CN109851852B - Low-corrosivity dialkyl phosphinate composition and application thereof - Google Patents
Low-corrosivity dialkyl phosphinate composition and application thereof Download PDFInfo
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Abstract
The invention discloses a low-corrosivity dialkyl phosphinate composition and application thereof, wherein the low-corrosivity dialkyl phosphinate composition comprises the following raw materials in percentage by weight: 99-99.999 wt% of a dialkylphosphinate mixture; 0.001-1 wt% of sulfate; the mixture of dialkylphosphinic salts comprises at least diethylphosphinic salt; the sulfate is selected from inorganic sulfate. When the low-corrosivity dialkyl phosphinate composition is used alone or in combination with other flame retardants, the degradation effect on polymers can be reduced, and the corrosion on equipment can be reduced.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to a low-corrosivity dialkyl phosphinate composition and application thereof.
Background
The dialkyl phosphinate has high phosphorus content and good flame retardance, and simultaneously, as alkyl is introduced into the molecular structure, compared with inorganic phosphinate, the dialkyl phosphinate has greatly improved hydrophobicity and thermal decomposition temperature, can not migrate and absorb moisture when applied to a high polymer material, can tolerate high processing temperature, can not cause the reduction of the insulating property of the material, has good compatibility with matrix resin, and can maintain the mechanical property of the matrix material. Due to the characteristics of the flame retardant, the flame retardant is widely applied to the fields of polymer flame retardance such as high flame retardance, high processing temperature, high shear strength and high CTI value.
The synthesis of dialkylphosphinic salts is generally carried out by alkylating inorganic hypophosphites by addition to olefins and converting them into organic phosphinic salts. The reaction mechanism is as follows: the free radical initiator is heated and decomposed in a medium to generate free radicals, the free radicals attack relatively active phosphorus-hydrogen bonds firstly to break the phosphorus-hydrogen bonds and generate hydrogen free radicals and hypophosphite free radicals, the hydrogen free radicals attack double bonds of olefin, the double bonds are opened and combined to form new alkyl free radicals, and the free radicals are easily coupled with the hypophosphite free radicals to finish addition. For example, chinese patent publication No. CN 1284787C discloses a method for preparing dialkylphosphinic salts, wherein the reaction is carried out in acetic acid, and the obtained product contains dialkylphosphinic salt products in addition to diethylphosphinic salt, and acetic acid residue. When the product is used as a flame retardant, acetic acid can cause polymer degradation and affect the mechanical properties of the material; in order to eliminate the effect of acetic acid, chinese patent publication No. CN 1660857B proposes that dialkylphosphinic salts undergo an addition reaction in water to obtain a multicomponent dialkylphosphinic salt mixture, and that water remains, and the residual water has a lower degradation effect on the polymer than acetic acid, thereby reducing the effect on the polymer.
Although the residual amount of impurities is reduced by the above-mentioned variation of the synthesis process, the degradation of the polymer is also reduced. However, due to the synthesis process and the physical properties of the aluminum diethylphosphinate, the flame retardant mixture synthesized by the method with the aluminum diethylphosphinate as the main component still shows strong acidity, degrades polymers and corrodes equipment, and particularly has larger negative effects when an application system needs to undergo a high-temperature heating process.
Therefore, there is a need to develop methods to reduce the negative effects of dialkylphosphinate flame retardant mixtures.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a dialkyl phosphinate composition, which can reduce the degradation effect on polymers and reduce the corrosion on equipment when used alone or in combination with other flame retardants.
The specific technical scheme is as follows:
the low-corrosivity dialkyl phosphinate composition comprises the following raw materials in percentage by weight:
99-99.999 wt% of a dialkylphosphinate mixture;
0.001-1 wt% of sulfate;
the dialkylphosphinate mixture includes at least diethylphosphinate;
the sulfate is selected from inorganic sulfates.
The present invention has been made in an extensive and intensive manner with a view to overcoming various disadvantages of the existing dialkylphosphinic salt mixtures. Aiming at the problems that the existing dialkyl phosphinate mixture system based on the diethyl phosphinate is easy to cause polymer degradation and has corrosion effect on equipment, the influence of other components on the dialkyl phosphinate mixture system is investigated, and the result shows that the problems can be better solved by adding a trace amount of sulfate into the dialkyl phosphinate mixture mainly based on the diethyl phosphinate.
The dialkylphosphinic salts have the following molecular structural formula:
wherein R is1、R2Independently selected from aliphatic saturated alkyl or unsaturated alkyl of C1-C10, or is aromatic radical; m is a metal element such as Al, Zn, Ca, Mg, Ti, Fe, Sn, Mn, Li, Na, K, etc.; m is 1 to 4.
In the invention, the dialkyl phosphinate mixture takes diethyl phosphinate as a main component and also comprises a secondary component, preferably, the secondary component comprises one or more of ethyl butyl phosphinate, butyl phosphinate, ethyl hexyl phosphinate, butyl hexyl phosphinate and hexyl phosphinate.
Further preferably, the dialkyl phosphinate mixture takes diethyl aluminum phosphinate as a main component, and further comprises one or more of ethyl butyl aluminum phosphinate, butyl aluminum phosphinate, ethyl hexyl aluminum phosphinate, butyl hexyl aluminum phosphinate and hexyl aluminum phosphinate.
The above-mentioned minor component may be a by-product produced during the synthesis of the diethyl phosphinate, or may be synthesized separately and added to the diethyl phosphinate. Preferably, the proportion of the secondary component is 0.01-10 wt%, more preferably 0.1-5 w%, and even more preferably 0.2-2.5 w%, based on the total weight of the mixture of dialkyl phosphinate salts.
The dialkyl phosphinate is characterized by high phosphorus content, good flame retardance, higher initial decomposition temperature, low water solubility, migration resistance and no moisture absorption, and is widely applied to engineering plastics such as nylon, PBT and the like at present, in particular to glass fiber reinforced engineering plastics. However, when the dialkyl phosphinate composition mainly containing diethyl phosphinate is applied to a polymer, the polymer is degraded, and the melt index of the polymer after the flame retardant is added can be obviously improved by testing the melt index of the polymer; secondly, the dialkylphosphinate compositions are somewhat corrosive to processing equipment, increasing the corrosive wear of equipment parts.
The inventor finds that trace sulfate is added into a dialkyl phosphinate mixture mainly containing dialkyl phosphinate, the trace sulfate can generate a synergistic effect with the dialkyl phosphinate flame-retardant mixture, the degradation of a flame-retardant system to polymers and the corrosion to equipment are reduced, meanwhile, the flame-retardant performance of the dialkyl phosphinate mixture is not reduced by the trace sulfate, other negative effects are not brought, and under the regulation and control of the trace sulfate, even if trace acetic acid exists, the degradation effect of the flame retardant composition to materials is still low, and the corrosion to the equipment is also reduced.
Preferably, the average particle size D50 of the dialkyl phosphinate mixture is 0.1-1000 μm. Too fine particle size is difficult to disperse, and too coarse particle size may reduce the mechanical properties of the material.
Preferably, the dialkylphosphinic salt mixture has a residual moisture content of 0.01 to 5wt%, more preferably 0.1 to 1wt%, and even more preferably 0.1 to 0.5 wt%, and controlling the moisture content at a lower level increases the drying cost, while too high a moisture content affects the flame retardant properties and degrades the polymer.
Preferably, in the low-corrosiveness dialkyl phosphinate composition, the raw material composition further comprises ethyl phosphinate.
The sulfate used in the invention is selected from inorganic sulfate, is salt formed by combining sulfate ions and various metal ions, and comprises at least one of sodium sulfate, aluminum sulfate, zinc sulfate, calcium sulfate, magnesium sulfate, potassium sulfate and ferric sulfate.
The inorganic sulfate is not combustible and has higher decomposition temperature, and more importantly, trace sulfate can be cooperated with the dialkyl phosphinate composition, so that the degradation effect of the dialkyl phosphinate composition on polymers is reduced, and the corrosion to equipment is reduced. However, the inorganic sulfate is not a flame retardant, and if the content is too high, the flame retardant performance is reduced, and the inorganic sulfate is compatible with a polymer matrix, and if the content is too high, the risk of migration and precipitation exists.
Preferably, the sulphate is selected from aluminium sulphate and/or sodium sulphate.
The invention also discloses the application of the dialkyl phosphinate composition with low corrosivity.
The flame retardant composition comprises the dialkyl phosphinate composition, and comprises the following raw materials in percentage by weight:
20-99.9 wt% of a dialkylphosphinate composition;
0.1-80 wt% of additive;
the additive comprises at least one of melamine derivatives, zinc-containing compounds and phosphites.
The melamine derivative comprises at least one of Melamine Cyanurate (MCA), Melamine Phosphate (MP) and melamine polyphosphate (MPP);
the zinc-containing compound comprises at least one of zinc oxide, zinc hydroxide, zinc borate and zinc stannate;
the phosphites include inorganic phosphites and organic phosphites; the inorganic phosphites include aluminum phosphite, zinc phosphite, calcium phosphite, magnesium phosphite, and the like, and the organic phosphites include aluminum methyl phosphite, aluminum ethyl phosphite, calcium methyl phosphite, magnesium methyl phosphite, and the like.
Preferably, the average particle diameter D50 of the flame retardant composition is 0.1-1000 μm.
The invention also discloses the dialkyl phosphinate composition and further application of the flame retardant composition in preparing flame-retardant polymers.
The polymer comprises a thermoplastic polymer and a thermosetting polymer, wherein the thermoplastic polymer comprises at least one of polyamide, polyester, polyolefin, polystyrene, TPE, TPU and TPEE; the thermosetting polymer comprises at least one of polyurethane, epoxy resin and unsaturated polyester.
The preparation of the flame-retardant polymer specifically comprises the following steps:
the dialkylphosphinate compositions, or alternatively the flame retardant compositions, are mixed with other additives in a mixer, homogenized in a polymer melt at relatively high temperature in a compounding assembly, and drawn into strands, cooled, chopped, etc.
The compounding assembly is preferably selected from a single screw extruder or a twin screw extruder.
Compared with the prior art, the invention has the following advantages:
the invention discloses a low-corrosivity dialkylphosphinate composition, which can generate a synergistic effect with a flame-retardant dialkylphosphinate mixture by adding trace sulfate into the dialkylphosphinate mixture, so that the degradation of a flame-retardant system to a polymer and the corrosion to equipment are reduced, and meanwhile, the flame-retardant performance of the dialkylphosphinate mixture is not reduced by the trace sulfate, and other negative effects are not brought; under the regulation of trace sulfate, even if the system also contains trace acetic acid, the degradation effect of the dialkyl phosphinate composition on materials is still low, and the corrosivity on equipment is also reduced.
The dialkyl phosphinate composition can be independently used for flame retardance of polymers, can also be used for flame retardance of polymers after being compounded with other common flame retardant additives, and can also achieve the effects of reducing the degradation effect on the polymers and reducing the corrosion on equipment.
Detailed Description
Raw materials:
(1) aluminum diethylphosphinate compositions (including aluminum diethylphosphinate, aluminum ethylbutylphosphinate, and aluminum ethylphosphinate in the ratios shown in table 1), Jiangsu Lisside New materials Co., Ltd;
(2) nylon 66, EPR27, platypodium;
(3) glass fiber, ECS301UW, Chongqing International composite Limited;
(4) antioxidant 1098, BASF;
(5) silicone, medium blue-morning light;
(6) aluminum sulfate, reagent grade, huadong medicine;
(7) sodium sulfate, reagent grade, huadong medicine
(8) MPP, Melapur 200, available from BASF;
(9) zinc borate, Firebake 500, available from Borax.
Example 1
(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 zone of the double-screw extruder at a preset temperature, adding a polymer base material 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 (4) performing injection molding on the dried material in an injection molding machine to obtain standard samples specified by various test standards, and performing performance test on the related materials. The following performance indicators are of primary concern:
flame-retardant
Tested according to the UL94V0 test standard.
② migration resistance test
The prepared flame-retardant glass fiber reinforced engineering 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.
(iii) 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.
Mechanical property test
The lower the impact strength, the more significant the degradation of the polymer matrix, as measured by ASTM D256.
Fifthly, 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 formulation of the dialkylphosphinate compositions in this example is shown in Table 1, and the components and test results for preparing flame retardant polymers are shown in Table 2.
Example 2
The procedure was as in example 1, except that aluminum sulfate was changed to sodium sulfate. The proportions of the dialkylphosphinate compositions are shown in Table 1, and the components and test results for preparing the flame retardant polymers are shown in Table 2.
Example 3
The procedure was as in example 1, except that the sulfate was changed to a mixed sulfate having two kinds of sulfate. The proportions of the dialkylphosphinate compositions are shown in Table 1, and the components and test results for preparing the flame retardant polymers are shown in Table 2.
Example 4
The procedure was the same as in example 1 except that a small amount of acetic acid was added to the composition. The proportions of the dialkylphosphinate compositions are shown in Table 1, and the components and test results for preparing the flame retardant polymers are shown in Table 2.
Comparative example 1
The procedure was carried out as in example 1, except that aluminum sulfate was not used. The proportions of the dialkylphosphinate compositions are shown in Table 1, and the components and test results for preparing the flame retardant polymers are shown in Table 2.
Comparative example 2
The procedure was carried out as in example 1, except that no sulfate was added and a small amount of acetic acid was added. The proportions of the dialkylphosphinate compositions are shown in Table 1, and the components and test results for preparing the flame retardant polymers are shown in Table 2.
Comparative example 3
The procedure was carried out as in example 1, except that the aluminum sulfate content was adjusted to 1.5%. The proportions of the dialkylphosphinate compositions are shown in Table 1, and the components and test results for preparing the flame retardant polymers are shown in Table 2.
Comparative example 4
The procedure was carried out as in example 2, except that the sodium sulfate content was adjusted to 1.5%. The proportions of the dialkylphosphinate compositions are shown in Table 1, and the components and test results for preparing the flame retardant polymers are shown in Table 2.
TABLE 1
TABLE 2
Claims (10)
1. The low-corrosivity dialkyl phosphinate composition is characterized by comprising the following raw materials in percentage by weight:
99-99.999 wt% of a dialkylphosphinate mixture;
0.001-1 wt% of sulfate;
the dialkylphosphinate mixture includes at least diethylphosphinate;
the sulfate is selected from inorganic sulfate, and the inorganic sulfate comprises at least one of sodium sulfate, aluminum sulfate, zinc sulfate, calcium sulfate, magnesium sulfate, potassium sulfate and ferric sulfate.
2. The low corrosiveness dialkylphosphinate composition of claim 1, wherein the dialkylphosphinate mixture further comprises one or more of ethylbutylphosphinate, butylbutylphosphinate, ethylhexylphosphinate, butylhexylphosphinate, and hexylhexylhexylphosphinate.
3. The low corrosiveness dialkylphosphinate composition of claim 1, wherein the dialkylphosphinate mixture has an average particle size D50 of 0.1 to 1000 μm and a residual moisture content of 0.01 to 5 wt.%.
4. The low corrosiveness dialkylphosphinate composition of claim 1, wherein the feedstock composition further comprises ethylphosphonite.
5. A flame retardant composition, comprising the dialkylphosphinic salt composition according to any one of claims 1 to 4, wherein the flame retardant composition comprises the following raw materials in percentage by weight:
20-99.9 wt% of a dialkylphosphinate composition;
0.1-80 wt% of additive;
the additive comprises at least one of melamine derivatives, zinc-containing compounds and phosphites.
6. The flame retardant composition of claim 5, wherein:
the melamine derivative comprises at least one of melamine cyanurate, melamine phosphate and melamine polyphosphate;
the zinc-containing compound comprises at least one of zinc oxide, zinc hydroxide, zinc borate and zinc stannate;
the phosphites include inorganic phosphites and organic phosphonites.
7. Use of the dialkylphosphinate composition according to any one of claims 1 to 4 in the preparation of a flame retardant polymer.
8. Use of a flame retardant composition according to claim 5 or 6 for the preparation of a flame retardant polymer.
9. Use according to claim 7 or 8, wherein the polymer comprises a thermoplastic polymer and a thermosetting polymer;
the thermoplastic polymer comprises at least one of polyamide, polyester, polyolefin, TPE, TPU and TPEE;
the thermosetting polymer comprises at least one of polyurethane, epoxy resin and unsaturated polyester.
10. Use according to claim 9, wherein the polyolefin comprises polystyrene.
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| CN112662171B (en) * | 2020-12-01 | 2022-10-14 | 聚石化学(苏州)有限公司 | Halogen-free flame-retardant reinforced polyamide composite material and preparation method and application thereof |
| CN114539621B (en) * | 2022-03-10 | 2022-10-21 | 江苏利思德新材料有限公司 | Phosphorus-aluminum salt-containing complex and preparation method and application thereof |
| JP2023177156A (en) * | 2022-06-01 | 2023-12-13 | 日華化学株式会社 | Flame-retardant composition, and flame-retardant synthetic leather using the same |
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