CN107857883B - Phosphorus-nitrogen-containing high-molecular flame retardant with char-forming function and preparation method and application thereof - Google Patents
Phosphorus-nitrogen-containing high-molecular flame retardant with char-forming function and preparation method and application thereof Download PDFInfo
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- CN107857883B CN107857883B CN201711174866.4A CN201711174866A CN107857883B CN 107857883 B CN107857883 B CN 107857883B CN 201711174866 A CN201711174866 A CN 201711174866A CN 107857883 B CN107857883 B CN 107857883B
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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
- 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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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- 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
Abstract
The invention discloses a macromolecular flame retardant containing phosphorus and nitrogen elements and having a char-forming function, which is an insoluble and infusible cross-linked polymer, and the cross-linked point structure is shown as the following formula (I). The invention develops a novel macromolecular flame retardant integrating acid source, gas source and char formation functions, and the macromolecular flame retardant has the characteristics of good flame retardance, high molecular weight, migration resistance, no moisture absorption, high temperature resistance, no influence on the mechanical properties of matrix materials and the like. Can be used independently, can also be used in cooperation with phosphorus-nitrogen flame retardants in materials such as nylon, polyester, polyurethane and the like;
Description
Technical Field
The invention relates to the technical field of high-molecular flame retardants, in particular to a high-molecular flame retardant containing phosphorus and nitrogen elements and having a carbon forming function, 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 addition, 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 the selectable space is not large. 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 low water solubility high temperature resistant charring compound is particularly important, and the phosphorus nitrogen element is introduced into the charring compound, so that the acid source, the gas source and the charring function of the flame retardant are integrated, the cooperativity of the phosphorus nitrogen halogen-free flame retardant system can be improved, the flame retardant efficiency is improved, the using amount is reduced, the mechanical property of the base material cannot be influenced, and the requirements on material processing equipment and process are reduced.
Disclosure of Invention
Aiming at the problems of the existing halogen-free flame retardant system, the invention develops a novel macromolecular flame retardant integrating an acid source, a gas source and a char forming function. The high molecular flame retardant has the characteristics of good flame retardance, high molecular weight, migration resistance, no moisture absorption, high temperature resistance, no influence on the mechanical property of a base material and the like. Can be used alone or in cooperation with phosphorus-nitrogen flame retardant, and can be applied to materials such as nylon, polyester, polyurethane and the like.
The specific technical scheme is as follows:
a high-molecular flame retardant containing phosphorus and nitrogen elements and having a char-forming function 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 phosphorus-nitrogen-containing high-molecular flame retardant with the char-forming function comprises the following steps:
the material is trihydroxyethyl isocyanurate and methyl phosphonic acid with equivalent weight, and the material is prepared after polycondensation reaction.
The preparation of the high-molecular flame retardant is that a trihydroxy-containing compound and dibasic acid are used as monomers to perform polycondensation reaction under the condition of equivalent weight to form a polyester compound with a cross-linking structure and a carbon forming 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 disadvantages of the conventional halogen-free flame retardant system and to develop a novel flame retardant, 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 inventors propose that the polyhydroxy characteristic of the existing char-forming agent is utilized, which has multiple functionality, and esterification condensation is performed with acid to form a thermosetting compound having a cross-linked structure, which still has a char-forming effect, while esterification allows hydroxyl groups in the molecular structure to be esterified without hydrophilicity, and the thermosetting compound having a cross-linked structure has a high decomposition temperature, and third, the thermosetting polymer has a non-melting characteristic, 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 finds out through research that the phosphorus and nitrogen element is introduced into the molecular structure of the flame retardant, and the contained phosphorus and nitrogen element of the polyester can be an acid source and a gas source besides the carbon forming effect to form intramolecular synergy, so that the phosphorus-containing dibasic acid can be considered. In addition, the inventor also finds that the condensation of the trihydroxyethyl isocyanurate and the methylphosphonic acid can obtain a thermosetting polyester condensate with a crosslinking structure, the molecular structure contains phosphorus and nitrogen elements and has a carbon forming effect, the water solubility is low, and the thermal decomposition temperature is high.
The preparation method of the phosphorus-nitrogen-containing high-molecular flame retardant with the char-forming function comprises the following steps:
(1) enabling equivalent trihydroxyethyl isocyanurate and methyl phosphonic acid to react for 4-8 hours at 150-220 ℃ under the action of a phase transfer catalyst to prepare an esterified prepolymer;
(2) vacuumizing and heating to 260-280 ℃, and carrying out polycondensation and solidification on the esterified prepolymer and then 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, belongs to a trifunctional compound, and the methylphosphonic acid belongs 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.
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 obtained after 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 prepared by the method has good char forming 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 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 taking the polymer flame retardant and the optionally added phosphorus-nitrogen flame retardant as flame retardants comprises the following raw materials in percentage by 100 percent of total mass:
the base material is selected from nylon, polyester or polyurethane;
the phosphorus-nitrogen flame retardant is selected from diethyl aluminum hypophosphite.
Still more preferably, the polymeric flame retardant has a nitrogen content of 10.4% and a phosphorus content of 11.5%. Further application tests show that the high-molecular flame retardant can obtain excellent flame retardant effect when being applied to the base materials singly or after being compounded with the phosphorus-nitrogen flame retardant, and can respectively meet the flame retardant standards of UL94V0(1.0mm) and VW-1.
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 alone or in combination with phosphorus-nitrogen flame retardant, and can be applied to nylon, polyester, polyurethane and other materials.
Detailed Description
Example 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 ℃ to be melted, then 2.7 g of tetrabutylammonium bromide and 288g (3 mol) of methyl phosphonic acid are added, the mixture is stirred strongly, the temperature is increased from 150 ℃ to 210 ℃ within 6 hours, water in the reaction process is discharged, the condensation is measured, the temperature is kept at 210 ℃ for 1 hour, the temperature is reduced to 150 ℃, the melt is discharged to a metal tray, and a light yellow brittle solid is obtained after the melt is cooled, the melting point ranges from 100-120 ℃, and the residual acid value is 7 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 phosphorus content of the polymeric flame retardant prepared in this example is: 10.5%, nitrogen content: 10.1 percent (the content of phosphorus and nitrogen is actually measured value and is slightly lower than the theoretical calculation value in the specification), the solubility is less than 0.1 percent, and the 1 percent weight loss decomposition temperature is 320 ℃.
Unless otherwise specified, the flame retardants in the following examples are all the polymeric flame retardants prepared in this example.
Example 2 flame retardant application in 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 flame retardant property is tested to reach UL94V 1 (thickness of 1 mm). And testing the migration and precipitation conditions under the conditions of constant temperature and constant humidity, and displaying no migration as a result.
Example 3 application of aluminum diethylphosphinate composite 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 flame retardant property is tested to reach UL94V0 (thickness of 1 mm). The flame retardant is compounded with diethyl aluminum hypophosphite, so that a better flame retardant grade can be achieved under the condition of less addition amount, and better cooperativity is achieved. And testing the migration and precipitation conditions under the conditions of constant temperature and constant humidity, and displaying no migration as a result.
Example 4 flame retardant application to glass fiber reinforced PA6,6
The materials are prepared according to the formula table in the table 1, all the components are uniformly mixed in a high-speed mixer, the uniformly mixed materials are extruded and granulated through a double-screw extruder, standard sample strips are prepared, and the flame retardant property is tested. It can reach UL94V 2(1mm thick). And testing the migration and precipitation conditions under the conditions of constant temperature and constant humidity, and displaying no migration as a result.
Example 5 application of compounding with aluminum diethylphosphinate to glass fiber reinforced PA6,6
The materials are prepared according to the formula table in the table 1, all the components are uniformly mixed in a high-speed mixer, the uniformly mixed materials are extruded and granulated through a double-screw extruder, standard sample strips are prepared, and the flame retardant property is tested. It can reach UL94V0(1 mm thick). The flame retardant is compounded with diethyl aluminum hypophosphite, so that a better flame retardant grade can be achieved under the condition of less addition amount, and better cooperativity is achieved. And testing the migration and precipitation conditions under the conditions of constant temperature and constant humidity, and displaying no migration as a result.
Example 6 application of flame retardant to TPU Cable Material
The preparation method comprises the following steps of preparing materials according to a formula table in table 1, uniformly mixing all components in a high-speed mixer, extruding and granulating the uniformly mixed materials through a double-screw extruder, preparing the cable on cable equipment, and testing the flame retardant property. VW-1 can be achieved, and no molten drop exists. And testing the migration and precipitation conditions under the conditions of constant temperature and constant humidity, and displaying no migration as a result.
Example 7 compounding with diethyl aluminum hypophosphite for use in TPU cable materials
The preparation method comprises the following steps of preparing materials according to a formula table in table 1, uniformly mixing all components in a high-speed mixer, extruding and granulating the uniformly mixed materials through a double-screw extruder, preparing the cable on cable equipment, and testing the flame retardant property. VW-1 can be achieved, and no molten drop exists. The flame retardant is compounded with diethyl aluminum hypophosphite, can achieve the same flame retardant effect under the condition of less addition amount, and shows better cooperativity. And testing the migration and precipitation conditions under the conditions of constant temperature and constant humidity, and displaying no migration as a result.
TABLE 1
Claims (9)
1. A high molecular flame retardant containing phosphorus and nitrogen elements and having a carbon forming function 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 phosphorus-nitrogen-containing high-molecular flame retardant with the char-forming function is to use trihydroxyethyl isocyanurate and methyl phosphonic acid with equivalent weight as raw materials and prepare the flame retardant after polycondensation reaction.
2. The polymeric flame retardant containing phosphorus and nitrogen elements and having char-forming function according to claim 1, wherein the nitrogen content is 10.4% and the phosphorus content is 11.5%.
3. The phosphorus-nitrogen-containing polymeric flame retardant with a char-forming function according to claim 1, wherein the preparation method of the phosphorus-nitrogen-containing polymeric flame retardant with a char-forming function comprises:
(1) enabling equivalent trihydroxyethyl isocyanurate and methyl phosphonic acid to react for 4-8 hours at 150-220 ℃ under the action of a phase transfer catalyst to prepare an esterified prepolymer;
(2) vacuumizing and heating to 260-280 ℃, performing polycondensation and solidification on the esterified prepolymer, and crushing to obtain the phosphorus-nitrogen-containing element and the high-molecular flame retardant with the char forming function.
4. The polymeric flame retardant containing phosphorus and nitrogen elements and having char-forming function according to claim 3, wherein in step (1), said phase transfer catalyst is selected from quaternary ammonium salts.
5. The polymeric flame retardant containing phosphorus and nitrogen elements and having char-forming function according to claim 3, wherein in the step (2), vacuum is applied until the vacuum degree is not higher than 50 KPa.
6. The phosphorus-nitrogen-containing polymeric flame retardant having a char-forming function according to claim 3, wherein in the step (2), the powder is pulverized to an average particle diameter D50<5 μm.
7. The use of the phosphorus-nitrogen-containing element and the polymer flame retardant with a char-forming function according to claim 1 or 2 in flame retardation of polymer materials.
8. The use according to claim 7, wherein the polymeric material is selected from at least one of polyester, nylon, and polyurethane.
9. The use of claim 8, wherein the phosphorus and nitrogen-containing polymeric flame retardant with a char-forming function is applied to the polymeric material in combination with diethyl aluminum hypophosphite.
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Address after: No. 88, Zhonghua East Road, Guanzhuang, Houbao Community, Tianmushan Street, Jiangyan District, Taizhou City, Jiangsu Province 225529 Patentee after: Jiangsu LISIDE New Materials Co.,Ltd. Address before: 225529 Houbao village, Guanzhuang, Shengao Town, Jiangyan District, Taizhou City, Jiangsu Province Patentee before: Jiangsu Liside New Material Co.,Ltd. |