CN114672009B - Flame-retardant unsaturated polyester resin and preparation method thereof - Google Patents
Flame-retardant unsaturated polyester resin and preparation method thereof Download PDFInfo
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6928—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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Abstract
The invention discloses a flame-retardant unsaturated polyester resin and a preparation method thereof. The method comprises the following steps: placing biobased dihydric alcohol, pentaerythritol, biobased unsaturated dibasic acid or anhydride, biobased saturated dibasic acid or anhydride, an amino acid flame retardant, a catalyst and one third of polymerization inhibitor into a reaction kettle, setting the stirring speed to be 70-90 rmp under the nitrogen atmosphere, setting the temperature to be 100-110 ℃, and stirring for 45-60 minutes; heating to 170-190 ℃ at a certain heating rate, and reacting for 3.5-4 hours; continuously heating to 220-230 ℃ to react for 2-3 hours, and taking the acid value of 28-32 mgKOH/g as a reaction end point; cooling to 140-150 deg.c and adding one third of polymerization inhibitor; and cooling to 80-100 ℃, adding one third of polymerization inhibitor, styrene and glycidyl POSS, and uniformly mixing to obtain the flame-retardant unsaturated polyester resin. The amino acid flame retardant is prepared as one of raw materials for preparing the polyester resin, and flame retardant molecules are embedded in a polyester main chain, so that the flame retardance is obviously improved; and simultaneously, the mechanical properties of the bio-based polyester resin are enhanced by the cooperation of pentaerythritol.
Description
Technical Field
The invention relates to the technical field of polyester resin, in particular to flame-retardant unsaturated polyester resin and a preparation method thereof.
Background
The unsaturated polyester resin is a linear high molecular compound formed by locking unsaturated dibasic acid or saturated dibasic acid and unsaturated dihydric alcohol or saturated dihydric alcohol, and then is mixed with a certain amount of vinyl monomer to form a polymer solution. The method has the advantages of green and environmental protection, and is advocated by the great force of the national development of green; is widely used in the industrial fields of construction, decoration and the like. The fire-resistant material is also high polymer, is sensitive to heat, is easy to burn when encountering a fire source, and brings hidden danger. Therefore, a preparation tool is required; an unsaturated polyester resin having flame retardancy.
At present, the introduction of unsaturated polyester resins is generally of the mixed type and of the reactive type; because the flame retardant in the mixed type is either an inorganic material or a small molecular polymer, the compatibility and the surface migration and precipitation problems exist; can affect the mechanical property and the long-term flame retardant property after curing. The reactive flame retardant is grafted on the polyester chain through direct reaction, so that the migration and compatibility problems are effectively solved; however, in the prior art, the mechanical properties of the reactive flame retardant resin are reduced after curing, which affects practical application. On the other hand, the shortage of petroleum resources leads to the development of bio-based polyester resins, but the reactive flame retardant can escape along with the rise of temperature due to the low melting point, high flexibility and low rigidity of the bio-based unsaturated polyester resin, which affects the flame retardant effect. The general method for modifying mechanical properties is to add inorganic nanoparticles, but the problems of compatibility and aggregation are also existed.
In summary, solving the problems described above, the preparation of a flame retardant unsaturated polyester resin is of great significance.
Disclosure of Invention
The invention aims to provide a flame-retardant unsaturated polyester resin and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a method for preparing flame-retardant unsaturated polyester resin, comprising the following steps:
placing biobased dihydric alcohol, pentaerythritol, biobased unsaturated dibasic acid or anhydride, biobased saturated dibasic acid or anhydride, an amino acid flame retardant, a catalyst and one third of polymerization inhibitor into a reaction kettle, setting the stirring speed to be 70-90 rmp under the nitrogen atmosphere, setting the temperature to be 100-110 ℃, and stirring for 45-60 minutes; heating to 170-190 ℃ at a certain heating rate, and reacting for 3.5-4 hours; continuously heating to 220-230 ℃ to react for 2-3 hours, and taking the acid value of 28-32 mgKOH/g as a reaction end point; cooling to 140-150 deg.c and adding one third of polymerization inhibitor; and cooling to 80-100 ℃, adding one third of polymerization inhibitor, styrene and glycidyl POSS, and uniformly mixing to obtain the flame-retardant unsaturated polyester resin.
More preferably, the heating rate is a heating rate of 1 to 1.5 ℃/min.
More preferably, the unsaturated polyester resin comprises the following raw materials: 18 to 20 parts of bio-based dihydric alcohol, 5 to 8 parts of pentaerythritol, 16 to 24 parts of bio-based unsaturated dibasic acid or anhydride, 14 to 18 parts of bio-based saturated dibasic acid or anhydride, 10 to 14 parts of amino acid flame retardant, 2 to 3 parts of glycidyl POSS, 35 to 38 parts of styrene, 0.021 to 0.048 part of polymerization inhibitor and 0.02 to 0.05 part of catalyst.
More preferably, the bio-based diol comprises one or more of 1, 4-butanediol, 2, 3-butanediol, and 1, 3-propanediol; the bio-based unsaturated dibasic acid or anhydride comprises one or more of itaconic acid, itaconic anhydride, fumaric acid and fumaric anhydride; the bio-based saturated dibasic acid or anhydride comprises one or more of adipic acid, adipic anhydride, succinic acid and succinic anhydride.
More preferably, the polymerization inhibitor is 4-methoxyphenol; the catalyst is one of p-toluenesulfonic acid and tetrabutyl titanate.
More optimally, the preparation method of the amino acid flame retardant comprises the following steps: tyrosine is added into 0.02-0.03 g/mL sodium hydroxide solution in nitrogen atmosphere, and the temperature is set at 85-90 ℃ for stirring and dispersing; dropwise adding 5-hydroxymethylfurfural solution, and reacting for 2-3 hours; cooling to 25-28 ℃, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution, and reacting for 8-10 hours; concentrating, adding dilute hydrochloric acid to regulate pH value to 2.5-3, washing, filtering and drying to obtain the amino acid fire retardant.
More optimally, the mass ratio of the sodium hydroxide to the tyrosine to the 5-hydroxymethylfurfural to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1 (3.5-4), 2.2-2.5 and 2.5-3.
More preferably, the 5-hydroxymethylfurfural solution is 5-hydroxymethylfurfural ethanol solution with the concentration of 0.45-0.5 g/mL.
More preferably, the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution is a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ethanol solution with a concentration of 0.25-0.3 g/mL.
More optimally, the flame-retardant unsaturated polyester resin is prepared by the preparation method of the flame-retardant unsaturated polyester resin.
In the technical scheme, the amino acid flame retardant is prepared to serve as one of raw materials for preparing the polyester resin, flame retardant molecules are embedded in a polyester main chain, and the flame retardance is obviously improved; and simultaneously, the mechanical properties of the bio-based polyester resin are enhanced by the cooperation of pentaerythritol.
(1) In the scheme, tyrosine with a flexible chain segment and a rigid benzene ring is used as a basis, the tyrosine is mixed with 5-hydroxymethylfurfural, and Schiff base reaction is generated between amino and aldehyde groups to prepare Schiff base derivatives of the furfural; the amino acid flame retardant is prepared by utilizing the addition reaction between the generated Schiff base derivative and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; because one end of tyrosine contains hydroxyl, one section also contains carboxyl, and one end of 5-hydroxymethylfurfural also contains hydroxyl, the reaction compatibility is improved; the amino acid flame retardant can be embedded in the polyester chain segment through dehydration condensation with the raw materials of the bio-based alcohol, acid and anhydride; enhancing flame retardancy; meanwhile, the introduction of benzene rings increases the glass transition temperature and improves the mechanical properties of the cured polyester.
In the scheme, the 5-hydroxymethylfurfural is added in excess to promote the reaction grafting, and the material is not required to be removed by post-treatment, because the material and the introduced pentaerythritol can react to enhance the mechanical property of the polyester resin
(2) In the scheme, pentaerythritol is introduced, the pentaerythritol is used as a nucleation site of a part of polyester chain segments, and the crossover chain of the pentaerythritol is used for enhancing the interpenetration of the chain segments in the polyester resin; that is, functions as a crosslinking agent, since the movement of the molecular chain is partially restricted due to the interpenetration structure, a stable network structure is formed, so that the mechanical strength of the bio-based resin is improved; on the other hand, the catalyst is catalyzed by 5-hydroxymethyl furfural to form rigid diol with spiro structure, the glass transition temperature of the bio-based resin is increased, and the heat resistance and the rigidity are improved.
Because of the reaction between 5-hydroxymethylfurfural and pentaerythritol, the flame retardance and mechanical properties are reduced if an amino acid flame retardant is added as a chain extender. The 5-hydroxymethylfurfural has low boiling point, is easy to gasify and is easy to react with pentaerythritol unevenly, so that the scheme has a slow temperature rising process in the early stage to promote the reaction. Of course, the amount of 5-hydroxymethylfurfural is not excessive, otherwise excessive pentaerythritol is consumed, and other reactions of pentaerythritol are affected.
(3) In addition, glycidyl POSS is added in the process of adding the diluent finally, so that the polyester resin can be crosslinked and grafted by utilizing the ring opening process of carboxyl and hydroxyl to epoxy groups during curing; the mechanical property, heat resistance and flame retardance of the epoxy resin are enhanced, and the epoxy resin has adhesion with other materials. However, the amount of the catalyst to be added should not be excessive.
(4) In the scheme, 4-methoxyphenol is used as a polymerization inhibitor, and even if the reaction is carried out at the temperature of more than 230 ℃, the 4-methoxyphenol can retain carbon-carbon double bonds to the greatest extent. The polyester resin is convenient to be used for ultraviolet curing subsequently.
Flame retardant mechanism: 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-can be decomposed to generate phosphorus oxide, so that the hydrothermal degradation of polyester to generate carboxylic acid and phenolic hydroxyl is promoted; a dense carbon layer is formed. Meanwhile, the introduction of glycidyl POSS increases a silicon oxide layer, and the ether bond contained in the silicon oxide layer has an adsorption function on carbon dioxide; the flame retardant property is synergistically enhanced.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
(1) Tyrosine is added into 0.025g/mL sodium hydroxide solution under nitrogen atmosphere, and the temperature is set at 88 ℃ for stirring and dispersion; dropwise adding 0.48g/mL of 5-hydroxymethylfurfural ethanol solution, and reacting for 2.5 hours; cooling to 25 ℃, adding 0.26g/mL of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ethanol solution, and reacting for 9 hours; concentrating, adding dilute hydrochloric acid to adjust pH=2.6, washing, filtering and drying to obtain the amino acid flame retardant.
(2) Weighing 0.03 part of polymerization inhibitor, and dividing into three parts for standby; placing 19 parts of bio-based dihydric alcohol, 7 parts of pentaerythritol, 22 parts of bio-based unsaturated dibasic acid or anhydride, 15 parts of bio-based saturated dibasic acid or anhydride, 12 parts of amino acid flame retardant, 0.03 part of catalyst and one third of polymerization inhibitor in a reaction kettle, setting the stirring speed to be 80rmp under the nitrogen atmosphere, setting the temperature to be 110 ℃, and stirring for 50 minutes; heating to 180 ℃ at a heating rate of 1.2 ℃/min, and reacting for 3.8 hours; continuously heating to 225 ℃ to react for 2.5 hours, and taking the acid value of 30mgKOH/g as the reaction end point; cooling to 145 ℃ and adding one third of polymerization inhibitor; and then cooling to 90 ℃, adding one third of polymerization inhibitor, 36 parts of styrene and 2 parts of glycidyl POSS, and uniformly mixing to obtain the flame-retardant unsaturated polyester resin.
In the technical scheme, the mass ratio of the sodium hydroxide to the tyrosine to the 5-hydroxymethylfurfural to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:3.8:2.4:2.8; the bio-based diol comprises 1, 4-butanediol; the biobased unsaturated dibasic acid or anhydride comprises itaconic acid; the bio-based saturated dibasic acid or anhydride comprises adipic acid; the polymerization inhibitor is 4-methoxyphenol; the catalyst is p-toluenesulfonic acid.
Example 2:
(1) Tyrosine is added into 0.02g/mL sodium hydroxide solution under the nitrogen atmosphere, and the temperature is set at 85 ℃ for stirring and dispersion; dropwise adding 0.45g/mL of 5-hydroxymethylfurfural ethanol solution, and reacting for 2 hours; cooling to 25 ℃, adding 0.25g/mL of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ethanol solution, and reacting for 8 hours; concentrating, adding dilute hydrochloric acid to adjust pH=2.5, washing, filtering and drying to obtain the amino acid flame retardant.
(2) Weighing 0.021 part of polymerization inhibitor, and dividing into three parts for later use; 18 parts of bio-based dihydric alcohol, 5 parts of pentaerythritol, 16 parts of bio-based unsaturated dibasic acid or anhydride, 14 parts of bio-based saturated dibasic acid or anhydride, 10 parts of amino acid flame retardant, 0.02 part of catalyst and one third of polymerization inhibitor are placed in a reaction kettle, and under the nitrogen atmosphere, the stirring speed is set to be 70rmp, the temperature is set to be 100 ℃, and the stirring is carried out for 45 minutes; heating to 170 ℃ at a heating rate of 1 ℃/min, and reacting for 3.5 hours; continuously heating to 220 ℃ to react for 2 hours, and taking the acid value of 28mgKOH/g as the reaction end point; cooling to 140 ℃ and adding one third of polymerization inhibitor; and cooling to 80 ℃, adding one third of polymerization inhibitor, 35 parts of styrene and 2 parts of glycidyl POSS, and uniformly mixing to obtain the flame-retardant unsaturated polyester resin.
In the technical scheme, the mass ratio of the sodium hydroxide to the tyrosine to the 5-hydroxymethylfurfural to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:3.5:2.2:2.5; the bio-based diol comprises 2, 3-butanediol; the biobased unsaturated dibasic acid or anhydride comprises itaconic anhydride; the bio-based saturated dibasic acid or anhydride comprises adipic acid; the polymerization inhibitor is 4-methoxyphenol; the catalyst is p-toluenesulfonic acid.
Example 3:
(1) Tyrosine is added into 0.03g/mL sodium hydroxide solution under the nitrogen atmosphere, and the temperature is set to 90 ℃ for stirring and dispersion; dropwise adding 0.5g/mL of 5-hydroxymethylfurfural ethanol solution, and reacting for 3 hours; cooling to 28 ℃, adding 0.3g/mL of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ethanol solution, and reacting for 10 hours; concentrating, adding dilute hydrochloric acid to adjust pH to be 3, washing, filtering and drying to obtain the amino acid flame retardant.
(2) Weighing 0.048 part of polymerization inhibitor, and dividing into three parts for standby; placing 20 parts of bio-based dihydric alcohol, 8 parts of pentaerythritol, 24 parts of bio-based unsaturated dibasic acid or anhydride, 18 parts of bio-based saturated dibasic acid or anhydride, 14 parts of amino acid flame retardant, 0.05 part of catalyst and one third of polymerization inhibitor in a reaction kettle, setting the stirring speed to be 90rmp under the nitrogen atmosphere, setting the temperature to be 110 ℃, and stirring for 60 minutes; heating to 190 ℃ at a heating rate of 1.5 ℃/min, and reacting for 4 hours; continuously heating to 230 ℃ to react for 3 hours, and taking the acid value of 32mgKOH/g as the reaction end point; cooling to 150 ℃ and adding one third of polymerization inhibitor; and cooling to 100 ℃, adding one third of polymerization inhibitor, 38 parts of styrene and 3 parts of glycidyl POSS, and uniformly mixing to obtain the flame-retardant unsaturated polyester resin.
In the technical scheme, the mass ratio of the sodium hydroxide to the tyrosine to the 5-hydroxymethylfurfural to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:4:2.5:3; the bio-based diol comprises 1, 4-butanediol; the biobased unsaturated dibasic acid or anhydride comprises fumaric acid; the bio-based saturated dibasic acid or anhydride comprises succinic anhydride; the polymerization inhibitor is 4-methoxyphenol; the catalyst is p-toluenesulfonic acid.
Comparative example 1: the mass ratio of sodium hydroxide, tyrosine, furfural and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:3.8:1.8:2.8;
(1) Tyrosine is added into 0.025g/mL sodium hydroxide solution under nitrogen atmosphere, and the temperature is set at 88 ℃ for stirring and dispersion; dropwise adding 0.48g/mL of 5-hydroxymethylfurfural ethanol solution, and reacting for 2.5 hours; cooling to 25 ℃, adding 0.26g/mL of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ethanol solution, and reacting for 9 hours; concentrating, adding dilute hydrochloric acid to adjust pH=2.6, washing, filtering and drying to obtain the amino acid flame retardant.
(2) Weighing 0.03 part of polymerization inhibitor, and dividing into three parts for standby; placing 19 parts of bio-based dihydric alcohol, 7 parts of pentaerythritol, 22 parts of bio-based unsaturated dibasic acid or anhydride, 15 parts of bio-based saturated dibasic acid or anhydride, 12 parts of amino acid flame retardant, 0.03 part of catalyst and one third of polymerization inhibitor in a reaction kettle, setting the stirring speed to be 80rmp under the nitrogen atmosphere, setting the temperature to be 110 ℃, and stirring for 50 minutes; heating to 180 ℃ at a heating rate of 1.2 ℃/min, and reacting for 3.8 hours; continuously heating to 225 ℃ to react for 2.5 hours, and taking the acid value of 30mgKOH/g as the reaction end point; cooling to 145 ℃ and adding one third of polymerization inhibitor; and then cooling to 90 ℃, adding one third of polymerization inhibitor, 36 parts of styrene and 2 parts of glycidyl POSS, and uniformly mixing to obtain the flame-retardant unsaturated polyester resin.
In the technical scheme, the mass ratio of the sodium hydroxide to the tyrosine to the furfural to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:3.8:1.8:2.8; the bio-based diol comprises 1, 4-butanediol; the biobased unsaturated dibasic acid or anhydride comprises itaconic acid; the bio-based saturated dibasic acid or anhydride comprises adipic acid; the polymerization inhibitor is 4-methoxyphenol; the catalyst is p-toluenesulfonic acid.
Comparative example 2: the mass ratio of sodium hydroxide, tyrosine, 5-hydroxymethyl furfural and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:3.8:3:2.8;
(1) Tyrosine is added into 0.025g/mL sodium hydroxide solution under nitrogen atmosphere, and the temperature is set at 88 ℃ for stirring and dispersion; dropwise adding 0.48g/mL of 5-hydroxymethylfurfural ethanol solution, and reacting for 2.5 hours; cooling to 25 ℃, adding 0.26g/mL of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ethanol solution, and reacting for 9 hours; concentrating, adding dilute hydrochloric acid to adjust pH=2.6, washing, filtering and drying to obtain the amino acid flame retardant.
(2) Weighing 0.03 part of polymerization inhibitor, and dividing into three parts for standby; placing 19 parts of bio-based dihydric alcohol, 7 parts of pentaerythritol, 22 parts of bio-based unsaturated dibasic acid or anhydride, 15 parts of bio-based saturated dibasic acid or anhydride, 12 parts of amino acid flame retardant, 0.03 part of catalyst and one third of polymerization inhibitor in a reaction kettle, setting the stirring speed to be 80rmp under the nitrogen atmosphere, setting the temperature to be 110 ℃, and stirring for 50 minutes; heating to 180 ℃ at a heating rate of 1.2 ℃/min, and reacting for 3.8 hours; continuously heating to 225 ℃ to react for 2.5 hours, and taking the acid value of 30mgKOH/g as the reaction end point; cooling to 145 ℃ and adding one third of polymerization inhibitor; and then cooling to 90 ℃, adding one third of polymerization inhibitor, 36 parts of styrene and 2 parts of glycidyl POSS, and uniformly mixing to obtain the flame-retardant unsaturated polyester resin.
In the technical scheme, the mass ratio of the sodium hydroxide to the tyrosine to the 5-hydroxymethylfurfural to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:3.8:3:2.8; the bio-based diol comprises 1, 4-butanediol; the biobased unsaturated dibasic acid or anhydride comprises itaconic acid; the bio-based saturated dibasic acid or anhydride comprises adipic acid; the polymerization inhibitor is 4-methoxyphenol; the catalyst is p-toluenesulfonic acid.
Comparative example 3: directly reacting 5-hydroxymethylfurfural with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to prepare an amino acid flame retardant without adding tyrosine;
(1) Adding 0.26g/mL of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ethanol solution into the 5-hydroxymethylfurfural ethanol solution in a nitrogen atmosphere, and reacting for 9 hours at room temperature; concentrating, washing, filtering and drying to obtain the amino acid flame retardant.
(2) Weighing 0.03 part of polymerization inhibitor, and dividing into three parts for standby; placing 19 parts of bio-based dihydric alcohol, 7 parts of pentaerythritol, 22 parts of bio-based unsaturated dibasic acid or anhydride, 15 parts of bio-based saturated dibasic acid or anhydride, 12 parts of amino acid flame retardant, 0.03 part of catalyst and one third of polymerization inhibitor in a reaction kettle, setting the stirring speed to be 80rmp under the nitrogen atmosphere, setting the temperature to be 110 ℃, and stirring for 50 minutes; heating to 180 ℃ at a heating rate of 1.2 ℃/min, and reacting for 3.8 hours; continuously heating to 225 ℃ to react for 2.5 hours, and taking the acid value of 30mgKOH/g as the reaction end point; cooling to 145 ℃ and adding one third of polymerization inhibitor; and then cooling to 90 ℃, adding one third of polymerization inhibitor, 36 parts of styrene and 2 parts of glycidyl POSS, and uniformly mixing to obtain the flame-retardant unsaturated polyester resin.
In the technical scheme, the mass ratio of the sodium hydroxide to the tyrosine to the 5-hydroxymethylfurfural to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:3.8:2.4:2.8; the bio-based diol comprises 1, 4-butanediol; the biobased unsaturated dibasic acid or anhydride comprises itaconic acid; the bio-based saturated dibasic acid or anhydride comprises adipic acid; the polymerization inhibitor is 4-methoxyphenol; the catalyst is p-toluenesulfonic acid.
Comparative example 4: pentaerythritol is added, and biobased dihydric alcohol is adjusted to 28 parts; the remainder was the same as in example 1.
Comparative example 5: glycidyl POSS was not incorporated and the remainder was the same as in example 1.
Comparative example 6: commercially available general unsaturated polyesters.
Experiment: the flame retardant resin polyesters prepared in examples 1 to 3 and comparative examples 1 to 5 were applied to molding compounds, and subjected to performance test, and the obtained data are shown below:
conclusion: from the data in the table above, it can be seen that: the data of examples 1 to 3 are compared with comparative example 6, the limiting oxygen index of the prepared polyester resin reaches 32.8%, and the impact strength reaches 389KJ/m 2 The scheme is shown that: ammoniaThe flame retardant properties and mechanical properties of bio-based polyester resins are indeed promoted by the base acid flame retardants, pentaerythritol, glycidyl POSS.
Comparing the data of examples 1-3 with comparative examples 1-5, it can be found that: in comparative example 1, the addition amount of 5-hydroxymethylfurfural is small, so that the grafting rate of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is low, and the reaction between 5-hydroxymethylfurfural and pentaerythritol is reduced, so that the mechanical property and the flame retardant property are both reduced. In comparative example 2, since the 5-hydroxymethylfurfural was added in an excessive amount, the reaction with pentaerythritol increased, but the cross-structure chain having pentaerythritol as a site was reduced, and the chain break was shortened, and the small amount was increased, so that the mechanical properties were lowered. In comparative example 3, since tyrosine was not introduced, the chain break of the amino acid flame retardant in the polyester main chain was decreased, and the rigidity was decreased, thereby the mechanical properties were decreased. In comparative example 4, since pentaerythritol was not added, the flexibility of chain scission of polyester was increased, and at the same time, reaction grafting with 5-hydroxymethylfurfural was not generated, so that rigidity was lowered, thereby remarkably lowering impact strength. In the same comparative example 5, the mechanical properties and mechanical properties are significantly reduced without the addition of glycidyl POSS.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of flame-retardant unsaturated polyester resin is characterized in that: the method comprises the following steps:
placing biobased dihydric alcohol, pentaerythritol, biobased unsaturated dibasic acid or anhydride, biobased saturated dibasic acid or anhydride, an amino acid flame retardant, a catalyst and one third of polymerization inhibitor into a reaction kettle, setting the stirring speed at 70-90 rpm under nitrogen atmosphere, setting the temperature at 100-110 ℃, and stirring for 45-60 minutes; heating to 170-190 ℃ at a certain heating rate, and reacting for 3.5-4 hours; continuously heating to 220-230 ℃ to react for 2-3 hours, and taking the acid value of 28-32 mgKOH/g as a reaction end point; cooling to 140-150 deg.c and adding one third of polymerization inhibitor; then cooling to 80-100 ℃, adding one third of polymerization inhibitor, styrene and glycidyl POSS, and uniformly mixing to obtain flame-retardant unsaturated polyester resin;
the preparation method of the amino acid flame retardant comprises the following steps: tyrosine is added into 0.02-0.03 g/mL sodium hydroxide solution in nitrogen atmosphere, and the temperature is set at 85-90 ℃ for stirring and dispersing; dropwise adding 5-hydroxymethylfurfural solution, and reacting for 2-3 hours; cooling to 25-28 ℃, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution, and reacting for 8-10 hours; concentrating, adding dilute hydrochloric acid to regulate pH value to 2.5-3, washing, filtering and drying to obtain the amino acid fire retardant.
2. The method for preparing the flame-retardant unsaturated polyester resin according to claim 1, wherein: the heating rate is 1-1.5 ℃/min.
3. The method for preparing the flame-retardant unsaturated polyester resin according to claim 1, wherein: the unsaturated polyester resin comprises the following raw materials: 18 to 20 parts of bio-based dihydric alcohol, 5 to 8 parts of pentaerythritol, 16 to 24 parts of bio-based unsaturated dibasic acid or anhydride, 14 to 18 parts of bio-based saturated dibasic acid or anhydride, 10 to 14 parts of amino acid flame retardant, 2 to 3 parts of glycidyl POSS, 35 to 38 parts of styrene, 0.021 to 0.048 part of polymerization inhibitor and 0.02 to 0.05 part of catalyst.
4. The method for preparing the flame-retardant unsaturated polyester resin according to claim 1, wherein: the bio-based dihydric alcohol comprises one or more of 1, 4-butanediol, 2, 3-butanediol and 1, 3-propanediol; the bio-based unsaturated dibasic acid or anhydride comprises one or more of itaconic acid, itaconic anhydride, fumaric acid and fumaric anhydride; the bio-based saturated dibasic acid or anhydride comprises one or more of adipic acid, adipic anhydride, succinic acid and succinic anhydride.
5. The method for preparing the flame-retardant unsaturated polyester resin according to claim 1, wherein: the polymerization inhibitor is 4-methoxyphenol; the catalyst is one of p-toluenesulfonic acid and tetrabutyl titanate.
6. The method for preparing the flame-retardant unsaturated polyester resin according to claim 1, wherein: the mass ratio of the sodium hydroxide to the tyrosine to the 5-hydroxymethylfurfural to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1 (3.5-4): 2.2-2.5): 2.5-3.
7. The method for preparing the flame-retardant unsaturated polyester resin according to claim 1, wherein: the 5-hydroxymethylfurfural solution is 5-hydroxymethylfurfural ethanol solution with the concentration of 0.45-0.5 g/mL.
8. The method for preparing the flame-retardant unsaturated polyester resin according to claim 1, wherein: the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution is a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ethanol solution with the concentration of 0.25-0.3 g/mL.
9. A flame retardant unsaturated polyester resin produced by the method for producing a flame retardant unsaturated polyester resin according to any one of claims 1 to 8.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4742088A (en) * | 1986-09-12 | 1988-05-03 | Kolon Industries, Inc. | Phosphorus-containing nitrogen compounds as flame retardants and synthetic resins containing them |
| CN101386669A (en) * | 2008-10-29 | 2009-03-18 | 华南理工大学 | Reaction-type transparent halogen-free flameproof unsaturated polyester and preparation method thereof |
| CN109912650A (en) * | 2019-04-16 | 2019-06-21 | 中国科学院宁波材料技术与工程研究所 | A kind of phosphorus-nitrogen system biology based flameproofing and its synthetic method and application |
| CN112175294A (en) * | 2020-10-26 | 2021-01-05 | 江苏昊晟塑业科技有限公司 | Flame-retardant foamed polypropylene and preparation method thereof |
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- 2022-03-16 CN CN202210256915.3A patent/CN114672009B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4742088A (en) * | 1986-09-12 | 1988-05-03 | Kolon Industries, Inc. | Phosphorus-containing nitrogen compounds as flame retardants and synthetic resins containing them |
| CN101386669A (en) * | 2008-10-29 | 2009-03-18 | 华南理工大学 | Reaction-type transparent halogen-free flameproof unsaturated polyester and preparation method thereof |
| CN109912650A (en) * | 2019-04-16 | 2019-06-21 | 中国科学院宁波材料技术与工程研究所 | A kind of phosphorus-nitrogen system biology based flameproofing and its synthetic method and application |
| CN112175294A (en) * | 2020-10-26 | 2021-01-05 | 江苏昊晟塑业科技有限公司 | Flame-retardant foamed polypropylene and preparation method thereof |
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