CN112592468B - Preparation process of flame-retardant polyester resin and application of flame-retardant polyester resin in flame-retardant coating - Google Patents
Preparation process of flame-retardant polyester resin and application of flame-retardant polyester resin in flame-retardant coating Download PDFInfo
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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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- 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
- C08G63/91—Polymers modified by chemical after-treatment
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a preparation process of flame-retardant polyester resin, which is characterized by comprising the following specific preparation processes of: adding a flame-retardant reinforcing agent, absolute ethyl alcohol and a sodium hydroxide solution with the mass concentration of 18% into a reaction kettle, stirring and dissolving, then adding a saturated polyester resin solution, reacting for a period of time, adding a saturated solution of sodium carbonate, stirring and reacting for 4 hours, then dropwise adding diaminosilane, continuously adding diethylene glycol ethyl ether acetate into the reaction kettle in the reaction process, and washing a product to be neutral after rotary evaporation and solvent recovery to obtain the flame-retardant polyester resin. The flame-retardant polyester resin prepared by the invention is prepared by carrying out cross-linking polymerization on saturated polyester resin through a flame-retardant reinforcing agent, then carrying out addition reaction on two amino groups in the added diaminosilane and an olefin group, further crosslinking the flame-retardant reinforcing agent through the diaminosilane after cross-linking to form a net structure, and further enabling the prepared resin to have stronger performance.
Description
Technical Field
The invention belongs to the field of paint preparation, and relates to a preparation process of flame-retardant polyester resin and application of the flame-retardant polyester resin in flame-retardant paint.
Background
Polyester resins are generally prepared by esterification and polycondensation of dibasic acids and glycols. A common feature of the structure of these polymers is that the various chain segments of the macromolecules are connected by ester groups, and are therefore commonly referred to as polyesters. The polyester has the advantages of brightness, fullness, high hardness, good physical and mechanical properties, good chemical corrosion resistance, adhesive force, impact resistance, wear resistance and the like. With the development of science and technology, more and more saturated polyester resin products are applied to the field of high performance. However, polyester resin is easy to hydrolyze due to ester group, acidic gas dissolved in water can catalyze resin ester bonds to be hydrolyzed and broken more rapidly, so that the structure of the polyester resin is changed to influence the performance of the prepared coating.
The existing polyester resin has wide application in the preparation of coatings, flame retardant is usually directly added into the flame-retardant polyester resin, but the flame retardant is mixed by mechanical stirring after being added, and the compatibility between a plurality of flame retardants and matrix resin is poor, so that the flame retardant property of the coatings is reduced.
Disclosure of Invention
The invention aims to provide a preparation process of a flame-retardant polyester resin, wherein the polyester resin is prepared by polymerizing dihydroxyacetophenone and brominated adipic acid, so that a large amount of acetophenone groups and bromine groups are uniformly distributed on a prepared saturated polyester resin chain, then the saturated polyester resin is subjected to cross-linking polymerization through a flame-retardant reinforcing agent, and as a polymerized product contains olefin groups, two amino groups in added diaminosilane can perform addition reaction with the olefin groups, and then the flame-retardant reinforcing agent is crosslinked through the diaminosilane after being crosslinked to form a net structure, so that the prepared resin has high mechanical property, and simultaneously the flame-retardant reinforcing agent contains terminal aldehyde groups and can perform condensation reaction with the acetophenone groups in the saturated polyester resin liquid to generate unsaturated ketene
At the same timeUnder the alkaline condition, phenolic hydroxyl in the flame retardant reinforcing agent can be subjected to etherification reaction with bromine on a polyester resin chain, so that one end of the flame retardant reinforcing agent is grafted to one side of carboxyl of an ester group in the polyester resin, the other end of the flame retardant reinforcing agent is grafted to one side of hydroxyl of the ester group, dislocation crosslinking is realized, allyl in a generated ketene group directly reacts with carbonyl with an electron-withdrawing function, so that the allyl has higher activity and can be subjected to alkylation reaction with amino in diaminosilane, so that the flame retardant reinforcing agent is subjected to crosslinking polymerization through the diaminosilane, when the ester group is hydrolyzed and broken, a polymer can still be crosslinked through the flame retardant reinforcing agent, and the dislocation crosslinking agent is subjected to crosslinking through the diaminosilane, so that the polymer still keeps a compact network structure, and the hydrolyzed hydroxyl and carboxyl cannot become free small molecules, so that the structural characteristics of the resin can not be changed, and the mechanical property weakening caused by the change of the network structural characteristics of the resin after the ester group in the resin is hydrolyzed can be effectively prevented.
The purpose of the invention can be realized by the following technical scheme:
a preparation process of flame-retardant polyester resin comprises the following specific preparation processes:
step one, continuously introducing nitrogen into a reaction kettle, then adding dihydroxy acetophenone, adipic acid bromide and monobutyl tin oxide, slowly heating to melt the materials, then carrying out heat preservation reaction for 1h, then heating to 230-; the dihydroxy acetophenone and the brominated adipic acid are polymerized through esterification reaction, bromine and acetophenone groups are uniformly distributed on a chain polymer chain, the bromine is positioned on one side of a carboxyl group, and the acetophenone group is positioned on one side of a hydroxyl group;
further, 0.93-0.94kg of brominated adipic acid is added into each kg of dihydroxy acetophenone, and 1.87-1.93g of monobutyl tin oxide is added;
secondly, adding the flame-retardant reinforcing agent, absolute ethyl alcohol and 18% sodium hydroxide solution by mass concentration into a reaction kettle, stirring and dissolving, and then adding the mixture into the reaction kettleAdding saturated polyester resin liquid, heating to 50-55 ℃, stirring for reaction for 4-5h, heating to 90-95 ℃, adding saturated solution of sodium carbonate, stirring for reaction for 4h, dropwise adding diaminosilane, continuously adding diethylene glycol ethyl ether acetate in the reaction process to keep the material always in fluidity, performing rotary evaporation to recover the solvent, washing the product to be neutral, drying with anhydrous magnesium sulfate, adding diethylene glycol ethyl ether acetate into the product, stirring and mixing until the solid content is 55%, and obtaining the flame-retardant polyester resin; because the flame retardant reinforcing agent contains tertiary aldehyde group, the flame retardant reinforcing agent can be firstly subjected to condensation reaction with an ethyl ketone group in an acetophenone group in a saturated polyester resin solution under an alkaline condition to generate unsaturated ketene
Because the ortho-position of the aldehyde group is directly connected with a tertiary hydrocarbon group, the flame retardant reinforcing agents can not drink more than one person per se, meanwhile, phenolic hydroxyl in the flame retardant reinforcing agents can be subjected to etherification reaction with bromine on a polyester resin chain under an alkaline condition, one end of each flame retardant reinforcing agent is grafted to one side of carboxyl of an ester group in the polyester resin, the other end of each flame retardant reinforcing agent is grafted to one side of hydroxyl of the ester group, dislocation crosslinking is realized, allyl in generated ketene groups is directly reacted with carbonyl with an electron-withdrawing function, so that the allyl has higher activity and can be subjected to alkylation reaction with amino in diaminosilane, then the flame retardant reinforcing agents are subjected to crosslinking polymerization through the diaminosilane, when the ester group is hydrolyzed and fractured, polymers can still be crosslinked through the flame retardant reinforcing agents, and the dislocation crosslinking agents are crosslinked through the diaminosilane, so that the polymer still keeps a compact network structure, and the hydrolyzed hydroxyl and carboxyl can not become small molecules to be free, so that the structural characteristics of the polymer can not be changed, and the mechanical property reduction caused by the change of the network structure characteristics after the ester group in the resin is hydrolyzed can be effectively prevented; because the flame-retardant reinforcing agent is uniformly introduced into the prepared flame-retardant polyester resin, a large amount of phosphate groups are introduced into the prepared flame-retardant polyester resin net structure, and the prepared flame-retardant polyester resin has the function of the phosphate groupsThe flame retardant property is high;
furthermore, 96-102g of flame retardant enhancer, 250mL of absolute ethyl alcohol 240-250mL, 31-36mL of sodium hydroxide solution with the mass concentration of 18%, 31-34g of saturated solution of sodium carbonate and 42-49g of diaminosilane are added into each kilogram of saturated polyester resin solution.
The preparation process of the brominated adipic acid comprises the following steps: adding adipic acid into benzene, stirring for dissolving, heating to 70-80 ℃, dropwise adding bromine and phosphorus trichloride into the benzene, heating at constant temperature for reaction until no red bromine liquid vapor appears, slowly heating to 100-105 ℃, then carrying out heat preservation reaction for 3-4h, carrying out reduced pressure distillation, cooling and crystallization on the product, and obtaining adipic bromide; carboxylic acid generates a Hell-Volhard-Zelinsky reaction under the catalytic action of phosphorus trichloride, so that bromine is introduced to the alpha position of the carboxylic acid;
furthermore, 100-105mL of bromine, 4.5-5mL of phosphorus trichloride and 150-160mL of benzene are added to each mole of adipic acid.
The preparation process of the dihydroxyacetophenone is as follows: adding 4-aminoacetophenone, acetic acid with the mass concentration of 35% and ethanol into a reaction kettle at the same time, stirring and dissolving, then dropwise adding propylene oxide into the mixture at the temperature of 5 ℃, controlling the dropwise adding to be completed within 2h, then heating to 30 ℃ for reaction for 2h, then heating to 110 ℃ and 120 ℃ for reaction for 6-7h, and removing unreacted propylene oxide and solvent by rotary evaporation to obtain the dihydroxyacetophenone, wherein under the catalytic action of acetic acid, the amino group in the 4-aminoacetophenone can perform a ring-opening reaction with the epoxy group in the propylene oxide, so that two hydroxyl groups are introduced into the amino group in the 4-aminoacetophenone;
further, 4-aminoacetophenone and propylene oxide were mixed in a ratio of 1:2.4-2.5, while 150mL of ethanol and 45-50mL of acetic acid were added per mole of 4-aminoacetophenone.
The specific preparation process of the flame-retardant reinforcing agent is as follows:
step 1: adding acetone, copper chloride and isobutyraldehyde into a reaction kettle, stirring and reacting for 2-3h at 5-10 ℃, heating to evaporate the solvent, cooling to 0 ℃, filtering and recovering cuprous chloride to obtain chloroisobutyraldehyde;
further, isobutyraldehyde and copper chloride are added according to the mass ratio of 1: 2-2.3;
step 2: adding benzene and dimethyl phosphite into a reaction kettle at the same time, adding a methanol solution of sodium methoxide into the reaction kettle, uniformly stirring, heating to 55-60 ℃, dropwise adding N-allylmethylamine into the reaction kettle, controlling the dropwise addition within 1h, carrying out reflux reaction for 3-4h after the addition is finished, adjusting the pH value of the solution to 7-7.5, adding the product into water, standing for layering, separating out benzene, and carrying out reduced pressure distillation on the water solution to obtain aminated phosphate; the olefin group in the N-allylmethylamine can perform addition reaction with dimethyl phosphite;
further, dimethyl phosphite: sodium methoxide and N-allylmethylamine in a mass ratio of 1: 0.98-0.99, and simultaneously adding 500mL of benzene into each mol of dimethyl phosphite;
and step 3: adding hydroquinone, aminated phosphate, paraformaldehyde, ethanol and concentrated hydrochloric acid into a reaction kettle at the same time, heating to 80-85 ℃ for reaction for 14-16h, cooling to 5 ℃, adjusting the pH value to 8 with a sodium hydroxide solution, cooling in an ice water bath, crystallizing, filtering, washing with water, and drying to obtain phosphate-based hydroquinone;
furthermore, hydroquinone and aminated phosphate are added according to the mass ratio of 1:1.23-1.31, and simultaneously 38-42g of paraformaldehyde, 2.3-2.4mL of concentrated hydrochloric acid and 240mL of absolute ethyl alcohol are added into each mole of hydroquinone;
and 4, step 4: adding phosphate-based hydroquinone, absolute ethyl alcohol and sodium hydroxide into a reaction kettle simultaneously, stirring and heating until refluxing, adding chloroisobutyraldehyde into the reaction kettle, carrying out heat preservation reaction for 3-4h, carrying out rotary evaporation to recover part of ethanol, cooling to 0 ℃, freezing overnight, then carrying out filtration and washing with water, adding the obtained product into ethanol for recrystallization, filtering and drying to obtain a flame-retardant reinforcing agent, wherein the flame-retardant reinforcing agent is introduced with phosphate groups, so that the prepared product has a certain flame-retardant property;
further, the mass ratio of phosphate-based hydroquinone, chloroisobutyraldehyde and sodium hydroxide is 1: 0.97-0.98: 1.13-1.15, and adding 300-310mL of ethanol per mole of phosphate-based hydroquinone.
Wherein the preparation process of the diamino silane comprises the following steps: mixing chloroplatinic acid hexahydrate and isopropanol to prepare a catalyst solution, adding 2-methylallylamine and 1,1,3, 3-tetramethyldisiloxane into a reaction kettle, adding the catalyst solution into the reaction kettle, heating to 75-80 ℃ for refluxing, monitoring the reaction process by using a gas chromatograph in the reaction process, and carrying out reduced pressure distillation after the reaction is completed to obtain diaminosilane;
further, 2-methylallylamine and 1,1,3, 3-tetramethyldisiloxane in a ratio of the amounts of the substances of 3.4 to 3.7: 1, while adding the catalyst 6 x 10 per mole of 1,1,3, 3-tetramethyldisiloxane-5mol。
The invention has the beneficial effects that:
1. the flame-retardant polyester resin is prepared by polymerizing the dihydroxyacetophenone and the brominated adipic acid, so that a large amount of acetophenone groups and bromine groups are uniformly distributed on a chain of the prepared saturated polyester resin, then the saturated polyester resin is subjected to cross-linking polymerization through the flame-retardant reinforcing agent, and as the polymerized product contains olefin groups, two amino groups in the added diaminosilane can perform addition reaction with the olefin groups, and then the flame-retardant reinforcing agent is crosslinked through the diaminosilane after being crosslinked to form a net structure, so that the prepared resin has strong performance.
2. The flame-retardant reinforcing agent prepared by the invention contains terminal aldehyde groups, and can perform condensation reaction with ethyl ketone groups in acetophenone groups in saturated polyester resin liquid to generate unsaturated ketene
Meanwhile, phenolic hydroxyl in the flame-retardant reinforcing agent can be subjected to etherification reaction with bromine on a polyester resin chain under an alkaline condition, so that one end of the flame-retardant reinforcing agent is grafted to one side of carboxyl of an ester group in the polyester resin, the other end of the flame-retardant reinforcing agent is grafted to one side of hydroxyl of the ester group, dislocation crosslinking is realized, and allyl in a generated ketene group is directly subjected to electron withdrawing with the allylThe carbonyl of function reacts, and then make the allyl have higher activity, can carry out the alkylation reaction with amino among the diamino silane, and then make through diamino silane cross-linking polymerization between the fire-retardant reinforcing agent, the polymer still can cross-link through the fire-retardant reinforcing agent when ester group hydrolytic breakdown, and cross-link through diamino silane between the cross-linking agent misplaces, and then make the polymer still keep inseparable network, hydroxyl and carboxyl after the hydrolysis can not become the micromolecule and free, make its structural feature can not change, and then effectively prevent in the resin that its network feature changes the mechanical properties that causes and weaken after ester group hydrolysis.
3. According to the preparation method, the flame retardant reinforcing agent is prepared, phosphate groups are introduced into the flame retardant reinforcing agent, saturated polyester resin is prepared through polymerization of dihydroxy acetophenone and brominated adipic acid, a large amount of bromine elements are introduced into a saturated polyester resin chain, the saturated polyester resin is crosslinked through the flame retardant reinforcing agent and then is crosslinked through diamino silane, and silane bonds are introduced into the flame retardant reinforcing agent.
Detailed Description
Example 1:
the specific preparation process of the flame-retardant reinforcing agent is as follows:
step 1: adding 265mL of acetone, 283g of cupric chloride and 72g of isobutyraldehyde into a reaction kettle, stirring and reacting for 83 hours at the temperature of 8 ℃, heating to evaporate the solvent, cooling to 0 ℃, filtering and recovering cuprous chloride to obtain chloroisobutyraldehyde; process for preparing chloroisobutyraldehyde1HNMR spectrogram analysis shows that the delta is 1.75ppm and is-CH3Radical (I)1Absorption peak of H,. delta. delta.9.72 ppm aldehyde group1The absorption peak of H;
step 2: 500mL of benzene and 1mol of dimethyl phosphite were simultaneously charged into a reaction vessel, and then added theretoAdding sodium methoxide in a methanol solution of sodium methoxide, wherein the adding amount of the sodium methoxide is 1mol, uniformly stirring, heating to 60 ℃, dropwise adding 0.98mol of N-allylmethylamine into the methanol solution, controlling the dropwise adding within 1h, carrying out reflux reaction for 4h after the addition is finished, then adjusting the pH value of the solution to be 7-7.5, then adding a product into water, standing and layering, separating out benzene, and then carrying out reduced pressure distillation on the water solution to obtain aminated phosphate; process for preparation of aminated phosphoric acid esters1HNMR spectrogram analysis shows that the delta is 1.75ppm and is-CH2-P group1Absorption peak of H, delta-3.32 ppm-NH-)1Absorption peak of H,. delta. DELTA.3.65 ppm P-O-CH3In1The absorption peak of H;
and step 3: adding 1mol of hydroquinone, 1.26mol of aminated phosphate, 40g of paraformaldehyde, 240mL of ethanol and 2.4mL of concentrated hydrochloric acid into a reaction kettle at the same time, heating to 85 ℃ for reaction for 15h, cooling to 5 ℃, adjusting the pH value to 8 with a sodium hydroxide solution, cooling in an ice water bath for crystallization, filtering, washing with water and drying to obtain phosphate-based hydroquinone; process for preparing phosphate-based hydroquinone1HNMR spectrogram analysis shows that the delta is 3.66ppm and is Ar-CH2-CH in the-N radical2Of (A) to1The absorption peak of H;
and 4, step 4: simultaneously adding 1mol of phosphate-based hydroquinone, 300mL of anhydrous ethanol and 1.14mol of sodium hydroxide into a reaction kettle, stirring and heating until reflux, adding 0.97mol of chloroisobutyraldehyde into the reaction kettle, carrying out heat preservation reaction for 4 hours, carrying out rotary evaporation to recover part of ethanol, cooling to 0 ℃, freezing overnight, filtering, washing with water, adding the obtained product into ethanol for recrystallization, filtering and drying to obtain a flame-retardant reinforcing agent; of flame-retardant reinforcing agents1HNMR spectrogram analysis shows that the delta is 1.46ppm and the delta is 9.72ppm
In the radical-CH3And of aldehyde groups1H absorption peak, delta 9.74ppm, is phenolic hydroxyl1Absorption peak of H.
Example 2:
the specific preparation process of the brominated adipic acid is as follows: adding 1mol of adipic acid into 150mL of benzene, stirring for dissolving, then heating to 80 ℃, dropwise adding 100mL of bromine and 4.8mL of phosphorus trichloride, and keeping constant temperatureHeating to react until no red bromine liquid vapor appears, slowly heating to 100 ℃, then preserving heat to react for 4 hours, and carrying out reduced pressure distillation, cooling and crystallization on the product to obtain adipic bromide; process for brominating adipic acid1HNMR spectrogram analysis shows that the delta-4.23 ppm and the delta-12.22 ppm are carboxyl1Absorption peak of H.
Example 4:
the preparation process of the dihydroxyacetophenone is as follows: simultaneously adding 4-aminoacetophenone 1mol, 35% acetic acid solution 50mL and ethanol 160mL into a reaction kettle, stirring and dissolving, then dropwise adding propylene oxide 2.4mol at 5 ℃, controlling the dropwise addition within 2h, then heating to 30 ℃ for reaction for 2h, heating to 110 ℃ for reaction for 7h, and removing unreacted propylene oxide and solvent by rotary evaporation to obtain dihydroxyacetophenone; process for preparing dihydroxyacetophenone1HNMR spectrum analysis shows that delta 2.5ppm and delta 5.37ppm are-CH in ethyl ketone group with benzene ring connected3And of hydroxy groups1The absorption peak of H;
example 5:
the specific preparation process of the flame-retardant polyester resin comprises the following steps:
in a first step, 1mol of 2-methylallylamine and 1mol of 1,1,3, 3-tetramethyldisiloxane are charged into a reaction vessel, to which 6X 10 are then added-5Heating the mol catalyst to 75-80 ℃ for reflux, monitoring the reaction process by using a gas chromatograph in the reaction process, and carrying out reduced pressure distillation after the reaction is completed to obtain the diamino silane; the catalyst is prepared by mixing chloroplatinic acid hexahydrate and isopropanol;
secondly, continuously introducing nitrogen into a reaction kettle, then adding 100g of the dihydroxy acetophenone prepared in the embodiment 4, 93.5g of the brominated adipic acid prepared in the embodiment 1 and 0.19g of monobutyl tin oxide, slowly heating until the materials are molten, then carrying out heat preservation reaction for 1h, then heating to 240 ℃ while stirring, carrying out heat preservation reaction for 5h, vacuumizing, controlling the acid value to be less than 10mgKOH/g, cooling, adding a diluent S-100, adjusting the solid content to be 40%, and discharging to obtain a saturated polyester resin solution;
and thirdly, adding 100g of the flame-retardant reinforcing agent prepared in the example 1, 250mL of absolute ethyl alcohol and 35mL of sodium hydroxide solution with the mass concentration of 18% into a reaction kettle, stirring and dissolving, then adding 1kg of saturated polyester resin solution into the reaction kettle, heating to 55 ℃, stirring and reacting for 4.5h, then heating to 90 ℃, adding 32g of saturated solution of sodium carbonate into the reaction kettle, stirring and reacting for 4h, dropwise adding 46g of diaminosilane into the reaction kettle, continuously adding diethylene glycol ethyl ether acetate into the reaction kettle in the reaction process, so that the material always keeps fluidity, carrying out rotary evaporation to recover the solvent, washing the product to be neutral, drying the product by using anhydrous magnesium sulfate, then adding the diethylene glycol ethyl ether acetate into the product, stirring and mixing until the solid content is 55%, and obtaining the flame-retardant polyester resin.
Comparative example 1:
the specific procedure for preparing the flame retardant polyester resin was the same as in example 5 except that the flame retardant enhancer added in the third step of example 5 was replaced with p-hydroxybenzaldehyde.
Comparative example 2:
the specific procedure for preparing a flame-retardant polyester resin was the same as in example 5 except that hydroquinone was used instead of the flame-retardant reinforcing agent added in the third step of example 5.
Comparative example 3:
the specific procedure for preparing the flame retardant polyester resin was the same as in example 5 except that the flame retardant enhancer added in the third step of example 5 was replaced with terephthalaldehyde.
Comparative example 4:
the specific procedure for preparing a flame-retardant polyester resin was the same as in example 5 except that 1, 8-octanediamine was used instead of diaminosilane added in the third step of example 5.
Application example 1:
the preparation method of the flame-retardant coating comprises the following steps:
470g of the flame-retardant polyester resin prepared in example 5, 170g of a pigment, 50g of precipitated barium sulfate, 6g of a dispersant, 2gAT168 antioxidant and 180g of diethylene glycol ethyl ether acetate were mixed, stirred and ground to obtain a slurry, and then 73g of an amino resin, 5g of a leveling agent, 4g of dodecylbenzene sulfonic acid, 8g of a matting agent, 9g of a defoaming agent and 90g of a solvent were added to the slurry to adjust the viscosity, thereby obtaining a flame-retardant coating.
Application example 2:
a flame retardant coating was prepared in the same manner as in application example 1 by replacing the flame retardant polyester resin prepared in example 5 used in application example 1 with the flame retardant polyester resin prepared in comparative example 1.
Application example 3:
a flame retardant coating was prepared in the same manner as in application example 1 by replacing the flame retardant polyester resin prepared in example 5 used in application example 1 with the flame retardant polyester resin prepared in comparative example 2.
Application example 4:
a flame retardant coating was prepared in the same manner as in application example 1 by replacing the flame retardant polyester resin prepared in example 5 used in application example 1 with the flame retardant polyester resin prepared in comparative example 3.
Application example 5:
a flame retardant coating was prepared in the same manner as in application example 1 by replacing the flame retardant polyester resin prepared in example 5 used in application example 1 with the flame retardant polyester resin prepared in comparative example 4.
Application example 6:
a flame retardant coating was prepared in the same manner as in application example 1 by replacing the flame retardant polyester resin prepared in example 5 used in application example 1 with the flame retardant polyester resin prepared in comparative example 1 while adding 11g of triphenyl phosphate thereto.
Test example:
(1) the coating prepared in application examples 1-6 is coated on the surface of a test piece, the test piece is placed in a humid heat aging box with the temperature of 60 ℃ and the humidity of 93% for a certain time after the coating is cured, then the test piece is taken out, the impact strength P1 and the initial impact strength P0 of the coating after being subjected to humid heat treatment for 60 hours are measured according to the GB/T1732-93 standard, then the impact strength attenuation rate I of the coating is calculated to be (P0-P1)/P0, and the impact strength attenuation rates of the coatings prepared in application examples 1, 2 and 6 are all less than 7% through calculation, so that the performance of the coating under the humid heat condition is not greatly influenced, the impact strength attenuation rate of the coating in application example 3 reaches 42.4%, the impact strength attenuation rate of the coating in application example 4 reaches 19.3%, and the impact strength attenuation rate of the coating in application example 5 reaches 15.2%, therefore, the coatings prepared in application examples 1 and 2 and application example 6 have high wet and heat resistance in a damp and hot environment, the prepared coating is prepared by crosslinking a flame retardant reinforcing agent and saturated polyester resin liquid, wherein the flame retardant reinforcing agent contains terminal aldehyde groups, and can perform condensation reaction with an ethyl ketone group in an acetophenone group in the saturated polyester resin liquid to form an ketene group, meanwhile, phenolic hydroxyl groups in the flame retardant reinforcing agent can perform etherification reaction with bromine elements on a polyester resin chain under an alkaline condition, so that one end of the flame retardant reinforcing agent is grafted on one side of carboxyl groups of ester groups in the polyester resin, the other end of the flame retardant reinforcing agent is grafted on one side of hydroxyl groups of the ester groups to realize dislocation crosslinking, the dislocation crosslinking agents are connected through diamino silane, and when the ester groups are hydrolyzed and broken, the polymer can still be crosslinked into a net structure through the flame retardant reinforcing agent, the structure of the polymer can not be changed due to hydrolysis, so that the mechanical property of the resin can be effectively prevented from being weakened, meanwhile, the silane bond contained in the diaminosilane can not only improve the hydrophobic property of the resin, but also improve the heat resistance of the resin, so that the prepared coating can still keep good performance in a damp and hot environment, in the flame-retardant polyester resin prepared in application example 3, the saturated polyester resin is crosslinked with hydroquinone and terephthalaldehyde, the hydroquinone can only be crosslinked on one side of carboxyl of the polyester resin, although the side of the carboxyl can still be crosslinked, the side of the hydroxyl can be hydrolyzed and dissociated into small molecular substances, and the crosslinked carboxyl chains can not be connected, and the added diaminosilane can not react and be grafted on the polyester resin, so that the added diaminosilane is dispersed in the resin and can not be crosslinked, so that the polymerization network structure of the polyester resin is damaged, the performance of the flame-retardant polyester resin is reduced, but in the application example 4, because two aldehyde groups in the terephthalaldehyde can only be crosslinked on one side of the hydroxyl group of the ester group, although the terephthalaldehyde can also be subjected to crosslinking polymerization through the diaminosilane, a free small molecular substance is formed after hydrolysis of one side of the carboxyl group, so that the original compact network structure of the flame-retardant polyester resin is damaged to a certain extent, and the network structure of the polymer is broken after hydrolysis of the ester group, so that the performance of the coating is reduced; in application example 5, since no silane bond was introduced, the hydrophobic property of the coating was lowered and the heat resistance was also lowered, and although the network structure was maintained after hydrolysis, the properties were still lowered.
(2) The coatings prepared in application examples 1 to 6 were poured into a mold and cured to form test specimens, and then the limiting oxygen index was measured, and the specific measurement results are shown in table 1:
TABLE 1 results of flame retardancy measurements of the coatings prepared in application examples 1-6
It can be seen from table 1 that the coating prepared in application example 1 has high flame retardant property, a large amount of nitrogen element, silicon element, phosphate group and part of unreacted bromine element are uniformly introduced into the network structure of the coating and are uniformly dispersed, and the high flame retardant property is realized through a synergistic effect, the flame retardant property is reduced due to the fact that no phosphate group is introduced in application examples 2-4, meanwhile, the condition that the introduced silane bond is dissociated in the resin to cause non-uniform dispersion is further caused in application example 3, the flame retardant property is reduced, the flame retardant property of the coating is reduced due to the fact that no silicon element is introduced in application example 5, and meanwhile, the flame retardant property is reduced due to the fact that the phosphate is directly added in application example 6, so that the phosphate and the coating are easily mixed and dispersed unevenly through mechanical mixing, and the flame retardant property is reduced.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (9)
1. The preparation process of the flame-retardant polyester resin is characterized by comprising the following specific preparation processes:
adding acetone, copper chloride and isobutyraldehyde into a reaction kettle, stirring and reacting for 2-3h at 5-10 ℃, heating to evaporate a solvent, cooling to 0 ℃, filtering and recovering cuprous chloride to obtain chloroisobutyraldehyde;
secondly, simultaneously adding benzene and dimethyl phosphite into a reaction kettle, adding a methanol solution of sodium methoxide into the reaction kettle, uniformly stirring, heating to 55-60 ℃, dropwise adding N-allylmethylamine into the reaction kettle, controlling the dropwise addition within 1h, performing reflux reaction for 3-4h after the addition is finished, adjusting the pH value of the solution to 7-7.5, adding the product into water, standing for layering, separating out benzene, and performing reduced pressure distillation on the water solution to obtain aminated phosphate;
step three, simultaneously adding hydroquinone, aminated phosphate, paraformaldehyde, ethanol and concentrated hydrochloric acid into a reaction kettle, heating to 80-85 ℃ for reaction for 14-16h, then cooling to 5 ℃, adjusting the pH value to 8 with a sodium hydroxide solution, cooling in an ice water bath, crystallizing, filtering, washing with water and drying to obtain phosphate-based hydroquinone;
step four, adding phosphate-based hydroquinone, absolute ethyl alcohol and sodium hydroxide into a reaction kettle at the same time, stirring and heating until reflux, adding chloroisobutyraldehyde into the reaction kettle, keeping the temperature for reaction for 3-4 hours, carrying out rotary evaporation to recover part of ethanol, cooling to 0 ℃, freezing overnight, filtering, washing with water, adding the obtained product into ethanol for recrystallization, filtering and drying to obtain a flame-retardant reinforcing agent;
step five, continuously introducing nitrogen into the reaction kettle, then adding dihydroxy acetophenone, adipic acid bromide and monobutyl tin oxide, slowly heating to melt the materials, then carrying out heat preservation reaction for 1h, then heating to 230-;
sixthly, adding a flame-retardant reinforcing agent, absolute ethyl alcohol and a sodium hydroxide solution with the mass concentration of 18% into a reaction kettle, stirring and dissolving, then adding saturated polyester resin liquid into the reaction kettle, heating to 50-55 ℃, stirring and reacting for 4-5h, then heating to 90-95 ℃, adding a saturated solution of sodium carbonate into the reaction kettle, stirring and reacting for 4h, then dropwise adding diaminosilane into the reaction kettle, continuously adding diethylene glycol ethyl ether acetate into the reaction kettle in the reaction process to enable the material to keep fluidity all the time, then carrying out rotary evaporation to recover the solvent, washing the product to be neutral, drying the product with anhydrous magnesium sulfate, then adding diethylene glycol ethyl ether acetate into the product, stirring and mixing until the solid content is 55%, thus obtaining the flame-retardant polyester resin;
wherein the preparation process of the diamino silane comprises the following steps: mixing chloroplatinic acid hexahydrate and isopropanol to prepare a catalyst solution, adding 2-methylallylamine and 1,1,3, 3-tetramethyldisiloxane into a reaction kettle, adding the catalyst solution into the reaction kettle, heating to 75-80 ℃ for refluxing, monitoring the reaction process by using a gas chromatograph in the reaction process, and carrying out reduced pressure distillation after the reaction is completed to obtain the diaminosilane.
2. The process for preparing a flame retardant polyester resin according to claim 1, wherein isobutyraldehyde and copper chloride are added in a mass ratio of 1:2 to 2.3 in the first step, and isobutyraldehyde and acetone are added in a mass ratio of 1: 2.5.
3. The process for preparing a flame retardant polyester resin according to claim 1, wherein in the second step, the ratio of dimethyl phosphite: sodium methoxide and N-allylmethylamine in a mass ratio of 1: 0.98-0.99, and 500mL of benzene per mole of dimethyl phosphite.
4. The process according to claim 1, wherein in the third step, hydroquinone and aminated phosphate are added in a ratio of 1:1.23-1.31, while paraformaldehyde 38-42g, concentrated hydrochloric acid 2.3-2.4mL and absolute ethanol 230-240mL are added per mole of hydroquinone.
5. The process for preparing a flame retardant polyester resin according to claim 1, wherein in the fourth step, the ratio of the amount of the phosphate-based hydroquinone to the amount of the chloroisobutyraldehyde to the amount of the sodium hydroxide is 1:0.97 to 0.98: 1.13-1.15, and adding 300-310mL of ethanol per mole of phosphate-based hydroquinone.
6. The process according to claim 1, wherein 0.93-0.94kg of adipic acid bromide and 1.87-1.93g of monobutyltin oxide are added to one kg of dihydroxy acetophenone in the fifth step.
7. The process for preparing flame-retardant polyester resin as claimed in claim 1, wherein in the sixth step, 96-102g of flame-retardant enhancer, 250mL of anhydrous ethanol, 31-36mL of 18% sodium hydroxide solution, 31-34g of saturated solution of sodium carbonate and 42-49g of diaminosilane are added to each kilogram of saturated polyester resin solution.
8. The process for preparing a flame retardant polyester resin according to claim 1, wherein the ratio of the amount of 2-methylallylamine to 1,1,3, 3-tetramethyldisiloxane is 3.4 to 3.7: 1, while adding the catalyst 6 x 10 per mole of 1,1,3, 3-tetramethyldisiloxane-5mol。
9. Use of a flame retardant polyester resin according to any of claims 1 to 8 in a flame retardant coating.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4085086A (en) * | 1974-06-27 | 1978-04-18 | Dainippon Ink And Chemicals, Inc. | Process for preparing flame retardant thermoplastic polyesters |
| IT1199681B (en) * | 1986-11-28 | 1988-12-30 | Montedipe Spa | POLYOLS-POLYESTERS AND THEIR USE IN THE PRODUCTION OF POLYURETHANE FOAMS |
| US5232471A (en) * | 1992-05-13 | 1993-08-03 | Air Products And Chemicals, Inc. | Membranes formed from nitrated polyarylates |
| WO2004046223A3 (en) * | 2002-11-19 | 2004-11-18 | Genzyme Corp | Polyionene polymers with hydrolyzable linkages |
| CN101514253A (en) * | 2008-12-31 | 2009-08-26 | 上海新天和树脂有限公司 | Environment-friendly flame-retarded unsaturated polyester resin and preparation method thereof |
| CN102212174A (en) * | 2011-05-11 | 2011-10-12 | 华南理工大学 | Transparent reaction type phosphorus-boron-silicon flame-retardant unsaturated polyester and preparation method thereof |
| CN102731952A (en) * | 2012-06-26 | 2012-10-17 | 常州市华润复合材料有限公司 | Halogen-free fire-retardant unsaturated polyester resin, preparation method and use thereof |
| CN104387571A (en) * | 2014-11-10 | 2015-03-04 | 杭州湘隽纺织阻燃科技有限公司 | Phosphorous-nitrogen-containing polyethylene glycol terephthalate flame retardant copolyester and application of flame retardant copolyester |
| CN107082876A (en) * | 2017-05-24 | 2017-08-22 | 黄山市向荣新材料有限公司 | A kind of flame retardant type polyester resin, its preparation method and the powdery paints comprising it |
| CN108329355A (en) * | 2018-02-11 | 2018-07-27 | 北京化工大学 | A kind of method of preparation and use of multi-functional type ring phosphonitrile fire retardant |
| CN108586719A (en) * | 2018-04-12 | 2018-09-28 | 黄山正杰新材料有限公司 | A kind of powdery paints flame retardant type polyester resin and preparation method thereof |
| CN110016054A (en) * | 2019-03-15 | 2019-07-16 | 四川大学 | The ion monomer of phosphorus-nitrogen containing benzheterocycle structure, with its fire-retardant copolymerization ester type ionomer and their preparation method and application |
| CN111533894A (en) * | 2020-06-15 | 2020-08-14 | 徐松波 | Phosphorus-nitrogen-containing flame-retardant polyester and preparation method thereof |
| CN111635513A (en) * | 2020-06-22 | 2020-09-08 | 马海社 | Crosslinked polymer flame retardant and preparation method thereof |
| CN111647298A (en) * | 2020-06-22 | 2020-09-11 | 徐毓敏 | Cable fireproof coating and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101319677B1 (en) * | 2011-10-28 | 2013-10-17 | 삼성전기주식회사 | Insulating resin composition for printed circuit board and printed circuit board comprising the same |
-
2020
- 2020-12-15 CN CN202011477908.3A patent/CN112592468B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4085086A (en) * | 1974-06-27 | 1978-04-18 | Dainippon Ink And Chemicals, Inc. | Process for preparing flame retardant thermoplastic polyesters |
| IT1199681B (en) * | 1986-11-28 | 1988-12-30 | Montedipe Spa | POLYOLS-POLYESTERS AND THEIR USE IN THE PRODUCTION OF POLYURETHANE FOAMS |
| US5232471A (en) * | 1992-05-13 | 1993-08-03 | Air Products And Chemicals, Inc. | Membranes formed from nitrated polyarylates |
| WO2004046223A3 (en) * | 2002-11-19 | 2004-11-18 | Genzyme Corp | Polyionene polymers with hydrolyzable linkages |
| CN101514253A (en) * | 2008-12-31 | 2009-08-26 | 上海新天和树脂有限公司 | Environment-friendly flame-retarded unsaturated polyester resin and preparation method thereof |
| CN102212174A (en) * | 2011-05-11 | 2011-10-12 | 华南理工大学 | Transparent reaction type phosphorus-boron-silicon flame-retardant unsaturated polyester and preparation method thereof |
| CN102731952A (en) * | 2012-06-26 | 2012-10-17 | 常州市华润复合材料有限公司 | Halogen-free fire-retardant unsaturated polyester resin, preparation method and use thereof |
| CN104387571A (en) * | 2014-11-10 | 2015-03-04 | 杭州湘隽纺织阻燃科技有限公司 | Phosphorous-nitrogen-containing polyethylene glycol terephthalate flame retardant copolyester and application of flame retardant copolyester |
| CN107082876A (en) * | 2017-05-24 | 2017-08-22 | 黄山市向荣新材料有限公司 | A kind of flame retardant type polyester resin, its preparation method and the powdery paints comprising it |
| CN108329355A (en) * | 2018-02-11 | 2018-07-27 | 北京化工大学 | A kind of method of preparation and use of multi-functional type ring phosphonitrile fire retardant |
| CN108586719A (en) * | 2018-04-12 | 2018-09-28 | 黄山正杰新材料有限公司 | A kind of powdery paints flame retardant type polyester resin and preparation method thereof |
| CN110016054A (en) * | 2019-03-15 | 2019-07-16 | 四川大学 | The ion monomer of phosphorus-nitrogen containing benzheterocycle structure, with its fire-retardant copolymerization ester type ionomer and their preparation method and application |
| CN111533894A (en) * | 2020-06-15 | 2020-08-14 | 徐松波 | Phosphorus-nitrogen-containing flame-retardant polyester and preparation method thereof |
| CN111635513A (en) * | 2020-06-22 | 2020-09-08 | 马海社 | Crosslinked polymer flame retardant and preparation method thereof |
| CN111647298A (en) * | 2020-06-22 | 2020-09-11 | 徐毓敏 | Cable fireproof coating and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| A novel flame-retardant-free copolyester: cross-linking towards self extinguishing and non-dripping;Hai-Bo Zhao等;《JOURNAL OF MATERIALS CHEMISTRY A》;20120808;第22卷(第37期);第19849-19857页 * |
| The high-temperature self-crosslinking contribution of azobenzene groups to the flame retardance and anti-dripping of copolyesters;Xin-Ke Jing等;《JOURNAL OF MATERIALS CHEMISTRY A》;20130523;第1卷(第32期);第9264-9272页 * |
| 自交联型阻燃不饱和树脂的制备;袁亮，刘旭东，***，于卓恒，秦梅;《化学工程师》;20190525;第33卷(第5期);第10-12页 * |
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