CN109054450B - Surface modified magnesium hydroxide and preparation method and application thereof - Google Patents
Surface modified magnesium hydroxide and preparation method and application thereof Download PDFInfo
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
The invention relates to the technical field of processing of magnesium hydroxide flame retardants, and discloses surface-modified magnesium hydroxide and a preparation method and application thereof, wherein the method comprises the following steps: (1) carrying out first contact on a modifier I and magnesium hydroxide; (2) carrying out second contact on a modifier II and the product obtained in the step (1); the modifier I is castor oil; the modifier II is phosphate or organic hypophosphorous acid metal salt. The method uses the castor oil and the phosphate compound for double coating, has simple process, easy operation, high controllability and simple equipment, has no pollution in the whole process, and meets the requirements of energy conservation and environmental protection; in addition, the surface modified magnesium hydroxide prepared by the method improves the compatibility and the thermal stability of the magnesium hydroxide and a high polymer material, and can obviously improve the mechanical property, the processing fluidity and the like of a high polymer compound.
Description
Technical Field
The invention relates to the technical field of processing of magnesium hydroxide flame retardants, in particular to surface-modified magnesium hydroxide and a preparation method and application thereof.
Background
The magnesium hydroxide fire retardant is widely applied to various organic materials, can prevent flame from burning and reduce the harm of harmful gas in the burning process of objects, and has the fire retardant principle that the temperature of the surface of a polymer is reduced and the decomposition of the polymer is inhibited by releasing crystal water through thermal decomposition and absorbing a large amount of heat.
The magnesium hydroxide has low flame-retardant efficiency, and the common addition amount of the magnesium hydroxide needs to account for more than 60% of the total mass of the compound to ensure that the flame retardance of the polymer material meets the requirement. Therefore, the mechanical property and the mechanical property of the polymer are greatly influenced, and meanwhile, the magnesium hydroxide has strong polarity and poor compatibility with matrix resin, so that the magnesium hydroxide needs to be modified to improve the compatibility and the processing fluidity of the magnesium hydroxide and the polymer material.
At present, the modification of magnesium hydroxide is mainly divided into surfactant modification, microcapsule coating and coupling agent modification.
The microcapsule coating process is complex and the implementation process is not environment-friendly, and modification implementation processes of surfactants and coupling agents commonly used in the industry at present, such as silane coupling agents, titanate coupling agents and the like, are simple but have limited improvement on the performance of magnesium hydroxide.
CN104371374A discloses that the lignosulfonate modified magnesium hydroxide is used, and the lignosulfonate and the magnesium hydroxide are placed in an internal mixer to be heated to 100-200 ℃ and subjected to constant-temperature internal mixing for 0.5-3 hours, so that the defects of high preparation temperature, high energy consumption and the like exist.
CN103965656A discloses that magnesium hydroxide is modified by using sodium dodecyl sulfate, oxidized polyethylene wax and the like which meet the requirements of an emulsifier and an auxiliary agent, the modification process is complex, and the controllability is poor.
Therefore, in order to overcome the problems of poor compatibility, thermal stability and processing fluidity of magnesium hydroxide and polymer materials in the prior art, the development and research of a method for modifying the surface of magnesium hydroxide are of great significance.
Disclosure of Invention
The invention aims to overcome the problems that the mechanical property and the mechanical property of a polymer are influenced by the high addition amount of magnesium hydroxide and the compatibility, the thermal stability and the processing fluidity of the magnesium hydroxide and a polymer material are poor in the prior art, and provides surface modified magnesium hydroxide and a preparation method and application thereof, wherein the method uses the castor oil and phosphate compound for double coating, and has the advantages of simple process, easiness in operation, high controllability, simple equipment, no pollution in the whole process and capability of meeting the requirements of energy conservation and environmental protection; in addition, the surface modified magnesium hydroxide prepared by the method improves the compatibility and the thermal stability of the magnesium hydroxide and a high polymer material, and can obviously improve the mechanical property, the processing fluidity and the like of a high polymer compound.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing surface-modified magnesium hydroxide, wherein the method comprises the steps of:
(1) carrying out first contact on a modifier I and magnesium hydroxide;
(2) carrying out second contact on a modifier II and the product obtained in the step (1);
wherein the modifier I is castor oil;
wherein the modifier II is phosphate or organic hypophosphorous acid metal salt.
The second aspect of the invention provides the surface modified magnesium hydroxide prepared by the preparation method.
The third aspect of the invention provides the application of the surface modified magnesium hydroxide as a flame retardant in the processing of polymer composite materials.
Through the technical scheme, the castor oil mainly comprises cis-ricinoleic acid, palmitic acid, stearic acid, linoleic acid, linolenic acid, dihydroxystearic acid and the like, can react with strong polar hydroxyl on the surface of magnesium hydroxide, and is coated on the surface of the magnesium hydroxide to improve the compatibility of the magnesium hydroxide and a polymer; the phosphate and/or organic metal hypophosphite has the characteristics of low smoke, no toxicity, no halogen and the like, and generates a cross-linked solid substance or a carbonized layer with a more stable structure when being heated, and the formation of the carbonized layer can prevent the polymer from further pyrolysis on the one hand and prevent the thermal decomposition products in the carbonized layer from entering a gas phase to participate in a combustion process on the other hand, so that the phosphate and/or organic metal hypophosphite is used as a modifier to be coated on the surface of magnesium hydroxide to form a double flame-retardant structure, and the flame-retardant efficiency is improved.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of surface modified magnesium hydroxide, which comprises the following steps:
(1) carrying out first contact on a modifier I and magnesium hydroxide;
(2) carrying out second contact on a modifier II and the product obtained in the step (1);
wherein the modifier I is castor oil;
wherein the modifier II is phosphate or organic hypophosphorous acid metal salt.
According to the invention, the main components of castor oil are cis-ricinoleic acid, palmitic acid, stearic acid, linoleic acid, linolenic acid and dihydroxystearic acid, and the inventor discovers through a large number of scientific experiments that: the castor oil can react with the strong polar hydroxyl on the surface of the magnesium hydroxide and is coated on the surface of the magnesium hydroxide to improve the compatibility of the castor oil with the polymer.
According to the present invention, the phosphate may be one or more of triethyl phosphate, trimethyl phosphate and phosphite; the organic hypophosphorous acid metal salt is one or more of diethyl aluminum hypophosphite, poly (triallyl isocyanurate) aluminum hypophosphite and poly (triallyl isocyanurate) zinc hypophosphite.
According to the present invention, the inventors of the present invention have unexpectedly found that: the phosphate or the organic hypophosphorous acid metal salt has the characteristics of low smoke, no toxicity, no halogen and the like, and generates a cross-linked solid substance or a carbonized layer with a more stable structure when being heated, and the formation of the carbonized layer can prevent the polymer from further pyrolysis on the one hand and prevent the thermal decomposition products in the carbonized layer from entering a gas phase to participate in the combustion process on the other hand, so that the phosphate and/or the organic hypophosphorous acid metal salt are used as a modifier to be coated on the surface of magnesium hydroxide to form a double flame-retardant structure, and the flame-retardant efficiency is.
According to the present invention, the conditions of the first contact may include: the stirring speed is 2000-5000r/min, the temperature is 40-110 ℃, and the time is 10-60 min; the conditions of the second contacting may include: the stirring speed is 2000-5000r/min, the temperature is 40-110 ℃, and the time is 10-60 min.
Preferably, the conditions of the first contacting include: the stirring speed is 2000-5000r/min, the temperature is 40-110 ℃, and the time is 10-60 min; the conditions of the second contacting include: the stirring speed is 3000-4000r/min, the temperature is 70-90 ℃, and the time is 30-60 min; in the present invention, it is preferable that the conditions of the first contact and the conditions of the second contact are the same.
Preferably, in the step (1), before the first contact, the magnesium hydroxide may be pretreated, i.e., stirred in a high-speed stirrer, to make the magnesium hydroxide more uniformly dispersed, wherein the stirring rate and the stirring time are not particularly limited, and for example, the magnesium hydroxide may be stirred at a stirring rate of 2000-.
According to the present invention, in the step (2), the second contacting may be performed in the presence of a solvent; preferably, the solvent is absolute ethyl alcohol and/or distilled water; more preferably, the solvent is used in an amount of 1 to 5% by weight, preferably 3 to 5% by weight, based on the amount of the magnesium hydroxide.
According to the invention, the particle size of the magnesium hydroxide can be 325-5000 meshes, preferably 1000-5000 meshes, more preferably 3000-5000 meshes, and most preferably 3000-4500 meshes. According to the invention, the modifier I can be used in an amount of 0.3 to 8% by weight, preferably 0.3 to 3% by weight, based on the amount of magnesium hydroxide; the modifier II may be used in an amount of 0.3 to 10% by weight, preferably 0.3 to 3% by weight, based on the amount of the magnesium hydroxide.
According to the invention, the modifier I can be brought into a first contact with the magnesium hydroxide in a dropwise manner; in the invention, the first contact is carried out in a dripping mode, so that the castor oil can react with the strong polar hydroxyl on the surface of the magnesium hydroxide and can be coated on the surface of the magnesium hydroxide to improve the compatibility of the castor oil and the polymer.
According to the invention, the modifier II can be in second contact with the reactant after the step (1) in a dropwise manner; in the invention, the second contact is carried out in a dropwise manner, so that the phosphate and/or organic hypophosphorous acid metal salt is coated on the surface of the magnesium hydroxide to form a flame-retardant structure as a modifier, and the flame-retardant efficiency is increased.
In the invention, the magnesium hydroxide can be better coated on the surface to form a double flame-retardant structure by controlling the dosage and the dropping rate of the modifier I and the modifier II, so that the flame-retardant efficiency is increased.
According to the invention, the dropping rate may be from 0.1 to 2ml/min, preferably from 0.5 to 1 ml/min.
In a second aspect, the invention provides a surface modified magnesium hydroxide prepared by the preparation method.
The third aspect of the invention provides an application of the surface modified magnesium hydroxide as a flame retardant in processing of a polymer composite material.
In the invention, the surface modified magnesium hydroxide is compounded with matrix resin as a flame retardant, so that the compatibility and the thermal stability of the surface modified magnesium hydroxide and a high polymer material can be improved, and the mechanical property, the processing flowability and the like of a high polymer compound can be obviously improved.
The surface modified magnesium hydroxide flame retardant disclosed by the invention is simple in preparation process and equipment and process, low in production cost, capable of being widely applied to industrial production processes on a large scale, capable of improving the compatibility and thermal stability of magnesium hydroxide and a high polymer material, simultaneously improving the flame retardant efficiency, and capable of remarkably improving the mechanical property and processing fluidity of a high polymer composite material.
The present invention will be described in detail below by way of examples.
In the following examples, the magnesium hydroxide is commercially available under the trade name MH-01 from Luoyang super New Material Ltd.
Example 1
This example illustrates the surface-modified magnesium hydroxide prepared by the preparation method of the present invention.
(1) Taking magnesium hydroxide with the particle size of 5000 meshes as a raw material, dispersing the magnesium hydroxide in a stirrer at a high speed under the condition that the stirring speed is 3500r/min, slowly adding castor oil at the dropping speed of 1ml/min after the temperature is raised to 60 ℃, and stirring for 30 min;
(2) adding triethyl phosphate to modify and coat the magnesium hydroxide, and continuously stirring for 60min at the temperature of 60 ℃ to obtain modified magnesium hydroxide;
wherein the amount of the castor oil is 1 weight percent of the mass of the magnesium hydroxide, and the amount of the triethyl phosphate is 3 weight percent of the magnesium hydroxide.
As a result, a white powdery surface-modified magnesium hydroxide is obtained, and
in the processing of a polymer composite material using PE and EVA as matrix resins, the surface-modified magnesium hydroxide was used as a flame retardant, and the addition amount thereof and the test results of the properties of the polymer composite material are shown in table 1.
Example 2
This example illustrates the surface-modified magnesium hydroxide prepared by the preparation method of the present invention.
(1) Taking magnesium hydroxide with the particle size of 5000 meshes as a raw material, dispersing the magnesium hydroxide in a stirrer at a high speed under the condition of stirring speed of 2000r/min, slowly adding castor oil at the dropping speed of 0.5ml/min after the temperature is raised to 70 ℃, and stirring for 50 min;
(2) adding triethyl phosphate to modify and coat the magnesium hydroxide, and continuously stirring for 30min at the temperature of 70 ℃ to obtain modified magnesium hydroxide;
wherein the amount of the castor oil is 1.5 wt% of the magnesium hydroxide, and the amount of the triethyl phosphate is 5 wt% of the magnesium hydroxide.
As a result, a white powdery surface-modified magnesium hydroxide is obtained, and
in the processing of a polymer composite material using PE and EVA as matrix resins, the amount of the surface-modified magnesium hydroxide as a flame retardant and the properties of the polymer composite material are shown in table 1.
Example 3
This example illustrates the surface-modified magnesium hydroxide prepared by the preparation method of the present invention.
(1) Taking magnesium hydroxide with the particle size of 2000 meshes as a raw material, dispersing the magnesium hydroxide in a stirrer at a high speed under the condition of the stirring speed of 5000r/min, slowly adding castor oil at the dropping speed of 1ml/min after the temperature is increased to 90 ℃, and stirring for 60 min;
(2) then adding trimethyl phosphate to modify and coat the magnesium hydroxide, and continuously stirring for 40min at the temperature of 90 ℃ to obtain modified magnesium hydroxide;
wherein, the use amount of the castor oil is 3 weight percent of the mass of the magnesium hydroxide, and the use amount of the trimethyl phosphate is 2 weight percent of the magnesium hydroxide.
As a result, a white powdery surface-modified magnesium hydroxide is obtained, and
in the processing of a polymer composite material using PE and EVA as matrix resins, the surface-modified magnesium hydroxide was used as a flame retardant, and the addition amount thereof and the test results of the properties of the polymer composite material are shown in table 1.
Example 4
This example illustrates the surface-modified magnesium hydroxide prepared by the preparation method of the present invention.
Surface-modified magnesium hydroxide was prepared in the same manner as in example 1, except that triethyl phosphate was replaced with diethyl aluminum hypophosphite;
as a result, a white powdery surface-modified magnesium hydroxide is obtained, and
in the processing of a polymer composite material using PE and EVA as matrix resins, the surface-modified magnesium hydroxide was used as a flame retardant, and the addition amount thereof and the test results of the properties of the polymer composite material are shown in table 1.
Example 5
This example illustrates the surface-modified magnesium hydroxide prepared by the preparation method of the present invention.
Surface-modified magnesium hydroxide was prepared in the same manner as in example 1, except that triethyl phosphate was replaced with phosphite;
as a result, a white powdery surface-modified magnesium hydroxide is obtained, and
in the processing of a polymer composite material using PE and EVA as matrix resins, the surface-modified magnesium hydroxide was used as a flame retardant, and the addition amount thereof and the test results of the properties of the polymer composite material are shown in table 1.
Example 6
This example illustrates the surface-modified magnesium hydroxide prepared by the preparation method of the present invention.
Surface-modified magnesium hydroxide was produced in the same manner as in example 1 except that castor oil was used in an amount of 0.3% by weight based on the mass of magnesium hydroxide, triethyl phosphate was used in an amount of 0.3% by weight based on the mass of magnesium hydroxide, and the modification treatment of triethyl phosphate was carried out in the presence of anhydrous ethanol in an amount of 1% by weight based on the amount of magnesium hydroxide;
as a result, a white powdery surface-modified magnesium hydroxide is obtained, and
in the processing of a polymer composite material using PE and EVA as matrix resins, the surface-modified magnesium hydroxide was used as a flame retardant, and the addition amount thereof and the test results of the properties of the polymer composite material are shown in table 1.
Example 7
This example illustrates the surface-modified magnesium hydroxide prepared by the preparation method of the present invention.
Surface-modified magnesium hydroxide was produced in the same manner as in example 1 except that castor oil was used in an amount of 8% by weight based on the mass of magnesium hydroxide and triethyl phosphate was used in an amount of 10% by weight based on the mass of magnesium hydroxide, and the modification treatment of triethyl phosphate was carried out in the presence of distilled water in an amount of 2% by weight based on the amount of magnesium hydroxide;
as a result, a white powdery surface-modified magnesium hydroxide is obtained, and
in the processing of a polymer composite material using PE and EVA as matrix resins, the surface-modified magnesium hydroxide was used as a flame retardant, and the addition amount thereof and the test results of the properties of the polymer composite material are shown in table 1.
Comparative example 1
Taking magnesium hydroxide with the grain diameter of 5000 meshes as a raw material, dispersing the magnesium hydroxide in a stirrer at a high speed, adding a silane coupling agent A172 after the temperature is raised to 90 ℃, and stirring for 30min to obtain modified magnesium hydroxide, wherein the dosage of the silane coupling agent is 1 weight percent of the magnesium hydroxide.
As a result, a white powdery surface-modified magnesium hydroxide is obtained, and
in the processing of a polymer composite material using PE and EVA as matrix resins, the surface-modified magnesium hydroxide was used as a flame retardant, and the addition amount thereof and the test results of the properties of the polymer composite material are shown in table 1.
Comparative example 2
Surface-modified magnesium hydroxide was prepared in the same manner as in example 1, except that triethyl phosphate was not added.
As a result, a white powdery surface-modified magnesium hydroxide is obtained, and
in the processing of a polymer composite material using PE and EVA as matrix resins, the surface-modified magnesium hydroxide was used as a flame retardant, and the addition amount thereof and the test results of the properties of the polymer composite material are shown in table 1.
Comparative example 3
Surface-modified magnesium hydroxide was prepared in the same manner as in example 1, except that castor oil was not added.
As a result, a white powdery surface-modified magnesium hydroxide is obtained, and
in the processing of a polymer composite material using PE and EVA as matrix resins, the surface-modified magnesium hydroxide was used as a flame retardant, and the addition amount thereof and the test results of the properties of the polymer composite material are shown in table 1.
Comparative example 4
Surface-modified magnesium hydroxide was prepared in the same manner as in example 1 except that castor oil was used in an amount of 0.2% by weight based on the mass of magnesium hydroxide and triethyl phosphate was used in an amount of 0.2% by weight based on the mass of magnesium hydroxide.
As a result, a white powdery surface-modified magnesium hydroxide is obtained, and
in the processing of a polymer composite material using PE and EVA as matrix resins, the surface-modified magnesium hydroxide was used as a flame retardant, and the addition amount thereof and the test results of the properties of the polymer composite material are shown in table 1.
Comparative example 5
Surface-modified magnesium hydroxide was prepared in the same manner as in example 1, except that castor oil was used in an amount of 8.5% by weight based on the mass of magnesium hydroxide, and triethyl phosphate was used in an amount of 10.5% by weight based on the mass of magnesium hydroxide.
As a result, a white powdery surface-modified magnesium hydroxide is obtained, and
in the processing of a polymer composite material using PE and EVA as matrix resins, the surface-modified magnesium hydroxide was used as a flame retardant, and the addition amount thereof and the test results of the properties of the polymer composite material are shown in table 1.
Comparative example 6
Surface-modified magnesium hydroxide was prepared in the same manner as in example 1, except that the temperature was 120 ℃ and the stirring time was 2.5 hours in total.
As a result, a white powdery surface-modified magnesium hydroxide is obtained, and
in the processing of a polymer composite material using PE and EVA as matrix resins, the surface-modified magnesium hydroxide was used as a flame retardant, and the addition amount thereof and the test results of the properties of the polymer composite material are shown in table 1.
TABLE 1
The results in table 1 show that the surface-modified magnesium hydroxide composite flame retardants prepared in examples 1 to 7, which are prepared by the method of the present invention, are added to resins in different proportions, so that the amount of magnesium hydroxide originally occupying 60% of the polymer mass can be reduced to 55%, the addition amount is small, the flame retardant efficiency is high, the flame retardant performance can be satisfied, the operation is simple and controllable, the environment is protected, no pollution is caused, and the processability of the polymer material is significantly improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A method for preparing surface modified magnesium hydroxide is characterized by comprising the following steps:
(1) carrying out first contact on a modifier I and magnesium hydroxide;
(2) carrying out second contact on a modifier II and the product obtained in the step (1);
wherein the modifier I is castor oil;
wherein the modifier II is phosphate or organic hypophosphorous acid metal salt; wherein the phosphate is one or more of triethyl phosphate, trimethyl phosphate and phosphite ester; the organic hypophosphorous acid metal salt is one or more of diethyl aluminum hypophosphite, poly (triallyl isocyanurate) aluminum hypophosphite and poly (triallyl isocyanurate) zinc hypophosphite;
wherein, the dosage of the modifier I is 0.3 to 8 weight percent and the dosage of the modifier II is 0.3 to 10 weight percent based on the dosage of the magnesium hydroxide.
2. The method of claim 1, wherein the conditions of the first contacting comprise: the stirring speed is 2000-5000r/min, the temperature is 40-110 ℃, and the time is 10-60 min; the conditions of the second contacting include: the stirring speed is 2000-5000r/min, the temperature is 40-110 ℃, and the time is 10-60 min.
3. The method of claim 1, wherein, in step (2), the second contacting is performed in the presence of a solvent.
4. The method of claim 3, wherein the solvent is absolute ethanol and/or distilled water.
5. A process according to claim 3 or 4, wherein the solvent is used in an amount of 1-5% by weight based on the amount of magnesium hydroxide.
6. The method according to claim 5, wherein in the step (1), the particle size of the magnesium hydroxide is 325-5000 mesh.
7. The method as claimed in claim 6, wherein the particle size of the magnesium hydroxide is 1000-5000 mesh.
8. The method according to claim 1, wherein in step (1), the modifier I is used in an amount of 0.3 to 3 wt% based on the amount of magnesium hydroxide; in the step (2), the amount of the modifier II is 0.3-3 wt% based on the amount of magnesium hydroxide.
9. The process according to claim 1 or 8, wherein the modifier I is first contacted with magnesium hydroxide in a dropwise manner; and the modifier II is in second contact with the reactant obtained in the step (1) in a dropwise manner.
10. The process of claim 9, wherein the dropping rate is 0.5-1 ml/min.
11. Surface-modified magnesium hydroxide obtainable by the process according to any one of claims 1 to 10.
12. Use of the surface-modified magnesium hydroxide according to claim 11 as a flame retardant in the processing of polymeric composites.
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| CN201810592985.XA CN109054450B (en) | 2018-06-11 | 2018-06-11 | Surface modified magnesium hydroxide and preparation method and application thereof |
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| CN109054450A CN109054450A (en) | 2018-12-21 |
| CN109054450B true CN109054450B (en) | 2020-05-15 |
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| CN112126125B (en) * | 2020-09-25 | 2022-04-26 | 广东金榜新材料有限公司 | Preparation method of composite plastic flame retardant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0255746A (en) * | 1988-08-19 | 1990-02-26 | Kyowa Chem Ind Co Ltd | Flame-retardant and flame-retardant resin composition |
| CN103819935A (en) * | 2014-01-31 | 2014-05-28 | 许营春 | Method for preparing magnesium hydrate fire retardant through surface modification treatment by using composite wet method |
| CN106280564A (en) * | 2016-08-18 | 2017-01-04 | 黄惠娟 | A kind of preparation method of surface modified superfine magnesium hydroxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0255746A (en) * | 1988-08-19 | 1990-02-26 | Kyowa Chem Ind Co Ltd | Flame-retardant and flame-retardant resin composition |
| CN103819935A (en) * | 2014-01-31 | 2014-05-28 | 许营春 | Method for preparing magnesium hydrate fire retardant through surface modification treatment by using composite wet method |
| CN106280564A (en) * | 2016-08-18 | 2017-01-04 | 黄惠娟 | A kind of preparation method of surface modified superfine magnesium hydroxide |
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