CN107698770B - Migration-resistant high-molecular flame-retardant charring agent containing phosphorus and nitrogen elements as well as preparation method and application thereof - Google Patents
Migration-resistant high-molecular flame-retardant charring agent containing phosphorus and nitrogen elements as well as preparation method and application thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Abstract
The invention discloses a migration-resistant high-molecular flame-retardant charring agent containing phosphorus and nitrogen elements, which is an insoluble and infusible cross-linked polymer, wherein the structure of a cross-linking point is shown as the following formula (I); the invention develops a migration-resistant high-molecular flame-retardant char-forming agent containing phosphorus and nitrogen elements, and the high-molecular flame-retardant char-forming agent has the characteristics of good char forming property, high molecular weight, migration resistance, no moisture absorption, high temperature resistance, no influence on the mechanical properties of a base material and the like. Can be used in conjunction with phosphorus-nitrogen flame retardant for nylon, polyester, polyurethane and other materials;
Description
Technical Field
The invention relates to the technical field of high-molecular flame retardants, in particular to a migration-resistant high-molecular flame-retardant charring agent containing phosphorus and nitrogen elements and a preparation method and application thereof.
Background
Most of high polymer materials are flammable, but in many application fields, flame retardant requirements are provided for the materials, such as the fields of electrical appliances and electronics, wires and cables, furniture, buildings, automotive interiors, textiles and the like, namely, the flammable and combustible high polymer materials are required to achieve flame retardant. Flame retarding of flammable polymeric materials is generally achieved by the addition of flame retardants to the materials. Traditionally, a brominated flame retardant is taken as a main flame retardant, but a great deal of research finds that after the flame-retardant high polymer material added with the brominated flame retardant is burnt in a fire, a great amount of dense smoke and toxic substances are generated, so that people suffocate and secondary damage is caused; in addition, when these wastes are recovered at high temperature, carcinogenic substances such as dioxin are easily generated, and environmental pollution is caused. Therefore, in view of the problems of the halogen-based flame retardant, the development of a novel halogen-free flame retardant has become a hotspot in recent years, and a large amount of novel halogen-free flame retardants appear and are well applied in a plurality of application fields.
Among halogen-free flame retardants, phosphorus-nitrogen flame retardants are most important, and such flame retardants have high flame retardant efficiency, low addition level, and do not affect the mechanical properties of the base material. Among the phosphorus-nitrogen-based flame retardants, according to their flame retardant mechanism, the phosphorus-nitrogen-based flame retardants generally include three functional components: an acid source, a carbon source, and a gas source. The acid source is generally used as a catalyst for high-temperature dehydration, and can rapidly dehydrate polymers into carbon, mainly containing phosphorus compounds; the gas source compound can be decomposed at high temperature to generate non-combustible gas, such as nitrogen, ammonia gas, carbon dioxide and the like, the high-temperature decomposition reaction is usually an endothermic reaction, the temperature of a combustion object can be reduced, the combustion is not facilitated, secondly, a large amount of non-combustible gas is generated, the oxygen concentration can be reduced, meanwhile, the gas can also enable a matrix polymer to generate a foaming effect, a formed foaming layer also has a barrier effect, the diffusion of the combustion is not facilitated, and the flame retardant effect is achieved, and the gas source compound is usually a nitrogen-containing compound, such as melamine, MCA and the like in triazine compounds; the carbon source is a char forming agent, which is easy to dehydrate and carbonize at high temperature, the high-temperature dehydration process is an endothermic process, which can reduce the temperature of the combustion products, the generated water vapor can dilute the concentration of oxygen, and the formed carbon layer is a compact layer, which can play the role of heat insulation and oxygen isolation, and avoid the development of combustion, usually polyhydroxy compounds. The three components are usually three substances which are mutually cooperated, and the mutual proportion is adjusted according to the flame retardant effect and the difference of the base materials, so that the high-efficiency flame retardant is realized. If the substances with these functions are independent of each other, good dispersion is needed when the flame retardant is applied to a high polymer material, and the components are uniformly dispersed in a matrix high polymer material according to a proportion, which puts high requirements on dispersion equipment.
In a phosphorus-nitrogen halogen-free flame retardant system, an acid source and a gas source compound develop relatively mature, a large number of commercial products exist, but the carbon source compound still has more problems and has little choice. The carbon source compound is usually a polyol such as pentaerythritol, dipentaerythritol, etc., but one of the greatest problems with these polyhydroxy carbon source compounds is water solubility. The water solubility can lead the flame retardant component to absorb moisture, reduce the insulativity of the material and limit the application in the field of electric and electronic fields; most of the polymer matrix materials are nonpolar materials, so that the water solubility of the flame-retardant component can cause the flame-retardant component to migrate and separate out to the surface, thereby affecting the appearance on one hand, and causing the non-uniform distribution of the flame-retardant component in the material on the other hand, gradually reducing the flame-retardant effect and affecting the lasting flame-retardant performance of the material; some high molecular compounds which can be used as a carbon forming agent, such as thermoplastic polyester compounds, have the problem of compatibility with a matrix material, so that the mechanical property of the material is greatly reduced and the application value is lost; the polyol or low molecular weight polyol also has a low thermal decomposition temperature and is therefore not suitable for use in substrates having a high processing temperature, such as nylon, polyester, and the like. Therefore, the development of the low-water-solubility high-temperature-resistant carbonized compound is particularly important, and the introduction of phosphorus and nitrogen elements into the carbonized compound can improve the cooperativity of a phosphorus and nitrogen halogen-free flame retardant system, improve the flame retardant efficiency, reduce the using amount and simultaneously can not influence the mechanical properties of the matrix material.
Disclosure of Invention
Aiming at the defects of the existing carbon forming component, the invention develops a migration-resistant high-molecular flame-retardant carbon forming agent containing phosphorus and nitrogen elements, and the high-molecular flame-retardant carbon forming agent has the characteristics of good carbon forming property, high molecular weight, migration resistance, no moisture absorption, high temperature resistance, no influence on the mechanical property of a matrix material and the like. Can be used in conjunction with phosphorus-nitrogen flame retardant for nylon, polyester, polyurethane and other materials.
The specific technical scheme is as follows:
a migration-resistant high-molecular flame-retardant charring agent containing phosphorus and nitrogen elements is an insoluble and infusible cross-linked polymer, and the structure of a cross-linking point is shown as the following formula (I):
the preparation method of the migration-resistant high-molecular flame-retardant charring agent containing the phosphorus and the nitrogen comprises the following steps:
the material is prepared by taking equivalent trihydroxyethyl isocyanurate and mixed dibasic acid as raw materials and carrying out polycondensation reaction;
the mixed dibasic acid comprises terephthalic acid and methyl phosphonic acid.
The preparation of the high molecular flame-retardant charring agent takes trihydroxy-containing compound and dibasic acid as monomers, and the polycondensation reaction is carried out under the condition of equivalent weight to form polyester compound with a cross-linking structure, and the polyester compound has a charring function; and because hydroxyl groups do not exist in the molecular structure, the water solubility is very low; meanwhile, as a thermosetting compound, the material has the characteristic of non-melting and non-dissolving, only one filler is used in the matrix material, and the mechanical property of the matrix material is not influenced; meanwhile, the molecule contains phosphorus and nitrogen elements, so that the flame retardant has the functions of an acid source and an air source, and the flame retardant property is further improved.
The present invention will be described in detail below.
The present invention has been made in an effort to solve various drawbacks of the conventional flame retardant char-forming agents and to develop a novel flame retardant char-forming agent, and the inventors have made extensive and intensive studies. The existing carbon forming agents are all polyhydroxy compounds and mainly comprise small molecular substances, and the substances as the carbon forming agents have good carbon forming effects, but have the defects of strong water solubility and low decomposition temperature, and are limited in a plurality of fields. However, from the viewpoint of the mechanism of char formation, the char-forming agent cannot be separated from the hydroxyl compound, and it is naturally thought that the hydroxyl group is esterified with some carboxyl group-containing compounds to reduce the amount of the hydroxyl group and increase the decomposition temperature, whereas the molecular weight needs to be increased to increase the thermal decomposition temperature, and if a thermoplastic high molecular weight compound is formed, there is a problem of compatibility with the matrix material during application, and the mechanical properties are reduced.
Based on the foregoing analysis, the inventor proposes that the polyhydroxy characteristic of the existing char-forming agent is utilized, the char-forming agent has multiple functionality, and the char-forming agent and the acid undergo esterification condensation to form a thermosetting compound with a cross-linked structure, so that the hydroxyl group in the molecular structure is esterified without hydrophilicity, and the thermosetting compound with the cross-linked structure has a high decomposition temperature, and thirdly, the thermosetting polymer has the characteristic of non-melting, and has no compatibility problem with the matrix material during application, and does not affect the mechanical properties of the material.
There are many molecular structure schemes that can satisfy the above analysis, for example, polyhydroxy compounds can be selected from pentaerythritol containing tetrahydroxy group, dipentaerythritol containing hexahydroxy group, and trihydroxy triethyi isocyanurate, which are condensed with dibasic acid, but among these polyhydroxy compounds, trihydroxy ethyl isocyanurate can improve flame retardancy because it contains nitrogen atoms in its molecular structure, and thus trihydroxy ethyl isocyanurate is selected; the dibasic acid can be selected from various kinds, including aromatic carboxylic acid, aliphatic carboxylic acid, dibasic organic phosphoric acid and the like. The inventor of the patent finds that phosphorus and nitrogen elements are introduced into the molecular structure of the carbon forming agent, the carbon forming agent contains the phosphorus and nitrogen elements which can generate a synergistic effect on flame retardance besides the carbon forming effect, and the addition amount of an acid source and an air source can be reduced in the flame retardance application, so that the phosphorus-containing dibasic acid can be considered. The inventor of the present invention finds that the condensation of trihydroxyethyl isocyanurate and mixed dibasic acid of terephthalic acid and methyl phosphonic acid can obtain thermosetting polyester condensate with a cross-linking structure, wherein the molecular structure contains phosphorus and nitrogen elements and has a carbon forming effect, low water solubility and high thermal decomposition temperature.
The preparation method of the migration-resistant high-molecular flame-retardant charring agent containing the phosphorus and the nitrogen elements comprises the following specific steps:
(1) the method comprises the following steps of (1) reacting trihydroxyethyl isocyanurate and mixed dibasic acid with equivalent weight for 4-8 hours at 150-220 ℃ under the action of a phase transfer catalyst to obtain an esterified prepolymer;
in the mixed dibasic acid, the molar ratio of terephthalic acid to methyl phosphonic acid is 1-5: 1;
(2) vacuumizing and heating to 260-280 ℃, performing polycondensation and solidification on the esterified prepolymer, and crushing to obtain the high-molecular flame-retardant charring agent containing phosphorus and nitrogen and having a charring function.
The trihydroxyethyl isocyanurate has three hydroxyl groups and belongs to a trifunctional compound, and the terephthalic acid and the methylphosphonic acid both belong to dibasic acid and a difunctional compound, and can form a thermosetting polyester condensate with a crosslinking structure under equivalent weight. The condensation reaction is carried out in 2 steps, firstly, polyester prepolymer is prepared at a lower temperature, and then, polycondensation and solidification are carried out at a high temperature, so as to obtain the macromolecular flame-retardant charring agent.
In the preparation of the prepolymer in the step (1), a phase transfer catalyst is used in order to accelerate the reaction rate. Preferably, the phase transfer catalyst is selected from quaternary ammonium salts, such as tetrabutylammonium bromide.
Meanwhile, the water generated in the esterification reaction needs to be drained in time. To prevent discoloration of the prepolymer, the reaction may be carried out in a nitrogen atmosphere.
In the step (2), the prepolymer is subjected to high-temperature polycondensation and solidification, and high vacuum and high-temperature conditions are required. Preferably, the vacuum is pumped to the vacuum degree not higher than 50 KPa. The reaction may be carried out in an oven or using a high-power kneader having a stirring function.
The flame-retardant char-forming agent obtained by polycondensation and solidification is a block, and in order to be added to a base material, it is necessary to conduct a pulverization treatment by using a mechanical pulverization device while controlling the average particle diameter D50 of the flame retardant to be less than 5 μm.
The macromolecular flame-retardant charring agent prepared by the method has a good charring effect, contains phosphorus and nitrogen elements in a molecular structure, has good flame-retardant efficiency, does not contain hydroxyl in the molecular structure due to the cross-linking structure, has low water solubility and high thermal decomposition temperature, and can be applied to flame retardance of macromolecular materials. Especially in matrix materials with higher processing temperatures, such as nylon, polyester, polyurethane, etc.
Preferably, the high molecular flame-retardant charring agent can be compounded with a phosphorus-nitrogen flame retardant, such as organic hypophosphite and the like, and is jointly applied to materials such as nylon, polyester, polyurethane and the like to realize a good flame-retardant effect.
Further preferably, the flame-retardant polymer material prepared by using the polymer flame-retardant char-forming agent and the phosphorus-nitrogen flame retardant as a flame-retardant system comprises the following raw materials in 100% by total mass:
the base material is selected from nylon, polyester or polyurethane;
the phosphorus-nitrogen flame retardant is selected from diethyl aluminum hypophosphite.
Still further preferably, in the polymeric flame-retardant charring agent, the nitrogen content is 8.5-9.2%, and the phosphorus content is 1.6-5.1%. Further application tests show that the macromolecular flame-retardant charring agent with the phosphorus and nitrogen content can further reduce the dosage of the phosphorus and nitrogen flame retardant compounded with the macromolecular flame-retardant charring agent.
Compared with the prior art, the invention has the following advantages:
the invention provides a macromolecular flame retardant containing phosphorus and nitrogen elements and having a char-forming function, which integrates an acid source, a gas source and the char-forming function into a whole and has excellent flame retardant property; hydroxyl groups do not exist in the molecular structure, so that the water solubility is very low; the molecular structure has a cross-linking structure, the decomposition temperature is high, the material is not melted or dissolved, the problem of compatibility with a matrix material does not exist during application, and the mechanical property of the material is not influenced. Can be used in conjunction with phosphorus-nitrogen flame retardant for nylon, polyester, polyurethane and other materials.
Detailed Description
Example 1 terephthalic acid to methylphosphonic acid molar ratio of 2:1
522 g (2 mol) of trihydroxyethyl isocyanurate is added into a 1L flask, nitrogen is introduced for protection, the trihydroxyethyl isocyanurate is heated to 150 ℃ for melting, then 2.7 g of tetrabutylammonium bromide, 332 g (2 mol) of terephthalic acid and 96g (1 mol) of methylphosphonic acid are added, the mixture is stirred vigorously, the temperature is increased from 150 ℃ to 210 ℃ within 6 hours, water in the reaction process is discharged, the mixture is measured by condensation, the temperature is kept at 210 ℃ for 1 hour, the temperature is reduced to 150 ℃, the melt is discharged to a metal tray, and after cooling, a white brittle solid is obtained, the melting point ranges from 100 to 120 ℃, and the residual acid value is 6 mg KOH/g.
And (3) placing the prepolymer and the tray into a vacuum oven, vacuumizing, keeping the vacuum degree at 50KPa, heating to 270 ℃, keeping for 2 hours, completing solidification, cooling and discharging. The material is comminuted to an average particle size D50<5 microns for use.
After analysis: the high molecular flame retardant char-forming agent (marked as char-forming agent-1) prepared in this example had a phosphorus content of: 3.1%, nitrogen content: 8.5% (the phosphorus and nitrogen contents are actually measured values and are slightly lower than the theoretical calculation values in the specification), the solubility is less than 0.1%, and the 1% weight loss decomposition temperature is 330 ℃.
Example 2 terephthalic acid to methylphosphonic acid molar ratio of 4:1
The procedure was carried out as in example 1, except that the molar ratio of terephthalic acid to methylphosphonic acid was changed to 4: 1.
After analysis: the high molecular flame retardant char-forming agent (marked as char-forming agent-2) prepared in this example had a phosphorus content of: 1.7%, nitrogen content: 8.4%, solubility < 0.1%, 1% weight loss decomposition temperature 325 ℃.
Example 3 application of char-forming agent-1 to glass fiber reinforced PBT
The materials are prepared according to the formula table in the table 1, the components are uniformly mixed in a high-speed mixer, the uniformly mixed materials are extruded and granulated through a double-screw extruder to prepare standard sample strips, and the standard sample strips are tested for flame retardant property, can reach UL 94V 0 (thickness of 1 mm), and have no molten drops. The migration precipitation is tested under the conditions of constant temperature and constant humidity, and the result shows that no migration exists. Migration and precipitation can be found by using a conventional compound system of diethyl aluminum hypophosphite and MPP.
Example 4 application of char-forming agent-2 to glass fiber reinforced PBT
The materials are prepared according to the formula table in the table 1, the components are uniformly mixed in a high-speed mixer, the uniformly mixed materials are extruded and granulated through a double-screw extruder to prepare standard sample strips, and the standard sample strips are tested for flame retardant property, can reach UL 94V 0 (thickness of 1 mm), and have no molten drops. With char-forming agent-2, more diethyl aluminum hypophosphite was needed to achieve the same flame retardant effect. The migration precipitation is tested under the conditions of constant temperature and constant humidity, and the result shows that no migration exists. Migration and precipitation can be found by using a conventional compound system of diethyl aluminum hypophosphite and MPP.
EXAMPLE 5 application of char-forming agent-1 to glass fiber reinforced PA6,6
Preparing materials according to the formula table in table 1, uniformly mixing the components in a high-speed mixer, extruding and granulating the uniformly mixed materials through a double-screw extruder, preparing standard sample strips, and testing the flame retardant property. Can reach UL 94V 0(1mm thickness) without molten drops. The migration precipitation is tested under the conditions of constant temperature and constant humidity, and the result shows that no migration exists. Migration and precipitation can be found by using a conventional compound system of diethyl aluminum hypophosphite and MPP.
EXAMPLE 6 application of char-forming agent-2 to glass fiber reinforced PA6,6
Preparing materials according to the formula table in table 1, uniformly mixing the components in a high-speed mixer, extruding and granulating the uniformly mixed materials through a double-screw extruder, preparing standard sample strips, and testing the flame retardant property. Can reach UL 94V 0(1mm thickness) without molten drops. With char-forming agent-2, more diethyl aluminum hypophosphite was needed to achieve the same flame retardant effect. The migration precipitation is tested under the conditions of constant temperature and constant humidity, and the result shows that no migration exists. Migration and precipitation can be found by using a conventional compound system of diethyl aluminum hypophosphite and MPP.
Example 7 application of char-forming agent-1 in TPU Cable Material
The formula is prepared according to the formula table in table 1, the components are uniformly mixed in a high-speed mixer, the uniformly mixed materials are extruded and granulated through a double-screw extruder, the cable is prepared on cable equipment, and the flame retardant property is tested. VW-1 can be achieved, and no molten drop exists. The migration precipitation is tested under the conditions of constant temperature and constant humidity, and the result shows that no migration exists. Whereas with conventional diethyl aluminum hypophosphite, a droplet was found.
EXAMPLE 8 application of char-forming agent-2 in TPU Cable Material
The formula is prepared according to the formula table in table 1, the components are uniformly mixed in a high-speed mixer, the uniformly mixed materials are extruded and granulated through a double-screw extruder, the cable is prepared on cable equipment, and the flame retardant property is tested. VW-1 can be achieved, and no molten drop exists. With char-forming agent-2, more diethyl aluminum hypophosphite was needed to achieve the same flame retardant effect. The migration precipitation is tested under the conditions of constant temperature and constant humidity, and the result shows that no migration exists. Whereas with conventional diethyl aluminum hypophosphite, a droplet was found. TABLE 1
Claims (8)
1. A migration-resistant high-molecular flame-retardant charring agent containing phosphorus and nitrogen elements is characterized by being an insoluble and infusible cross-linked polymer, wherein the cross-linking point structure is shown as the following formula (I):
the preparation method of the migration-resistant high-molecular flame-retardant charring agent containing the phosphorus and the nitrogen elements comprises the following steps:
(1) the method comprises the following steps of (1) reacting trihydroxyethyl isocyanurate and mixed dibasic acid with equivalent weight for 4-8 hours at 150-220 ℃ under the action of a phase transfer catalyst to obtain an esterified prepolymer;
in the mixed dibasic acid, the molar ratio of terephthalic acid to methyl phosphonic acid is 1-5: 1;
(2) vacuumizing and heating to 260-280 ℃, performing polycondensation and solidification on the esterified prepolymer, and crushing to obtain the migration-resistant high-molecular flame-retardant charring agent containing the phosphorus and the nitrogen.
2. The migration-resistant polymer flame retardant char-forming agent containing phosphorus and nitrogen elements according to claim 1, wherein the nitrogen content is 8.5-9.2%, and the phosphorus content is 1.6-5.1%.
3. The migration-resistant polymer flame retardant char-forming agent containing phosphorus and nitrogen elements according to claim 1, wherein in step (1), the phase transfer catalyst is selected from quaternary ammonium salts.
4. The migration resistant polymer flame retardant char-forming agent containing phosphorus and nitrogen element according to claim 1, wherein in step (2), vacuum is applied until the vacuum degree is not higher than 50 KPa.
5. The migration-resistant polymeric flame retardant char-forming agent containing phosphorus and nitrogen elements according to claim 1, wherein in step (2), the pulverized material is pulverized to an average particle size D50<5 μm.
6. The use of the migration-resistant polymeric flame retardant char-forming agent containing phosphorus and nitrogen elements according to claim 1 or 2 in flame retardancy of polymeric materials.
7. The use according to claim 6, wherein the polymeric material is selected from at least one of polyester, nylon, and polyurethane.
8. The application of the flame-retardant charring agent as claimed in claim 7, wherein the migration-resistant polymer flame-retardant charring agent containing phosphorus and nitrogen elements is compounded with diethyl aluminum hypophosphite and applied to the polymer material.
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| CN104211986A (en) * | 2014-08-25 | 2014-12-17 | 华东理工大学 | Crosslinking macromolecular flame-retardant charring agent containing isocyanurate and preparation method of crosslinking macromolecular flame-retardant charring agent |
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