocyanurate and 140mol of tetrabromophthalic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 60 ℃, reacting for 7h, cooling, extracting and separating by ethyl acetate, drying an organic phase by anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain brominated isocyanurate modified chlorinated paraffin 42 dibasic acid.
(5) Preparing a cross-linked polymer flame retardant: and (3) adding 90mol of brominated isocyanurate modified chlorinated paraffin 42 dibasic acid prepared in the step (4), 60mol of tris (2-hydroxyethyl) isocyanurate, a proper amount of water-carrying agent toluene or cyclohexane and p-toluenesulfonic acid with the mass fraction being 1-5% of the total mass of the reactants into a reaction kettle, heating to 150 ℃ under stirring, reacting for 6h, and drying and crushing the product to obtain the high-molecular flame retardant T1.
Example 2
(1) Preparation of chlorinated paraffin 52 containing carboxyl group: dissolving 20g of chlorinated paraffin 52 in 200mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 30g of potassium carbonate, and reacting at 80 ℃ for 10 hours under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 52 containing carboxyl.
(2) Preparation of chlorinated paraffin 52 containing acid chloride: adding 70mol of carboxyl-containing chlorinated paraffin 52 into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 50 ℃, reacting for 6 hours, cooling to room temperature, standing and layering to obtain the chlorinated paraffin 52 containing acyl chloride.
(3) Preparation of the chlorinated paraffin 52 modified by the isocyanuric ester containing the dibasic hydroxyl: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding dichloromethane solution containing 102mol of chlorinated paraffin 52 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 4h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the chlorinated paraffin 52 containing the binary hydroxyl isocyanurate modification.
(4) Preparation of brominated isocyanurate-modified chlorinated paraffin 52 dibasic acid: adding 100mol of carbon tetrachloride, 70mol of chlorinated paraffin 52 modified by dibasic hydroxyl isocyanurate and 140mol of tetrabromophthalic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 80 ℃, reacting for 3h, cooling, extracting and separating by using ethyl acetate, drying an organic phase by using anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain brominated isocyanurate modified chlorinated paraffin 52 dibasic acid.
(5) Preparing a cross-linked polymer flame retardant: and (3) adding 90mol of brominated isocyanurate modified chlorinated paraffin 52 dibasic acid prepared in the step (4), 60mol of tris (2-hydroxyethyl) isocyanurate, a proper amount of water-carrying agent toluene or cyclohexane and p-toluenesulfonic acid with the mass fraction being 1-5% of the total mass of the reactants into a reaction kettle, heating to 220 ℃ under stirring, reacting for 3h, and drying and crushing the product to obtain the high-molecular flame retardant T2.
Example 3
(1) Preparation of carboxyl group-containing chlorinated paraffin 70: dissolving 20g of chlorinated paraffin 70 in 200mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 30g of potassium carbonate, and reacting at 65 ℃ for 24h under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 70 containing carboxyl.
(2) Preparation of acid chloride-containing chlorinated paraffin 70: adding 70mol of carboxyl-containing chlorinated paraffin 52 into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 60 ℃, reacting for 5 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 70 containing acyl chloride.
(3) Preparation of the dihydric hydroxyl isocyanurate-containing modified chlorinated paraffin 70: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 202mol of chlorinated paraffin 70 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 3h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying the organic phase with anhydrous calcium chloride, drying the organic phase for 8h, filtering the organic phase under reduced pressure, and distilling the filtrate to remove the solvent to obtain the chlorinated paraffin 70 containing the binary hydroxyl isocyanurate modification.
(4) Preparation of brominated isocyanurate-modified chlorinated paraffin 70 dibasic acid: adding 100mol of carbon tetrachloride, 70mol of chlorinated paraffin containing dihydroxy isocyanurate modification and 70mol of tetrabromophthalic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 70 ℃, reacting for 5h, cooling, extracting and separating by using ethyl acetate, drying an organic phase by using anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain brominated isocyanurate modified chlorinated paraffin 70 dibasic acid.
(5) Preparing a cross-linked polymer flame retardant: and (3) adding 90mol of brominated isocyanurate modified chlorinated paraffin 70 dibasic acid prepared in the step (4), 60mol of tris (2-hydroxyethyl) isocyanurate, a proper amount of water-carrying agent toluene or cyclohexane and p-toluenesulfonic acid with the mass fraction being 1-5% of the total mass of the reactants into a reaction kettle, heating to 210 ℃ under stirring, reacting for 4h, and drying and crushing the product to obtain the high-molecular flame retardant T3.
The inventor applies the prepared isocyanurate modified chlorinated paraffin polymer flame retardant to a polyurethane material (TPU). Reference is made to: GB/T2406-2008 'Plastic burning Performance test method-oxygen index method' measures the flame retardant property of the product in TPU. Testing the migration and precipitation of the flame retardant under the conditions of constant temperature and constant humidity. Antimony trioxide (Sb) with different flame retardants and synergistic flame retardant2O3) And TPU are uniformly mixed according to the proportion in the formula, extruded by an extruder, made into sample strips, and tested for physical and flame retardant properties, wherein the test results are shown in Table 1. Formula (by mass): 70 parts of TPU, antimony trioxide (Sb)2O3)5 parts of flame retardant and 25 parts of flame retardant.
Table 1 performance data for the cross-linked polymeric flame retardants synthesized in examples 1-3:
in conclusion, the novel high-molecular flame retardant is synthesized by connecting the traditional chlorinated paraffin and tetrabromophthalic anhydride by taking the isocyanurate as a bridge chain, three excellent flame-retardant elements, namely nitrogen, bromine and chlorine, are simultaneously embedded into the branched chlorinated paraffin molecules, and the three elements generate synergistic interaction from different flame-retardant mechanisms in a synergistic manner, so that the flame-retardant flame retardant has higher flame-retardant efficiency, has a cross-linked structure, is insoluble and infusible, and has good migration resistance.
Claims (7)
1. A cross-linked polymer flame retardant, characterized in that the cross-linked polymer flame retardant has a structure represented by formula (I):
wherein, in the formula (I), R1、R2、R3、R4Is a chlorinated paraffin chain segment.
2. The preparation method of the cross-linked polymer flame retardant is characterized by comprising the following steps:
step (1): preparation of chlorinated paraffins containing carboxyl groups
Dissolving chlorinated paraffin in butanone, adding a certain amount of p-hydroxybenzoic acid and potassium carbonate, and heating to react under the protection of nitrogen to obtain chlorinated paraffin containing carboxyl;
step (2): preparation of chlorinated paraffins containing acid chlorides
Adding the chlorinated paraffin containing carboxyl obtained in the step (1) into a reaction kettle, and dropwise adding excessive phosphorus trichloride into the reaction kettle to react to obtain chlorinated paraffin containing acyl chloride;
and (3): preparation of chlorinated paraffin modified by isocyanuric ester containing dihydroxy
Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of tris (2-hydroxyethyl) isocyanurate and triethylamine serving as an acid-binding agent for esterification reaction, wherein the molar ratio of the chlorinated paraffin containing acyl chloride to the tris (2-hydroxyethyl) isocyanurate is 1-1.2: 1, and reacting to obtain chlorinated paraffin containing dihydroxy isocyanurate modification;
and (4): preparation of brominated isocyanurate-modified chlorinated Paraffin dibasic acid
Adding the chlorinated paraffin containing the dihydroxy isocyanurate modification obtained in the step (3) and tetrabromophthalic anhydride into a reaction kettle, and reacting at the temperature of 60-80 ℃ for 3-7 h to obtain brominated isocyanurate modified chlorinated paraffin dibasic acid;
and (5): preparation of high molecular flame retardant
And (3) adding brominated isocyanurate modified chlorinated paraffin dibasic acid prepared in the step (4), tris (2-hydroxyethyl) isocyanurate and a proper amount of water-carrying agent toluene or cyclohexane into a reaction kettle, adding p-toluenesulfonic acid with the mass fraction being 1-5% of the total mass of reactants, heating to 150-220 ℃ under stirring, reacting for 3-6 h, and drying and crushing the product to obtain the high-molecular flame retardant.
3. The method according to claim 2, wherein the chlorinated paraffin containing carboxyl group is prepared by reacting the chlorinated paraffin with p-hydroxybenzoic acid in the step (1) at a temperature of 55-80 ℃ for 10-30 hours.
4. The preparation method of claim 2, wherein the chlorinated paraffin containing carboxyl in the step (2) reacts with excess phosphorus trichloride at a temperature of 50-70 ℃ for 4-6 h to obtain chlorinated paraffin containing acyl chloride.
5. The preparation method of claim 2, wherein the esterification reaction in the step (3) is carried out under the reaction conditions that chlorinated paraffin containing acyl chloride is slowly added dropwise into the mixed solution of tris (2-hydroxyethyl) isocyanurate and the acid-binding agent in an ice-water bath for reaction, and after the dropwise addition is completed, the reaction is continued in the ice-water bath for 2-4 hours.
6. The method of claim 2, wherein the molar ratio of the dihydroxy isocyanurate-modified chlorinated paraffin-containing compound to tetrabromophthalic anhydride in step (4) is 1: 2.
7. The method according to claim 2, wherein the molar ratio of the brominated isocyanurate-modified chlorinated paraffin dibasic acid reacted with the carboxyl group and the hydroxyl group in tris (2-hydroxyethyl) isocyanurate in the step (5) is 1: 1.
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| CN112795275A (en) * | 2021-01-20 | 2021-05-14 | 李艳艳 | Steel structure fireproof epoxy coating and preparation method thereof |
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| CN112795275A (en) * | 2021-01-20 | 2021-05-14 | 李艳艳 | Steel structure fireproof epoxy coating and preparation method thereof |
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