CN108997611B - Method for improving high-temperature thermal stability of melamine derivative flame retardant by using metal alkyl phosphite, and product and application thereof - Google Patents
Method for improving high-temperature thermal stability of melamine derivative flame retardant by using metal alkyl phosphite, and product and application thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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- C08L2201/22—Halogen free composition
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Abstract
The invention discloses a method for improving high-temperature thermal stability of melamine derivative flame retardants by using metal alkylphosphonite, which comprises the steps of adding metal alkylphosphonite into raw materials; the addition amount of the metal alkylphosphonite is 0.1-40% based on the total weight of the melamine derivative flame retardant; the structural formula of the metal alkyl phosphite is shown as the following formula (I) or the following formula (II), wherein R is selected from aryl or linear aliphatic alkyl with 1-6 carbon atoms, and Me is selected from zinc, calcium or magnesium. The method disclosed by the invention enables the melamine derivative to have high thermal decomposition temperature, avoids the defects of decomposition, degradation of matrix polymer, migration, corrosion of equipment and the like of the flame retardant, simultaneously maintains the performance of the flame retardant, has flame retardant synergy with other flame retardants, and widens the application field of the flame retardant.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to a method for improving high-temperature thermal stability of a melamine derivative flame retardant by using an alkyl phosphite metal salt, a melamine derivative flame retardant with high-temperature thermal stability prepared by using the method and application of the flame retardant.
Background
The melamine derivative is generally used as a flame retardant or a synergistic flame retardant due to high nitrogen content, can be used alone or in combination with a phosphorus-containing flame retardant particularly in the field of halogen-free flame retardance, or is condensed with a phosphorus-containing compound to have a high synergistic flame retardance effect, and is widely used in flame retardance of polymer materials at present. Melamine derivative flame retardants, typically represented by Melamine Cyanurate (MCA) and melamine polyphosphate (MPP), are used in large amounts in the flame retardancy of materials such as nylon and polyester.
However, such compounds typically have a problem in use, that they are easily decomposed during high temperature processing, particularly under the action of high temperature and screw shearing force, and the decomposition of the flame retardant easily causes the following problems: the main points are as follows: firstly, the acidic components generated by decomposition can cause the degradation of the matrix polymer, and the obvious phenomenon is that the melting index of the material is large and easy to discolor, so that the mechanical property of the material is greatly influenced, and particularly the impact property of the material is greatly reduced; secondly, the acidic components generated by pyrolysis corrode metal parts of the equipment, the parts need to be replaced after a certain time, the agent cost is increased, and the production efficiency is reduced; thirdly, gaseous substances such as ammonia gas are generated by decomposition, so that a die head generates larger smoke in the processing process, and the processing environment and the health of workers are influenced; fourthly, the generated micromolecular substances are decomposed, the risk of precipitation is accelerated, the material has deposits on a mould after a product with a certain modulus is injected in the injection molding process, the appearance of the product can be influenced due to the deposits, the mould needs to be stopped and cleaned at the moment, the production efficiency can be reduced, and the precipitation can cause the flame retardant to migrate to the surface of the product, so that the flame retardant is unevenly distributed and lost, the flame retardance of the material is finally disabled, and the potential safety hazard exists.
In summary, the use of melamine derivative flame retardants has problems of color, generation of toxic gases, easy precipitation, corrosion, degradation, discoloration, reduction in mechanical properties of materials, and the like, some are fatal and cannot be used, and some are cost-increasing and efficiency-reducing. Despite these problems, there is no good solution at present and no new flame retardant alternative to melamine derivatives appears. Therefore, there is a need to find a way to increase the thermal stability of melamine derivatives during high temperature processing.
Although a large number of commercial heat stabilizers or antioxidant products for polymers exist, the effect is not obvious for melamine derivatives, and a large number of organic antioxidants such as hindered phenol, phosphate ester and the like have limited self temperature resistance and are firstly destroyed in a high-temperature environment to lose the effect.
Disclosure of Invention
The invention provides a method for improving the high-temperature thermal stability of melamine derivative flame retardants by utilizing alkyl phosphite metal salts, aiming at the defects of the existing melamine derivatives widely applied to halogen-free flame retardance of high polymer materials.
The specific technical scheme is as follows:
a method for improving the high-temperature thermal stability of melamine derivative flame retardants by using metal alkylphosphonite comprises the steps of adding metal alkylphosphonite into raw materials;
the addition amount of the metal alkylphosphonite is 0.1-40% based on the total weight of the melamine derivative flame retardant;
the metal alkylphosphonite salt has a structural formula shown as the following formula (I) or the following formula (II):
in the formula, R is selected from aryl or linear aliphatic alkyl with 1-6 carbon atoms, and Me is selected from zinc, calcium or magnesium.
Tests show that the alkyl phosphite metal salt with the structure can greatly reduce the decomposition of the melamine derivative flame retardant, protect matrix polymer from being degraded by flame retardant decomposers, simultaneously has flame retardant synergistic effect with the melamine derivative flame retardant, and can improve flame retardant efficiency, and the alkyl phosphite metal salt has high temperature resistance and does not change color at high temperature. The melamine derivative flame-retardant system with the synergic thermal stability of the alkyl phosphite can be independently applied to glass fiber reinforced nylon or polyester, can also be compounded with a diethylphosphinate flame retardant for use, has high flame retardance, thermal stability and migration resistance, and can reach the flame retardant standard of UL94V0 without color change at high temperature by utilizing the halogen-free flame-retardant glass fiber reinforced nylon and polyester prepared by the flame-retardant system.
The present invention will be described in detail below.
The present invention aims to overcome the defect of poor thermal stability of the existing melamine derivative flame retardants applied in the field of halogen-free flame retardancy, and the inventors have conducted extensive and intensive studies. Various schemes for improving the high temperature resistance are investigated aiming at the problem that the existing melamine derivative flame retardant is easy to decompose during high-temperature processing, thereby causing the series of problems of the processing process, the performance degradation of composite materials and the like, and the result shows that a small amount of alkyl phosphite is mixed in the melamine derivative flame retardant, so that the high-temperature thermal stability of the melamine derivative can be obviously improved, and a series of problems caused by high-temperature thermal decomposition are avoided.
The chemical structural formula of the melamine derivative is shown as the following formula (III):
the melamine derivative generally includes a melamine condensation product, a salt obtained by reacting melamine with an acid selected from at least one of phosphoric acid, pyrophosphoric acid, polyphosphoric acid, cyanuric acid, a salt obtained by reacting a melamine condensation product with an acid, and the like.
The melamine has high nitrogen content and good flame retardance, but because of high water solubility and slightly low decomposition temperature, the melamine is rarely directly applied to the flame retardance of high polymer materials. Melamine is generally reacted with acidic compounds to form melamine salts, which reduce water solubility and increase decomposition temperature, such compounds prepared from melamine precursors are known as melamine derivatives. The melamine derivative also has high nitrogen content and good flame retardance, and can be used as a flame retardant alone or in combination with other components. Because the melamine derivatives have low water solubility and high decomposition temperature, the melamine derivatives are usually some melamine derivatives in the flame retardant application of high molecular materials, and Melamine Cyanurate (MCA), Melamine Phosphate (MP), melamine pyrophosphate (MPP), melamine polyphosphate (MPP) and the like are mostly applied.
However, when the melamine derivatives are applied to polymers with higher processing temperature, such as nylon and polyester, the processing temperature exceeds 250 ℃, and the melamine derivatives are easily decomposed under the action of screw shear force, gaseous substances such as ammonia gas and acidic substances are released, smoke is generated in the processing process, the acidic substances can accelerate the degradation of a polymer matrix, the material melt index is increased, the mechanical property is reduced, and meanwhile, the acidic substances corrode metal parts of equipment at high temperature to strengthen the equipment, so that the equipment is damaged, and a series of problems are caused.
The inventor finds that a small amount of alkyl phosphite is added into the melamine derivative flame retardant to play a role in thermal stability, so that the problems of high-temperature decomposition of the melamine derivative and degradation of a matrix polymer are solved, the problems of corrosion, precipitation, discoloration, reduction of mechanical properties and the like are avoided, and the flame retardant property of the system is not influenced.
The alkyl phosphite metal salt with the structural formula shown as the formula (I) or the formula (II) has high thermal decomposition temperature, does not change color at high temperature, can be used for synergistically retarding flame with the melamine derivative, keeps higher flame retardance of the melamine derivative, and has low water solubility and migration resistance.
Preferably, said R is selected from methyl or ethyl; the smaller the molecular weight of the R group, the higher the phosphorus content, the more advantageous the flame retardancy.
The preparation method of the metal alkylphosphonite salt comprises the following steps:
(1) hydrolyzing alkyl phosphite ester under an acidic condition to prepare alkyl phosphite ester;
(2) reacting alkyl phosphorous acid with metal hydroxide in an aqueous medium under an acidic condition at a high pressure of 150-180 ℃;
(3) filtering, washing and drying the suspension at 200-240 ℃, and crushing to a certain particle size.
The prepared metal alkyl phosphite has high thermal decomposition temperature, can act synergistically with diethyl hypophosphite, and has low water solubility and migration resistance.
The metal salt of an alkylphosphonous acid is a white powder, preferably, in the particle size range: the average particle size 20< D50<50 μm can be well dispersed in the polymer matrix.
According to the research, in order to obtain the melamine derivative flame retardant with high heat stability, the amount of the alkyl phosphorous acid metal salt added is as follows: when the total weight of the melamine derivative flame retardant is 0.1-40%, the melamine derivative flame retardant has good high-temperature thermal stability and does not affect the flame retardant performance of the melamine derivative flame retardant.
Preferably, the alkyl phosphite metal salt is selected from methyl phosphite metal salt, and the addition amount is 4-20% of the total weight of the melamine derivative flame retardant; more preferably, the addition amount is 8-14%.
By using the method, the melamine derivative flame retardant with high-temperature thermal stability can be prepared only by blending the raw materials with special proportion and special composition.
The high-temperature heat stability effect of alkyl phosphite on a melamine derivative flame retardant is evaluated, a compound of the alkyl phosphite and the melamine derivative flame retardant in proportion is applied to a high polymer material to prepare a flame-retardant high polymer material, and the decomposition of the melamine derivative at high temperature and a series of problems caused by the decomposition are comprehensively evaluated by comparing the color, the melt index, the impact strength, the flame-retardant performance, the precipitation performance, the corrosion performance and the like of a test material.
Therefore, the invention also discloses a halogen-free flame-retardant glass fiber reinforced material which comprises a base material, a glass fiber reinforcement body, a flame retardant and other processing aids.
The flame retardant comprises the melamine derivative flame retardant having high temperature thermal stability;
the melamine derivative flame retardant with high temperature thermal stability is a functional auxiliary agent for endowing a high polymer material with flame retardant performance, and accounts for 10-30 wt% of the whole material system to meet related standard requirements.
Preferably, the flame retardant also comprises a diethyl hypophosphite flame retardant which is used for compounding and flame retarding with the melamine derivative flame retardant with high-temperature thermal stability.
Preferably, the substrate is selected from nylon or polyester. The nylon base material includes aliphatic polyamide, semi-aromatic polyamide, such as nylon 6, nylon 66, nylon MXD6, nylon 12, and high temperature nylon such as nylon 46, 4T, 6T, 9T, 10T, 12T; the polyester substrate includes PBT and PET.
In order to prepare the halogen-free flame-retardant glass fiber reinforced material, a flame-retardant system needs to be uniformly dispersed in the material. And (3) melting and blending the components in an extruder through a double-screw extruder with a glass fiber adding port and a flame retardant powder feeding port, and extruding and granulating.
Compared with the prior art, the invention has the following advantages:
the invention discloses a method for improving the high-temperature thermal stability of a melamine derivative flame retardant by utilizing alkyl phosphite, which is characterized in that the melamine derivative flame retardant with a special proportion and a specific composition is mixed with the alkyl phosphite to prepare the melamine derivative with high thermal decomposition temperature, so that the defects of decomposition, degradation of matrix polymers, migration, corrosion of equipment and the like of the flame retardant are avoided, and meanwhile, the performance of the flame retardant is also maintained; the halogen-free flame-retardant glass fiber reinforced plastic can be used as a halogen-free flame-retardant system of glass fiber reinforced engineering plastics to prepare novel halogen-free flame-retardant glass fiber reinforced special materials applied to the field of electric and electronics.
Detailed Description
Raw materials:
(1) MPP, Melapur 200 from BASF
(2) Aluminum methylphosphite, Jiangsu Risk New Material Co., Ltd
(3) Nylon 66, EPR27, Pingshan horse
(4) Glass fiber, ECS301UW, Chongqing International composite Co., Ltd
(5) Diethyl aluminum hypophosphite 8003, Jiangsu Risk New materials GmbH
(6) Antioxidant 1098, BASF
(7) Silicone, medium-blue-morning light
Example 1
The compound flame-retardant system is applied to glass fiber reinforced engineering plastics, and the performance of the flame retardant is inspected according to the following steps and test methods.
1. Compounding of halogen-free flame retardant systems
And (3) adding the components of the compound flame-retardant system and other auxiliary agents which are weighed in advance according to the proportion into a high-speed stirring machine, starting high-speed stirring, stirring for 10min, completing the mixing of the halogen-free flame-retardant system, and discharging.
2. Extrusion granulation of materials
Setting the temperature of each area of the double-screw extruder at a preset temperature, adding a polymer matrix from a hopper after the temperature is stabilized for 20min, adding glass fibers through a glass fiber adding port, feeding flame retardant powder through a powder feeding hole, starting a host and a feeder, and finishing the extrusion granulation of the material. And (4) sending the granulated materials into a storage bin through an air conveying system, and drying.
3. Application and testing of materials
And (3) injecting the dried material into an injection molding machine to obtain standard samples specified by various test standards, and testing the performance of the related material. The following performance indicators are of primary concern:
A. flame-retardant
Tested according to the UL94V0 test standard.
B. Migration resistance test
The prepared plastic sample is placed in a constant temperature and humidity box, the temperature is set to be 85 ℃, the relative humidity is 85%, and the state of the surface of the sample after 168 hours is observed visually.
C. Corrosion test
A metal block is arranged on a die head, a high-temperature material is contacted with the metal block in the die head, and the loss of the metal after 25Kg material granulation is tested, wherein the higher the loss is, the worse the corrosion resistance is. Corrosion was considered acceptable if the amount of corrosion was < 0.1%.
D. Mechanical Property test
The lower the impact strength, the more significant the degradation of the polymer matrix, as measured by ASTM D256.
E. Melt index test
And (3) testing conditions are as follows: 280 ℃/2.16Kg, the degree of degradation of the polymers was compared by melt finger size.
The materials and the mixture ratio in the example 1 are shown in the table 1, and the test results of the obtained materials are shown in the table 1.
Example 2
The procedure was as in example 1, except that the amount of aluminum methylphosphite was adjusted, the materials and the compounding ratio were as shown in Table 1, and the results of the obtained materials are as shown in Table 1.
Example 3
The procedure was as in example 1, except that the amount of aluminum methylphosphite was adjusted, the materials and the compounding ratio were as shown in Table 1, and the results of the obtained materials are as shown in Table 1.
Example 4
The aluminothermally stable melamine polyphosphate (MPP) methylphosphite was used in conjunction with aluminium diethylphosphinate in glass fiber reinforced nylon and the material results obtained are shown in Table 1.
Comparative example 1
The procedure was as in example 1, except that no aluminum methylphosphite was used. The other materials and the mixture ratio are shown in table 1, and the obtained material results are shown in table 1.
Comparative example 2
The procedure was carried out as in example 4, except that no aluminum methylphosphite was used. The other materials and the mixture ratio are shown in table 1, and the obtained material results are shown in table 1.
TABLE 1
Claims (6)
1. The application of the alkyl phosphite metal salt for improving the high-temperature thermal stability of the melamine derivative flame retardant is characterized in that the alkyl phosphite metal salt is added into the raw materials;
the addition amount of the metal alkylphosphonite is 0.1-40% based on the total weight of the melamine derivative flame retardant;
the metal alkylphosphonite salt has a structural formula shown as the following formula (I) or the following formula (II):
in the formula, R is selected from aryl or linear aliphatic alkyl with 1-6 carbon atoms, and Me is selected from zinc, calcium or magnesium.
2. Use of a metal salt of an alkyl phosphite according to claim 1 for increasing the high temperature thermal stability of melamine derivative flame retardants, wherein R is selected from methyl or ethyl.
3. The use of the metal alkylphosphonite salt as claimed in claim 1 for improving the high-temperature thermal stability of a melamine derivative flame retardant, wherein the average particle diameter D50 of the metal alkylphosphonite salt is 20 to 50 μm.
4. Use of a metal salt of an alkyl phosphorous acid according to claim 1 for improving the high temperature thermal stability of a melamine derivative flame retardant, wherein the melamine derivative flame retardant is selected from at least one of a melamine condensation product, a salt obtained by reacting melamine with an acid, a salt obtained by reacting a melamine condensation product with an acid;
the acid is at least one selected from phosphoric acid, pyrophosphoric acid, polyphosphoric acid and cyanuric acid.
5. Use of a metal salt of an alkyl phosphorous acid according to claim 1 for increasing the high temperature thermal stability of a melamine derivative flame retardant, wherein the melamine derivative flame retardant is selected from at least one of melamine cyanurate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate.
6. Use of a metal alkylphosphonite salt as claimed in any of claims 1, 4 or 5 for improving the high temperature thermal stability of a melamine derivative flame retardant, wherein said metal alkylphosphonite salt is selected from the group consisting of aluminum methylphosphonite;
the addition amount of the metal alkylphosphonite is 4-20% of the total weight of the melamine derivative flame retardant.
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| CN102171225A (en) * | 2008-12-18 | 2011-08-31 | 科莱恩金融(Bvi)有限公司 | Method for the production of alkylphosphonic acids, esters, and salts by oxidizing alkylphosphonous acids, and use thereof |
| CN103154110A (en) * | 2010-10-09 | 2013-06-12 | 科莱恩金融(Bvi)有限公司 | Flame retardant-stabilizer combination for thermoplastic polymers |
| CN107936055A (en) * | 2017-11-22 | 2018-04-20 | 浙江大学 | A kind of organic phosphorous acid aluminium and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102171225A (en) * | 2008-12-18 | 2011-08-31 | 科莱恩金融(Bvi)有限公司 | Method for the production of alkylphosphonic acids, esters, and salts by oxidizing alkylphosphonous acids, and use thereof |
| CN103154110A (en) * | 2010-10-09 | 2013-06-12 | 科莱恩金融(Bvi)有限公司 | Flame retardant-stabilizer combination for thermoplastic polymers |
| CN107936055A (en) * | 2017-11-22 | 2018-04-20 | 浙江大学 | A kind of organic phosphorous acid aluminium and its preparation method and application |
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Effective date of registration: 20230719 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: No. 88, Zhonghua East Road, Guanzhuang, Houbao Community, Tianmushan Street, Jiangyan District, Taizhou City, Jiangsu Province 225529 Patentee before: Jiangsu LISIDE New Materials Co.,Ltd. Patentee before: ZHEJIANG University |
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