CN115093554B - Special efficient halogen-free flame retardant for PBT (polybutylene terephthalate) and preparation method thereof - Google Patents
Special efficient halogen-free flame retardant for PBT (polybutylene terephthalate) and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a special efficient halogen-free flame retardant for PBT and a preparation method thereof. The flame retardant is applied to PBT resin, and has good flame retardant effect, good mechanical property, good compatibility with a matrix, good dispersibility and good precipitation resistance.
Description
Technical Field
The invention relates to the technical field of flame retardance, in particular to a special efficient halogen-free flame retardant for PBT and a preparation method thereof.
Background
PBT (polybutylene terephthalate) is an engineering plastic with excellent comprehensive properties, and is widely applied to the fields of electronic appliances, automobile industry, mechanical instruments, communication equipment, lamp elements and the like because of high temperature resistance, oil resistance and chemical corrosion resistance. And after the PBT is reinforced by the glass fiber, the notch impact strength of the PBT can be obviously improved, the molding shrinkage rate can be reduced, and the PBT has wider application fields. However, the PBT has inflammability, and the glass fiber is introduced to generate a 'wick effect', so that the PBT reinforced by the glass fiber is harder to flame retardant and is easy to burn when meeting open fire, and great harm is caused to life and property, so that the flame retardant modification treatment of the glass fiber reinforced PBT is particularly important.
Currently, halogen-free flame retardants for PBT products mainly include red phosphorus flame retardants, metal hydroxides, phosphorus flame retardants, nitrogen flame retardants, and phosphorus-nitrogen flame retardants. Wherein, the red phosphorus flame retardant is more used for making dark products, generates unpleasant smell in the processing process and has high storage requirement; the metal hydroxide has serious comprehensive performance loss due to larger addition amount; when the nitrogen flame retardant and the phosphorus flame retardant are used independently, the flame retardant efficiency is low; organic hypophosphites are expensive due to technical barriers and most manufacturers are in the possession of dust. Inorganic hypophosphite has low price and simple synthesis process, but is easy to cause discoloration, scorching and even ignition during the processing due to low thermal stability.
CN104231320B discloses a preparation method of halogen-free flame retardant for glass fiber reinforced PBT, CN104231575B discloses a halogen-free phosphine-free PBT reinforced composite material and a preparation method thereof, and the preparation methods mentioned in the two patents are: the flame retardant is prepared from cyanuric acid, melamine and inorganic hypophosphite, and then the flame retardant is extruded and granulated after being physically blended with an auxiliary agent and PBT, and the PBT halogen-free flame retardant and the composite material with good heat resistance, mechanical property and flame retardance are prepared, but the PBT is required to be subjected to working procedures such as pretreatment before blending extrusion, and the cost is increased. In addition, the PBT has the uneven mixing phenomenon in the physical blending process, and has strong hygroscopicity and poor uneven mixing and dispersion compatibility with powder because of the sensitivity of the PBT to water, so that the flame retardance of the material is damaged, and the mechanical property and the heat resistance of the material are reduced.
Disclosure of Invention
Aiming at the problems, the invention provides the special efficient halogen-free flame retardant for the PBT and the preparation method thereof by combining the structural characteristics and the processing conditions of the PBT. The flame retardant is applied to PBT resin, and has good flame retardant effect, good mechanical property, good compatibility with a matrix, good dispersibility and good precipitation resistance.
The technical scheme of the invention is as follows: a preparation method of a special efficient halogen-free flame retardant for PBT comprises an esterification reaction and a polycondensation reaction to prepare PBT, and is characterized in that a prepared phosphorus-nitrogen halogen-free flame retardant slurry is added in the polycondensation reaction process; the preparation method of the phosphorus-nitrogen halogen-free flame-retardant slurry comprises the following steps: firstly, preparing a trimethylol melamine prepolymer monomer, then slowly adding the trimethylol melamine prepolymer monomer into aluminum hypophosphite slurry, uniformly precipitating the prepolymer by utilizing the weak acidity of the aluminum hypophosphite slurry to cover the surface of aluminum hypophosphite molecules to form a coating layer, then adding zinc borate into the system to react for 4-8 hours at the temperature of 95-105 ℃ so as to enable the zinc borate to react with free naked aluminum hypophosphite to generate zinc hypophosphite or a blend of the zinc hypophosphite and the aluminum hypophosphite to carry out double-layer coating, and obtaining the phosphorus-nitrogen halogen-free flame retardant slurry.
The preparation method of the invention specifically comprises the following steps:
(a) Adding terephthalic acid and 1, 4-butanediol into a reactor, adding a catalyst, and carrying out esterification reaction at 220-260 ℃ and normal pressure to obtain an esterified substance monomer (A);
(b) Sequentially adding water, formaldehyde and melamine into a reaction kettle, regulating pH=8.0-9.0, reacting at 70-80 ℃ to prepare a trimethylol melamine prepolymer monomer solution, slowly adding the trimethylol melamine prepolymer monomer solution into aluminum hypophosphite slurry (the aluminum hypophosphite and the water are mixed according to a certain proportion), uniformly precipitating and covering a prepolymer by utilizing the weak acidity of the aluminum hypophosphite slurry to form a coating layer on the surface of aluminum hypophosphite molecules, reacting for 2-6 hours, adding zinc borate into the system, reacting for 4-8 hours at 95-105 ℃ to react with free bare aluminum hypophosphite to generate zinc hypophosphite or a blend of the zinc hypophosphite and the aluminum hypophosphite, and carrying out double-layer coating to obtain phosphorus-nitrogen halogen-free flame retardant slurry (B);
(c) Adding phosphorus-nitrogen halogen-free flame retardant slurry (B) into an esterified monomer (A), adding a carboxyl chain extender and glass chopped fibers for polycondensation reaction, and then continuously reacting for 1-3 hours at 235-255 ℃ to generate qualified PBT melt with higher polymerization degree, and cooling, granulating and drying the polymerized melt to obtain the special efficient halogen-free flame retardant for PBT.
The catalyst in the step (a) is one or more of dibutyl tin, tetrabutyl titanate and titanium sulfate.
The molar ratio of terephthalic acid, 1, 4-butanediol and catalyst in the step (a) is 1:1-2:0.02-0.06.
The mass ratio of formaldehyde, melamine and water in the step (b) is 1-3:0.95-1.05:5-15.
The mass ratio of the aluminum hypophosphite to the water in the aluminum hypophosphite slurry in the step (b) is 1:4-9.
The zinc borate in the step (b) is one or more of 2335 type, 411 type and 112 type, and the addition amount is 5-15% of the mass of the aluminum hypophosphite.
The mass ratio of the melamine, the aluminum hypophosphite and the zinc borate in the step (b) is 0.2-0.4:1:0.05-0.15.
The carboxyl chain extender in the step (c) is one or more of dimethylolpropionic acid, dicyclo imine ether compound and terephthaloyl caprolactam, and the dosage of the carboxyl chain extender is 5-10% of the mass of the monomer A (dry weight).
The glass chopped fiber diameter of the step (c) is 10-20 μm.
The mass ratio of A, B to glass chopped fibers in the step (c) is 3-4:1-1.5:1-2, and the mass of A, B is calculated by dry weight.
The invention also provides application of the special efficient halogen-free flame retardant for PBT prepared by the method in flame retardance of PBT resin.
The technical principle of the invention is as follows:
1. the phosphorus nitrogen halogen-free flame-retardant system utilizes the weak acidity of aluminum hypophosphite slurry and the combination of aluminum ions on the surfaces of aluminum hypophosphite particles and hydroxyl groups on organic alcohol to form aluminum alkoxide bonds, so that a trimethylol melamine prepolymer is evenly separated out and covered on the surfaces of aluminum hypophosphite molecules, a layer of organic melamine formaldehyde resin is coated on the surfaces of the aluminum hypophosphite molecules, then zinc borate reacts with free bare aluminum hypophosphite to generate a zinc hypophosphite/zinc aluminum hypophosphite blend for double-layer coating, so that the coating layer is more compact (shown in figure 1), the aluminum hypophosphite flame-retardant system has better compatibility with a high polymer substrate, and the influence of flame retardants on the mechanical properties of materials and the like is reduced. The problems of uneven mixing, poor dispersion and poor compatibility of powder in the base material and precipitation on the surface of the base material existing in the physical blending of the base material and the flame retardant are fundamentally solved; meanwhile, the flame retardant has better fluidity, improves the compatibility of the flame retardant in the PBT resin, improves the flame retardant performance by a phosphorus-nitrogen synergistic system, ensures the physical properties of the base material and widens the application range.
2. The reaction equation of the trimethylol melamine prepolymer prepared by the hydroxyl addition reaction of melamine and formaldehyde in alkaline environment is as follows:
the reaction equation for forming the coating layer is shown below by crosslinking the trimethylol melamine prepolymer on the surface of the aluminum hypophosphite molecule under the self acidity of the aluminum hypophosphite slurry.
3. The phosphorus-nitrogen halogen-free flame retardant slurry participates in the polycondensation reaction of the PBT, namely is inserted into the polymer, and the phosphorus-nitrogen synergistic efficient halogen-free flame retardant special for the PBT is obtained.
The beneficial effects of the invention are as follows: according to the invention, the PBT is prepared through esterification and polycondensation, and a phosphorus-nitrogen halogen-free flame retardant system is added in the reaction process to participate in the polycondensation of the PBT, namely, the phosphorus-nitrogen halogen-free flame retardant system is inserted in the polymer, so that the phosphorus-nitrogen synergistic efficient halogen-free flame retardant special for the PBT is obtained. The flame retardant is applied to PBT resin, and has good flame retardant effect, good mechanical property, good compatibility with a matrix, good dispersibility and good precipitation resistance.
Drawings
Fig. 1 is a comparative diagram of products before and after the reaction of the phosphorus-nitrogen halogen-free flame retardant, wherein a diagram a is aluminum hypophosphite particles before the reaction, and B diagram B is the double-layer coated phosphorus-nitrogen halogen-free flame retardant after the reaction.
Detailed Description
The present invention will be further described with reference to the following examples for better illustration of the technical scheme adopted by the present invention, but the embodiments of the present invention are not limited by the following examples.
Example 1
Adding terephthalic acid, 1, 4-butanediol and titanium sulfate in a molar ratio of 1:2:0.02 into a reactor provided with a stirrer, a condensation return pipe and a thermocouple, and reacting at 230 ℃ for 1.5 hours to obtain an esterified substance monomer A;
mixing and pulping aluminum hypophosphite and water according to a mass ratio of 1:5; adding water, formaldehyde and melamine into a reaction kettle in sequence according to the mass ratio of formaldehyde, melamine and water=2.5:1:10, regulating the pH value to be 8.5 by using a saturated potassium carbonate aqueous solution, starting steam heating and stirring, reacting for 1.5 hours at 75 ℃, slowly adding into aluminum hypophosphite slurry (the mass ratio of melamine to aluminum hypophosphite is 0.3:1), reacting for 4 hours, adding zinc borate (5% of the mass of aluminum hypophosphite) into the system, and reacting for 6 hours at 105 ℃ to obtain phosphorus-nitrogen halogen-free flame retardant slurry B;
adding the obtained B into the A, adding glass chopped fibers, wherein the mass ratio of A, B to the glass chopped fibers is 3:1:1, adding dimethylolpropionic acid (5% of the mass of the monomer A) for polycondensation, continuously reacting for 2 hours at the temperature of 240 ℃ to generate a polymerized PBT melt, and cooling, granulating and drying the polymerized melt to obtain the special efficient halogen-free flame retardant for the PBT.
Example 2
Adding terephthalic acid, 1, 4-butanediol and titanium sulfate in a molar ratio of 1:2:0.05 in a reactor provided with a stirrer, a condensation return pipe and a thermocouple, and reacting for 2 hours at 235 ℃ to obtain an esterified substance monomer A;
mixing and pulping aluminum hypophosphite and water according to a mass ratio of 1:8; adding water, formaldehyde and melamine into a reaction kettle in sequence according to the mass ratio of formaldehyde, melamine and water=2.8:1:10, regulating the pH value to be 8.0 by using a saturated potassium carbonate aqueous solution, starting steam heating and stirring, slowly adding into aluminum hypophosphite slurry (the mass ratio of melamine to aluminum hypophosphite is 0.25:1) after reacting for 2 hours at 80 ℃, adding zinc borate (8% of the mass of aluminum hypophosphite) into the system after reacting for 4 hours, and reacting for 6 hours at 100 ℃ to obtain phosphorus-nitrogen halogen-free flame retardant slurry B;
adding the obtained B into the A, adding glass chopped fibers, wherein the mass ratio of A, B to the glass chopped fibers is 3.5:1.2:1.3, adding a dicyclo imine ether compound (6% of the mass of a monomer A) for polycondensation reaction, continuously reacting for 2.5 hours at the temperature of 245 ℃ to generate a polymerized PBT melt, and cooling, granulating and drying the polymerized melt to obtain the special efficient halogen-free flame retardant for PBT.
Example 3
Adding terephthalic acid, 1, 4-butanediol and titanium sulfate in a molar ratio of 1:1.5:0.03 into a reactor provided with a stirrer, a condensation return pipe and a thermocouple, and reacting for 3 hours at 230 ℃ to obtain an esterified substance monomer A;
mixing and pulping aluminum hypophosphite and water according to a mass ratio of 1:5; adding water, formaldehyde and melamine into a reaction kettle in sequence according to the mass ratio of formaldehyde, melamine and water=2.6:1:12, regulating the pH value to be 9.0 by using a saturated potassium carbonate aqueous solution, starting steam heating and stirring, slowly adding into aluminum hypophosphite slurry (the mass ratio of melamine to aluminum hypophosphite is 0.32:1) after reacting for 2.5 hours at 75 ℃, adding zinc borate (10% of the mass of aluminum hypophosphite) into the system after reacting for 5 hours, and reacting for 5 hours at 105 ℃ to obtain phosphorus-nitrogen halogen-free flame retardant slurry B;
adding the obtained B into the A, adding glass chopped fibers, wherein the mass ratio of A, B to the glass chopped fibers is 4:1:1.5, adding dimethylolpropionic acid (8% of the mass of the monomer A) for polycondensation, continuously reacting for 2.5 hours at the temperature of 240 ℃ to generate a polymerized PBT melt, and cooling, granulating and drying the polymerized melt to obtain the special efficient halogen-free flame retardant for the PBT.
Test examples
The special efficient halogen-free flame retardants 1#, 2#, 3# and the composite flame retardants (melamine cyanurate and aluminum hypophosphite, which are compounded according to the mass ratio of 202:247) obtained in examples 1, 2 and 3 are respectively added into PBT resin (after being uniformly mixed in a high-speed mixer, a double-screw extruder is used for pelleting, glass fibers are added in the extrusion process, and flame-retardant PBT granules are prepared), and standard sample sheets are injected by an injection molding machine for testing and comparing flame retardance and mechanical properties, and the results are shown in the following table 1.
Table 1 comparison of product properties
Table 1 the results show that: the special efficient halogen-free flame retardant for PBT fully plays a flame retardant role through P-N synergism, realizes efficient flame retardance and improves the mechanical property of the PBT resin. On the premise of ensuring flame retardant property and mechanical property, the special efficient halogen-free flame retardant for PBT is good in compatibility in PBT resin, uniform in dispersion in a matrix, smooth in surface and free from precipitation phenomenon, and the compounded blending additive flame retardant is used for PBT resin, and is rough in surface and free from precipitation phenomenon.
Claims (8)
1. The preparation method of the efficient halogen-free flame retardant special for the PBT is characterized by comprising the following steps of:
(a) Adding terephthalic acid and 1, 4-butanediol into a reactor, adding a catalyst, and carrying out esterification reaction at 220-260 ℃ and normal pressure to obtain an esterified substance monomer;
(b) Sequentially adding water, formaldehyde and melamine into a reaction kettle, regulating pH to 8.0-9.0, reacting at 70-80 ℃ to obtain a trimethylol melamine pre-polymerization monomer solution, slowly adding the trimethylol melamine pre-polymerization monomer solution into aluminum hypophosphite slurry, uniformly separating out a pre-polymer by using the weak acidity of the aluminum hypophosphite slurry to cover the surface of aluminum hypophosphite molecules to form a coating layer, reacting for 2-6 hours, adding zinc borate into the system, reacting for 4-8 hours at 95-105 ℃ to react with free bare aluminum hypophosphite to generate zinc hypophosphite or a blend of zinc hypophosphite and aluminum hypophosphite, and carrying out double-layer coating to obtain phosphorus nitrogen halogen-free flame retardant slurry;
(c) Adding phosphorus-nitrogen halogen-free flame retardant slurry into an esterified monomer, adding a carboxyl chain extender and glass chopped fibers for polycondensation reaction, and then continuously reacting for 1-3 hours at 235-255 ℃ to generate qualified PBT melt with higher polymerization degree, and cooling, granulating and drying the polymerized melt to obtain the special efficient halogen-free flame retardant for PBT;
the mass ratio of formaldehyde, melamine and water in the step (b) is 1-3:0.95-1.05:5-15; the mass ratio of the aluminum hypophosphite to the water in the aluminum hypophosphite slurry is 1:4-9; the addition amount of the zinc borate is 5-15% of the mass of the aluminum hypophosphite; the mass ratio of the melamine to the aluminum hypophosphite to the zinc borate is 0.2-0.4:1:0.05-0.15.
2. The preparation method of the efficient halogen-free flame retardant special for the PBT, which is disclosed in claim 1, is characterized in that the catalyst in the step (a) is one or more of dibutyl tin, tetrabutyl titanate and titanium sulfate.
3. The method for preparing the efficient halogen-free flame retardant special for the PBT, which is disclosed in claim 1, is characterized in that the carboxyl chain extender in the step (c) is one or more of dimethylolpropionic acid, a dicyclo imine ether compound and terephthaloyl caprolactam.
4. The preparation method of the efficient halogen-free flame retardant special for PBT, as claimed in claim 1, wherein the glass chopped fiber diameter in the step (c) is 10-20 mu m.
5. The method for preparing the efficient halogen-free flame retardant special for the PBT, which is disclosed in claim 1, is characterized in that the molar ratio of terephthalic acid, 1, 4-butanediol and the catalyst in the step (a) is 1:1-2:0.02-0.06.
6. The preparation method of the efficient halogen-free flame retardant special for the PBT, which is disclosed in claim 1, is characterized in that the dry weight mass ratio of the esterified substance monomer, the phosphorus-nitrogen halogen-free flame retardant slurry and the glass chopped fiber in the step (c) is 3-4:1-1.5:1-2.
7. The high-efficiency halogen-free flame retardant special for PBT prepared by the method of any one of claims 1-6.
8. The application of the special efficient halogen-free flame retardant for PBT in flame retardance of PBT resin in claim 7.
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| CN112724618A (en) * | 2020-12-29 | 2021-04-30 | 金旸（厦门）新材料科技有限公司 | Low-cost halogen-free flame-retardant reinforced PBT (polybutylene terephthalate) material and preparation method thereof |
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Denomination of invention: A PBT specific high-efficiency halogen-free flame retardant and its preparation method Effective date of registration: 20231026 Granted publication date: 20230526 Pledgee: Bank of China Limited Jinan Tianqiao Branch Pledgor: Shandong Taixing New Materials Co.,Ltd. Registration number: Y2023370000121 |
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