阅读说明：本技术 一种钢结构防火环氧涂料及其制备方法 (Steel structure fireproof epoxy coating and preparation method thereof ) 是由 李艳艳 于 2021-01-20 设计创作，主要内容包括：本发明公开了一种钢结构防火环氧涂料,该环氧涂料包括一种具有阻燃功能的环氧树脂,该环氧树脂的制备方法是由氯化石蜡和对羟基苯甲酸反应制备含羧基氯化石蜡,再由含羧基氯化石蜡经酰化得含酰氯氯化石蜡,然后与[(6-氧代-6H-二苯并[C,E][1,2]氧磷杂己环-6-基)甲基]丁二醇反应,产物经酰化后再与三(2-羟乙基)异氰尿酸酯发生酯化反应得到含磷异氰尿酸酯改性的的氯化石蜡,然后与四氟对苯二甲酰氯和环氧氯丙烷反应制备得到环氧树脂,制备的钢结构防火涂料由于阻燃元素磷、氟、氯和氮的协同作用而具有优异的阻燃性能。(The invention discloses a steel structure fireproof epoxy coating, which comprises an epoxy resin with a flame retardant function, the preparation method of the epoxy resin comprises the steps of preparing chlorinated paraffin containing carboxyl by reacting the chlorinated paraffin with p-hydroxybenzoic acid, acylating the chlorinated paraffin containing carboxyl to obtain chlorinated paraffin containing acyl chloride, then reacting with [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol, acylating the product, and then carrying out esterification reaction with tris (2-hydroxyethyl) isocyanurate to obtain chlorinated paraffin modified by the phosphorus-containing isocyanurate, then reacting with tetrafluoroterephthaloyl chloride and epichlorohydrin to prepare epoxy resin, wherein the prepared steel structure fireproof coating has excellent flame retardant property due to the synergistic effect of flame retardant elements of phosphorus, fluorine, chlorine and nitrogen.)

1. The steel structure fireproof epoxy coating is characterized by comprising epoxy resin, polyamide resin, ammonium polyphosphate, talcum powder, antimony trioxide and butanone; the epoxy resin has a structure shown in a formula (I):

in the formula (I), R is a chlorinated paraffin chain segment.

2. The preparation method of the epoxy resin with the flame-retardant and fireproof functions is characterized by comprising the following steps of:

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

Acylating the chlorinated paraffin containing the carboxyl obtained in the step (1) by thionyl chloride to obtain chlorinated paraffin containing acyl chloride;

and (3): preparation of hydroxy-terminated phosphorus-containing chlorinated Paraffins

Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol and acid-binding agent triethylamine for esterification reaction to obtain chlorinated paraffin containing hydroxyl;

and (4): preparation of acid chloride terminated phosphorus-containing chlorinated Paraffin

Reacting the hydroxyl-terminated phosphorus-containing chlorinated paraffin obtained in the step (3) with succinyl chloride to obtain acyl chloride-terminated phosphorus-containing chlorinated paraffin;

and (5): preparation of phosphorus-containing isocyanurate-modified chlorinated Paraffin

Slowly dripping the acyl chloride-terminated phosphorus-containing chlorinated paraffin prepared in the step (4) into a mixed system of tris (2-hydroxyethyl) isocyanurate and triethylamine serving as an acid-binding agent for esterification reaction to obtain phosphorus-containing isocyanurate modified chlorinated paraffin;

and (6): preparation of tetrafluoroterephthaloyl chloride

Acylating tetrafluoroterephthalic acid by thionyl chloride to obtain tetrafluoroterephthaloyl chloride;

and (7): preparation of epoxy resins

Slowly dripping the tetrafluoroterephthaloyl chloride obtained in the step (6) into a mixed system of the phosphorus-containing isocyanurate modified chlorinated paraffin prepared in the step (5) and triethylamine serving as an acid-binding agent for esterification reaction to obtain dibasic acid;

and (8): preparation of epoxy resins

And (4) adding the dibasic acid obtained in the step (7) and epoxy chloropropane into a reaction kettle, adding a proper amount of catalyst cetyl trimethyl ammonium bromide, and reacting to obtain the catalyst.

3. The method according to claim 2, wherein the chlorinated paraffin containing a 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 according to claim 2, wherein the chlorinated paraffin containing carboxyl groups in the step (2) reacts with excess thionyl chloride under reflux conditions for 4-6h to obtain chlorinated paraffin containing acyl chloride.

5. The method according to claim 2, wherein the acid chloride-containing chlorinated paraffin in the step (3) is reacted with [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol at a molar ratio of 1 to 1.1: 1; and (3) slowly dripping chlorinated paraffin containing acyl chloride into a mixed solution of [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol and an acid binding agent in an ice water bath for reaction under the reaction condition of the esterification reaction in the step (3), and continuing to react for 2-4 hours in the ice water bath after the dripping is finished.

6. The preparation method according to claim 2, wherein the molar ratio of the hydroxyl-terminated phosphorus-containing chlorinated paraffin and the succinyl chloride in the step (4) is 1: 1-1.1; and (4) slowly dropwise adding succinyl chloride into the mixed solution of the hydroxyl-terminated phosphorus-containing chlorinated paraffin and the acid-binding agent in an ice water bath to react under the reaction condition of the esterification reaction in the step (4), and continuously reacting in the ice water bath for 2-4 hours after dropwise adding is finished.

7. The method according to claim 2, wherein the mole ratio of the reaction of the acid chloride-terminated phosphorus-containing chlorinated paraffin and tris (2-hydroxyethyl) isocyanurate in the step (5) is 1-1.1: 1; and (3) slowly dripping the phosphorus-containing chlorinated paraffin blocked by acyl chloride into the mixed solution of the tris (2-hydroxyethyl) isocyanurate and the acid binding agent in an ice water bath to react under the reaction condition of the esterification reaction in the step (5), and continuing to react for 2-4 hours in the ice water bath after the dripping is finished.

8. The method according to claim 2, wherein the tetrafluoroterephthalic acid in the step (6) is reacted with an excess amount of thionyl chloride under reflux conditions for 4 to 6 hours to produce tetrafluoroterephthaloyl chloride.

9. The preparation method according to claim 2, wherein the molar ratio of the tetrafluoroterephthaloyl chloride to the phosphorus-containing isocyanurate-modified chlorinated paraffin in the step (7) is 2 to 2.1: 1; and (3) slowly dripping tetrafluoroterephthaloyl chloride into the mixed solution of the phosphorus-containing isocyanurate modified chlorinated paraffin prepared in the step (5) and the acid binding agent in an ice-water bath to react, and continuing to react for 2-4 hours in the ice-water bath after dripping is finished.

10. The preparation method of claim 2, wherein the reaction conditions in the step (8) are that the dibasic acid prepared in the step (7) and epichlorohydrin are heated to 80-100 ℃ under stirring to react for 2-6 h, then cooled to room temperature, a proper amount of 50% NaOH solution is added dropwise, and the reaction is continued for 4-6h under stirring.

Technical Field

The invention relates to a steel structure fireproof epoxy coating and a preparation method thereof, belonging to the field of flame-retardant fireproof coatings.

Background

The frames of modern high-rise and large buildings are mostly made of steel structures, but steel materials used as building materials have the defects of fire prevention, such as yield point, tensile resistance, elastic modulus and the like which are all sharply reduced due to the rise of temperature, so that the bearing capacity is lost, and the collapse of the buildings is easily caused. Therefore, it is often necessary to apply fire retardant coatings to construction steel to ensure construction quality and durability.

The epoxy resin material has many outstanding characteristics, such as good thermal stability, insulation, adhesion, corrosion resistance and good mechanical properties, and is widely applied to the fields of buildings, electronics, electric appliances and the like. However, epoxy materials are flammable in air, which makes them a significant safety hazard in use. In recent years, many and intensive studies have been made to improve the flame retardancy of epoxy resin materials. In the prior art, a large amount of flame retardant is usually added to meet the requirements of epoxy resin in the field of steel structure fireproof paint, and the additive flame retardant causes poor paint film adhesion and easy falling off, and can migrate out of a polymer matrix along with the passage of time when used outdoors to cause the reduction of fireproof performance until the fireproof performance is lost.

Disclosure of Invention

Aiming at the defects of the epoxy resin in the application of the steel structure fireproof coating in the prior art, the invention aims to provide the epoxy resin containing the phosphorus-fluorine isocyanurate modified chlorinated paraffin with the flame retardant function.

The invention also aims to provide a method for preparing the flame-retardant epoxy resin, which has the advantages of wide raw material source, simple operation and mild reaction conditions.

The invention discloses a steel structure fireproof epoxy coating, which is characterized by comprising epoxy resin, polyamide resin, ammonium polyphosphate, talcum powder, antimony trioxide and butanone; the epoxy resin has a structure shown in a formula (I):

in the formula (I), R is a chlorinated paraffin chain segment.

The invention also provides a preparation method of the epoxy resin, 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

Acylating the chlorinated paraffin containing the carboxyl obtained in the step (1) by thionyl chloride to obtain chlorinated paraffin containing acyl chloride;

and (3): preparation of hydroxy-terminated phosphorus-containing chlorinated Paraffins

Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol and acid-binding agent triethylamine for esterification reaction to obtain chlorinated paraffin containing hydroxyl;

and (4): preparation of acid chloride terminated phosphorus-containing chlorinated Paraffin

Reacting the hydroxyl-terminated phosphorus-containing chlorinated paraffin obtained in the step (3) with succinyl chloride to obtain acyl chloride-terminated phosphorus-containing chlorinated paraffin;

and (5): preparation of phosphorus-containing isocyanurate-modified chlorinated Paraffin

Slowly dripping the acyl chloride-terminated phosphorus-containing chlorinated paraffin prepared in the step (4) into a mixed system of tris (2-hydroxyethyl) isocyanurate and triethylamine serving as an acid-binding agent for esterification reaction to obtain phosphorus-containing isocyanurate modified chlorinated paraffin;

and (6): preparation of tetrafluoroterephthaloyl chloride

Acylating tetrafluoroterephthalic acid by thionyl chloride to obtain tetrafluoroterephthaloyl chloride;

and (7): preparation of epoxy resins

Slowly dripping the tetrafluoroterephthaloyl chloride obtained in the step (6) into a mixed system of the phosphorus-containing isocyanurate modified chlorinated paraffin prepared in the step (5) and triethylamine serving as an acid-binding agent for esterification reaction to obtain dibasic acid;

and (8): preparation of epoxy resins

And (4) adding the dibasic acid obtained in the step (7) and epoxy chloropropane into a reaction kettle, adding a proper amount of catalyst cetyl trimethyl ammonium bromide, and reacting to obtain the catalyst.

The preparation method of the epoxy resin with flame-retardant and fireproof functions further comprises the following preferable scheme:

preferably, the chlorinated paraffin containing carboxyl is prepared by reacting the chlorinated paraffin with p-hydroxybenzoic acid in the step (1) at the temperature of 55-80 ℃ for 10-30 h.

Preferably, the chlorinated paraffin containing carboxyl in the step (2) reacts with excessive thionyl chloride under the reflux condition for 4-6h to obtain chlorinated paraffin containing acyl chloride.

Preferably, the mole ratio of the chlorinated paraffin containing acyl chloride in the step (3) to the [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol is 1-1.1: 1; and (3) slowly dripping chlorinated paraffin containing acyl chloride into a mixed solution of [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol and an acid binding agent in an ice water bath for reaction under the reaction condition of the esterification reaction in the step (3), and continuing to react for 2-4 hours in the ice water bath after the dripping is finished.

Preferably, the molar ratio of the hydroxyl-terminated phosphorus-containing chlorinated paraffin and the succinyl chloride in the step (4) is 1: 1-1.1; and (4) slowly dropwise adding succinyl chloride into the mixed solution of the hydroxyl-terminated phosphorus-containing chlorinated paraffin and the acid-binding agent in an ice water bath to react under the reaction condition of the esterification reaction in the step (4), and continuously reacting in the ice water bath for 2-4 hours after dropwise adding is finished.

Preferably, the mole ratio of the acyl chloride terminated phosphorus-containing chlorinated paraffin and the tris (2-hydroxyethyl) isocyanurate in the step (5) is 1-1.1: 1; and (3) slowly dripping the phosphorus-containing chlorinated paraffin blocked by acyl chloride into the mixed solution of the tris (2-hydroxyethyl) isocyanurate and the acid binding agent in an ice water bath to react under the reaction condition of the esterification reaction in the step (5), and continuing to react for 2-4 hours in the ice water bath after the dripping is finished.

Preferably, the tetrafluoroterephthalic acid and the excessive thionyl chloride in the step (6) react for 4-6 hours under the reflux condition to prepare the tetrafluoroterephthaloyl chloride.

Preferably, the molar ratio of the reaction of the tetrafluoroterephthaloyl chloride and the phosphorus-containing isocyanurate modified chlorinated paraffin in the step (7) is 2-2.1: 1; and (3) slowly dripping tetrafluoroterephthaloyl chloride into the mixed solution of the phosphorus-containing isocyanurate modified chlorinated paraffin prepared in the step (5) and the acid binding agent in an ice-water bath to react, and continuing to react for 2-4 hours in the ice-water bath after dripping is finished.

Preferably, the reaction condition in the step (8) is that the dibasic acid prepared in the step (7) and epoxy chloropropane are heated to 80-100 ℃ under stirring, the reaction is carried out for 2-6 h, then the reaction is cooled to room temperature, a proper amount of 50% NaOH solution is dropwise added, and the reaction is continued for 4-6h under stirring.

The invention has the beneficial effects that: the invention firstly uses the isocyanurate as a bridge chain to connect the traditional chlorinated paraffin and the fluorine-containing and phosphorus-containing flame retardant to synthesize the novel flame-retardant epoxy resin, four excellent flame-retardant elements of phosphorus, nitrogen, fluorine and chlorine are simultaneously embedded into the molecule of the epoxy resin, and the four elements generate synergistic interaction from different flame-retardant mechanisms in a synergistic manner, thereby showing higher flame-retardant efficiency.

Drawings

FIG. 1 is an infrared image of the epoxy resin obtained in example 1.

FIG. 1: 2920cm^-1And 2860cm^-1Is the absorption peak of stretching vibration of methyl and methylene, 1470cm^-1And 1370cm^-1Bending 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, 1600cm^-1Is P-C₆H₅1255cm of deformation vibration absorption peak of^-1Is the C-F stretching vibration absorption peak, 1230cm^-1And 1050cm^-1Is a characteristic absorption peak of a C-O-C ether bond of 1200cm^-1Where is P ═ O absorption peak of stretching vibration, 1150cm^-1Has a stretching vibration peak of 980cm of C-N single bond^-1Is the vibration characteristic absorption peak of P-C, 910cm^-1Is a characteristic absorption peak of an epoxy group, 755cm^-1Is a C-H out-of-plane bending vibration peak with disubstituted benzene ring, 710cm^-1Here is the stretching vibration peak of the C-Cl 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: and adding 70mol of chlorinated paraffin 42 containing carboxyl into the reaction kettle, dropwise adding 120mol of thionyl chloride, stirring, heating to reflux, and reacting for 6 hours to obtain chlorinated paraffin 42 containing acyl chloride.

(3) Preparation of the hydroxyl-terminated phosphorus-containing chlorinated paraffin 42: adding 100mol of [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol 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 101mol of chlorinated paraffin 42 containing acyl chloride at 0 ℃, reacting the reactant at 0 ℃ for 2H after dropwise adding, 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, drying an organic phase with anhydrous calcium chloride after washing the organic phase with distilled water, drying for 8H, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the hydroxyl-terminated chlorinated paraffin 42 containing phosphorus.

(4) Preparation of acid chloride terminated phosphorus-containing chlorinated paraffin 42: adding 80mol of hydroxyl-terminated phosphorus-containing chlorinated paraffin 42 into a reaction kettle, adding 50mol of dichloromethane, stirring for dissolving, then slowly dropwise adding a dichloromethane solution containing 81mol of succinyl chloride, and reacting reactants at 0 ℃ for 2 hours after dropwise adding to obtain the acyl chloride-terminated phosphorus-containing chlorinated paraffin 42.

(5) Preparation of the phosphorus-containing isocyanurate-modified chlorinated paraffin 42: 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 101mol of acyl chloride-terminated phosphorus-containing chlorinated paraffin 42 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 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 phosphorus-containing isocyanurate-modified chlorinated paraffin 42.

(6) Preparation of tetrafluoroterephthaloyl chloride: adding 50mol of tetrafluoroterephthalic acid into a reaction kettle, dropwise adding 100mol of thionyl chloride, stirring and heating until reflux, and reacting for 6 hours to obtain tetrafluoroterephthaloyl chloride.

(7) Preparation of chlorinated paraffin 42 dibasic acid modified by phosphorus-containing fluoroisocyanurate: 100mol of phosphorus-containing isocyanurate modified chlorinated paraffin 42 and a proper amount of acid-binding agent anhydrous triethylamine are added into a reaction kettle, nitrogen is introduced into the reaction kettle, a dichloromethane solution containing 201mol of tetrafluoroterephthaloyl chloride is dropwise added at 0 ℃, reactants react for 2h at 0 ℃, reaction products are washed by 4% sodium bicarbonate solution until the pH value is 7, then the reaction products are transferred to ethyl acetate for extraction and separation, an organic phase is washed by distilled water and dried by anhydrous calcium chloride, the drying is carried out for 8h, then the reduced pressure filtration is carried out, and the filtrate is distilled to remove the solvent, so that the phosphorus-containing isocyanurate modified chlorinated paraffin 42 dibasic acid is obtained.

(8) Preparation of chlorinated paraffin 42 epoxy resin modified by phosphorus-containing fluoroisocyanurate: 100g of phosphorus-containing fluoroisocyanurate modified chloroparaffin 42 dibasic acid, 200g of epichlorohydrin and a proper amount of hexadecyl trimethyl ammonium bromide are heated to 80 ℃ under stirring and react for 6 hours, then the mixture is cooled to room temperature, a proper amount of 50 percent NaOH solution is dripped, and the mixture is continuously stirred and reacted for 6 hours. Cooling, filtering, extracting with ethyl acetate, and rotary evaporating to obtain the chlorinated paraffin 42 modified by the phosphorus-containing fluoroisocyanurate H1.

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 chlorinated paraffin 52 containing carboxyl into a reaction kettle, dropwise adding 120mol of thionyl chloride, stirring, heating to reflux, and reacting for 4 hours to obtain chlorinated paraffin 52 containing acyl chloride.

(3) Preparation of hydroxyl-terminated phosphorus-containing chlorinated paraffin 52: adding 100mol of [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol 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 chloride-containing chlorinated paraffin 52 at 0 ℃, reacting the reactants at 0 ℃ for 4H after dropwise adding, 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, drying an organic phase with anhydrous calcium chloride after washing the organic phase with distilled water, drying for 8H, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the hydroxyl-terminated phosphorus-containing chlorinated paraffin 52.

(4) Preparation of acid chloride-terminated phosphorus-containing chlorinated paraffin 52: adding 80mol of hydroxyl-terminated phosphorus-containing chlorinated paraffin 52 into a reaction kettle, adding 60mol of dichloromethane, stirring for dissolving, then slowly dropwise adding a dichloromethane solution containing 80.5mol of succinyl chloride, and reacting reactants at 0 ℃ for 4 hours after dropwise adding to obtain the acyl chloride-terminated phosphorus-containing chlorinated paraffin 52.

(5) Preparation of the phosphorus-containing isocyanurate-modified chlorinated paraffin 52: 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 101mol of acyl chloride-terminated phosphorus-containing chlorinated paraffin 52 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 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 phosphorus-containing isocyanurate-modified chlorinated paraffin 52.

(6) Preparation of tetrafluoroterephthaloyl chloride: adding 50mol of tetrafluoroterephthalic acid into a reaction kettle, dropwise adding 100mol of thionyl chloride, stirring and heating until reflux, and reacting for 4 hours to obtain tetrafluoroterephthaloyl chloride.

(7) Preparation of chlorinated paraffin 52 dibasic acid modified by phosphorus-containing fluoroisocyanurate: 100mol of phosphorus-containing isocyanurate modified chlorinated paraffin, 52 and a proper amount of acid-binding agent anhydrous triethylamine are added into a reaction kettle, nitrogen is introduced into the reaction kettle, a dichloromethane solution containing 202mol of tetrafluoro terephthaloyl chloride is dripped at 0 ℃, reactants react for 4 hours at 0 ℃, reaction products are washed by a 4% sodium bicarbonate solution until the pH value is 7, then the reaction products are transferred to ethyl acetate for extraction and separation, an organic phase is washed by distilled water and dried by anhydrous calcium chloride, the drying is carried out for 8 hours, then the pressure reduction and filtration are carried out, and the filtrate is distilled to remove the solvent, so that the phosphorus-containing isocyanurate modified chlorinated paraffin 52 dibasic acid is obtained.

(8) Preparation of chlorinated paraffin 52 epoxy resin modified by phosphorus-containing fluoroisocyanurate: 100g of phosphorus-containing fluoroisocyanurate-modified chloroparaffin 52 dibasic acid, 250g of epichlorohydrin and a proper amount of hexadecyl trimethyl ammonium bromide are heated to 100 ℃ under stirring and react for 2 hours, then the mixture is cooled to room temperature, a proper amount of 50 percent NaOH solution is dripped, and the mixture is continuously stirred and reacted for 4 hours. Cooling, filtering, extracting with ethyl acetate, and rotary evaporating to obtain the chlorinated paraffin 52 modified by the phosphorus-containing fluoroisocyanurate H2.

Example 3

(1) Preparation of carboxyl group-containing chlorinated paraffin 70: 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 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 70 into a reaction kettle, dropwise adding 120mol of thionyl chloride, stirring, heating to reflux, and reacting for 5 hours to obtain the chlorinated paraffin 70 containing acyl chloride.

(3) Preparation of hydroxyl-terminated phosphorus-containing chlorinated paraffin 70: adding 100mol of [ (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanediol 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 chloride-containing chlorinated paraffin 70 at 0 ℃, reacting the reactant at 0 ℃ for 3H after dropwise adding, 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, drying an organic phase with anhydrous calcium chloride after washing the organic phase with distilled water, drying for 8H, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the hydroxyl-terminated phosphorus-containing chlorinated paraffin 70.

(4) Preparation of acid chloride terminated phosphorus-containing chlorinated paraffin 70: adding 80mol of hydroxyl-terminated phosphorus-containing chlorinated paraffin 70 into a reaction kettle, adding 50mol of dichloromethane, stirring for dissolving, then slowly dropwise adding a dichloromethane solution containing 81mol of succinyl chloride, and reacting reactants at 0 ℃ for 3 hours after dropwise adding to obtain the acyl chloride-terminated phosphorus-containing chlorinated paraffin 70.

(5) Preparation of the phosphorus-containing isocyanurate-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 dichloromethane solution containing 102mol of acyl chloride-terminated phosphorus-containing chlorinated paraffin 70 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 phosphorus-containing isocyanurate-modified chlorinated paraffin 70.

(6) Preparation of tetrafluoroterephthaloyl chloride: adding 50mol of tetrafluoroterephthalic acid into a reaction kettle, dropwise adding 100mol of thionyl chloride, stirring and heating until reflux, and reacting for 5 hours to obtain tetrafluoroterephthaloyl chloride.

(7) Preparation of chlorinated paraffin 70 dibasic acid modified by phosphorus-containing fluoroisocyanurate: adding 100mol of phosphorus-containing isocyanurate modified chlorinated paraffin 70 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 203mol of tetrafluoroterephthaloyl 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 phosphorus-containing isocyanurate modified chlorinated paraffin 70 dibasic acid.

(8) Preparation of chlorinated paraffin 70 epoxy resin modified by phosphorus-containing fluoroisocyanurate: 100g of phosphorus-containing fluoroisocyanurate-modified chlorinated paraffin 70 dibasic acid, 250g of epoxy chloropropane and a proper amount of hexadecyl trimethyl ammonium bromide are heated to 90 ℃ under stirring, reacted for 4 hours, cooled to room temperature, dropwise added with a proper amount of 50% NaOH solution and continuously stirred for reaction for 3 hours. Cooling, filtering, extracting with ethyl acetate, and rotary evaporating to obtain chlorinated paraffin 70 modified by the phosphorus-containing fluoroisocyanurate H3.

Preparation and testing of epoxy fire-retardant coating

Epoxy resin E42, polyamide 200, the prepared epoxy resin, chlorinated paraffin 52, ammonium polyphosphate, talcum powder, antimony trioxide and butanone are mixed and stirred uniformly according to the weight parts of the raw materials in the composition shown in the table 1 to obtain the epoxy fireproof coating. The performance of the prepared epoxy fire-retardant coating is detected by referring to steel structure fire-retardant coating specification GB14907-2002, and the results are shown in Table 2.

TABLE 1 epoxy fire-retardant coating formulation

Note: f is tris (2-hydroxyethyl) isocyanurate.

TABLE 2 epoxy fire-retardant coating Performance test results

In conclusion, the novel flame-retardant epoxy resin is synthesized by connecting the traditional chlorinated paraffin and the fluorine-containing and phosphorus-containing flame retardant by taking the isocyanurate as a bridge chain, four excellent flame-retardant elements, namely phosphorus, nitrogen, fluorine and chlorine, are simultaneously embedded into the epoxy resin molecule, and the four elements generate synergistic interaction from different flame-retardant mechanisms in a synergistic manner, so that higher flame-retardant efficiency can be shown, and the prepared epoxy fireproof coating has good mechanical properties and excellent flame-retardant and heat-resistant properties.