阅读说明：本技术 一种二乙烯三胺五亚甲基膦酸铝阻燃剂及其制备方法和用途 (Aluminum diethylenetriamine penta (methylene phosphonic acid) flame retardant and preparation method and application thereof ) 是由 陈林 柴生勇 李积德 汪廷洪 李坤泉 刘勤 李岩 刘振峰 于 2019-04-03 设计创作，主要内容包括：本发明公开了一种二乙烯三胺五亚甲基膦酸铝阻燃剂,其结构式如式(Ⅰ)所示。所述二乙烯三胺五亚甲基膦酸铝阻燃剂的分子结构稳定,每一个二乙烯三胺五亚甲基膦酸提供8个一价阴离子与铝离子形成盐,具有磷含量高、热稳定性好、阻燃效率高、成炭率高、不含卤素、绿色环保等优点,可作为一种磷氮系阻燃剂广泛应用在高分子材料、木材、纸张等领域。本发明还公开了一种二乙烯三胺五亚甲基膦酸铝阻燃剂的制备方法,制备方法中各原料易得,合成工艺简单,产率高,易于工业化生产。本发明还公开了所述阻燃剂在高分子材料、木材或纸张中的用途。本发明还公开了一种包含该阻燃剂的阻燃剂组合物。本发明还公开了一种包含该阻燃剂组合物的阻燃高分子材料。(The invention discloses an aluminum diethylenetriamine pentamethylene phosphonate flame retardant, the structural formula of which is shown as a formula (I). The aluminum diethylenetriamine pentamethylene phosphonate flame retardant has a stable molecular structure, each diethylenetriamine pentamethylene phosphonate provides 8 univalent anions to form salt with aluminum ions, has the advantages of high phosphorus content, good thermal stability, high flame retardant efficiency, high char yield, no halogen, environmental protection and the like, and can be widely applied to the fields of high polymer materials, wood, paper and the like as a phosphorus-nitrogen flame retardant. The invention also discloses a preparation method of the aluminum diethylenetriamine pentamethylenephosphonate flame retardant, and the preparation method has the advantages of easily obtained raw materials, simple synthesis process, high yield and easy industrial production. The invention also discloses application of the flame retardant in high polymer materials, wood or paper. The invention also discloses a flame retardant composition containing the flame retardant. The invention also discloses a flame-retardant high polymer material containing the flame retardant composition.)

1. The flame retardant is characterized by being aluminum diethylenetriamine pentamethylene phosphonate, and the structural formula of the flame retardant is shown as the formula (I):

2. the flame retardant according to claim 1, wherein at least one of the following (a) to (c):

(a) the particle size of the aluminum diethylenetriamine pentamethylene phosphonate is D50-5 mu m-100 mu m;

(b) the tap bulk density of the aluminum diethylenetriamine pentamethylene phosphonate is 0.4g/cm³～0.9g/cm³；

(c) The angle of repose of the aluminum diethylenetriamine pentamethylene phosphonate is 25-45 degrees.

3. The process for preparing a flame retardant according to claim 1 or 2, comprising the steps of:

(1) reacting diethylenetriamine pentamethylene phosphonic acid or an acid salt aqueous solution of diethylenetriamine pentamethylene phosphonic acid with an aqueous solution of an alkaline compound according to equivalent weight to obtain an alkali metal salt aqueous solution of diethylenetriamine pentamethylene phosphonic acid;

(2) reacting the aqueous solution of the alkali metal salt of diethylenetriamine pentamethylene phosphonic acid with the aluminum metal compound or the aqueous solution of the aluminum metal compound to prepare the aluminum diethylenetriamine pentamethylene phosphonic acid.

4. The method for producing a flame retardant according to claim 3, wherein at least one of the following (d) to (f):

(d) in the step (1), the alkaline compound is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acetate and potassium acetate;

(e) in the step (1), the acid salt of diethylenetriamine pentamethylene phosphonic acid is monosodium diethylenetriamine pentamethylene phosphonic acid, disodium diethylenetriamine pentamethylene phosphonic acid, trisodium diethylenetriamine pentamethylene phosphonic acid, tetrasodium diethylenetriamine pentamethylene phosphonic acid, pentasodium diethylenetriamine pentamethylene phosphonic acid, hexasodium diethylenetriamine pentamethylene phosphonic acid, heptasodium diethylenetriamine pentamethylene phosphonic acid, octasodium diethylenetriamine pentamethylene phosphonic acid, at least one of monopotassium diethylenetriamine pentamethylenephosphonic acid, dipotassium diethylenetriamine pentamethylenephosphonic acid, tripotassium diethylenetriamine pentamethylenephosphonic acid, tetrapotassium diethylenetriamine pentamethylenephosphonic acid, pentapotassium diethylenetriamine pentamethylenephosphonic acid, hexapotassium diethylenetriamine pentamethylenephosphonic acid, heptapotassium diethylenetriamine pentamethylenephosphonic acid, and octapotassium diethylenetriamine pentamethylenephosphonic acid;

(f) in the step (2), the aluminum metal compound is at least one of aluminum sulfate, aluminum chloride, aluminum acetate, aluminum nitrate, aluminum hydroxide and aluminum oxide.

5. Use of a flame retardant according to claim 1 or 2 in a polymeric material, wood or paper.

6. A flame retardant composition comprising the flame retardant of claim 1 or 2.

7. The flame retardant composition of claim 6, wherein the flame retardant composition comprises the following components in weight percent: 10 to 99.9% of the flame retardant of claim 1 or 2 and 0.1 to 90% of an additive; preferably, the flame retardant composition comprises the following components in percentage by weight: 20 to 70% of the flame retardant of claim 1 or 2 and 30 to 80% of the additive.

8. The flame retardant composition of claim 7, wherein the additive is at least one of aluminum diethylphosphinate, aluminum dipropylphosphinate, aluminum dibutylphosphinate, aluminum ethylbutylphosphinate, aluminum hypophosphite, piperazine pyrophosphate, piperazine polyphosphate, melamine pyrophosphate, melamine polyphosphate, melamine cyanurate, guanidine, and dicyandiamide.

9. A flame-retardant polymer material, comprising the flame retardant composition according to any one of claims 6 to 8.

10. The flame-retardant polymer material according to claim 9, wherein the flame-retardant polymer material comprises the following components in percentage by weight: 1-50% of the flame retardant composition of any one of claims 6-8, 30-99% of a polymer, 0-60% of an auxiliary agent and 0-60% of a filler; preferably, the flame-retardant polymer material comprises the following components in percentage by weight: 5-30% of the flame retardant composition of any one of claims 6-8, 40-95% of a polymer, 0-40% of an auxiliary agent and 0-40% of a filler.

11. The flame retardant polymer material according to claim 10, wherein the polymer is a thermoplastic polymer and/or a thermosetting polymer.

12. The flame retardant polymer material of claim 11, wherein the thermoplastic polymer is at least one of a polyester, a polyamide, and a polyolefin; preferably, the thermoplastic polymer is at least one of nylon 66, polybutylene terephthalate, and polypropylene.

Technical Field

The invention belongs to the technical field of flame retardant application and synthesis, and particularly relates to an aluminum diethylenetriamine pentamethylenephosphonate flame retardant, and a preparation method and application thereof.

Background

The polymer material has the characteristics of light weight, easy processing and forming and the like, and is widely applied to production and life. However, most of the high molecular materials are easy to burn, and the burning process is accompanied by the generation of toxic and harmful gases, so that the fire hazard is serious. In such an environment, it is particularly important to modify the flame retardancy of the polymer material. The flame retardant for the polymer material is usually selected from halogen-based, phosphorus-based, nitrogen-based, aluminum-magnesium-based, clay-based, boron-based, tin-based, intumescent, and silicon-based ones. At present, the flame-retardant high polymer material is mainly added with a brominated flame retardant, but the use amount is large. Although the high-efficiency flame-retardant effect can be ensured even if the addition amount is small, toxic and corrosive dense smoke can be generated, and great harm is caused to the environment and the health of human bodies. Therefore, the development of halogen-free flame retardants is increasing in various countries, and among them, halogen-free phosphorus-nitrogen flame retardants are one of the countermeasures. At high temperature, the halogen-free phosphorus-nitrogen flame retardant forms a compact carbon layer on the surface of the high polymer material, can isolate oxygen and heat, has low smoke generation amount, does not generate toxic or harmful gas, and has good flame retardant effect.

Phosphorus-nitrogen flame retardants, boron flame retardants, halogen flame retardants, and metal oxides or hydroxides such as aluminum, magnesium, and antimony are commonly used as the wood flame retardant. Flame retardant mechanisms of different types of flame retardants are different, and a compounding mode of several flame retardants is generally adopted. According to the development trend of wood flame retardants at home and abroad in recent years, research and development of long-acting flame retardants with low toxicity, low pollution, low moisture absorption and resistance to loss and multifunctional flame retardants with corrosion resistance, mildew resistance, insect resistance, dimensional stability and the like have been advanced. In addition to the above characteristics, the flame retardant effect and the influence of the flame retardant treatment on the physical and mechanical properties such as the strength of wood or the strength of a plywood sheet must be considered in practice, and the cost is one of the factors that must be considered.

Paper is generally made of plant fibers, which are flammable substances. With the development of society, flame retardant paper using plant fiber as a main raw material, such as flame retardant packaging paper and paperboard, flame retardant decorative paper, flame retardant automobile filter paper and the like, is used in more and more fields, so that the research on the flame retardant of plant fiber paper has become a research hotspot in the field of special paper. The existing flame-retardant method for vegetable fiber paper is usually prepared by adding a flame retardant, such as adding a water-insoluble flame retardant into paper pulp to make flame-retardant paper, or using a surface sizing method, a coating method or an impregnation method and the like to enable the flame-retardant paper to have flame retardancy. The existing flame-retardant paper produced in China mainly has the defects of large addition amount of flame retardant, use of halogen-containing flame retardant, easy moisture absorption of the flame retardant and the like.

Phosphorus-containing flame retardants are often used in combination with nitrogen-based flame retardants. In patent CN1660857B, aluminum diethylphosphinate flame retardant uses melamine polyphosphate as a synergist. The compounded synergistic flame retardant is intermolecular, and the synergistic effect of phosphorus and nitrogen elements in the molecule draws attention of chemists. Ammonium polyphosphate (also called ammonium polyphosphate or condensed ammonium phosphate (APP for short) is a phosphorus-nitrogen flame retardant with excellent performance, has higher phosphorus content and nitrogen content, and has an intramolecular P-N synergistic effect. Patent CN104497041A discloses a compound of formula (ii) in which each aminotrimethylene phosphonic acid provides three monovalent anions, which with melamine form a melamine aminotrimethylene phosphonate. Patent CN106632468A discloses a compound of formula (III), each aminotrimethylene phosphonic acid providing a monovalent anion, which is reacted with a metal salt to give the aminotrimethylene phosphonic acid metal salt. Although both of these compounds have a certain flame retardancy, they have disadvantages such as a large amount of addition, low flame retardant efficiency, and low char yield. German patent DE19532208A discloses the use of metal salts of diethylenetriamine pentamethylenephosphonic acid as coolant lubricants for metal working. Patent WO2007128745A discloses the use of magnesium diethylenetriamine pentamethylenephosphonate as an additive in textile detergents. GB2157279A discloses the use of calcium diethylenetriamine pentamethylenephosphonate as a flame retardant additive in drilling cements. However, few reports have been made on aluminum diethylenetriamine pentamethylenephosphonic acid as a flame retardant.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provides an aluminum diethylenetriamine pentamethylene phosphonate flame retardant, a preparation method and application thereof.

In order to achieve the purpose, the invention adopts the technical scheme that: a flame retardant is aluminum diethylenetriamine pentamethylene phosphonate, and the structural formula of the flame retardant is shown as the formula (I):

the invention synthesizes a series of aluminum diethylenetriamine pentamethylene phosphonate by reacting the aqueous solution of diethylenetriamine pentamethylene phosphonic acid or the acid salt of the diethylenetriamine pentamethylene phosphonic acid with a metal compound or the aqueous solution thereof under different pH values, and obtains a compound with a structure shown in a formula (IV):

wherein n is 1 to 10.

In the molecular structure of the compound (IV), each diethylenetriamine pentamethylene phosphonic acid provides 1 to 10 univalent anions to react with aluminum ions.

Through a large number of synthetic and fire retardant screening researches, the aluminum diethylenetriamine pentamethylene phosphonate with the structure (I) has the best fire retardant effect, high phosphorus content, good thermal stability, high char yield, no halogen, greenness, environmental protection and the like when n is 8. The compound with the structure (I) is prepared by reacting diethylenetriamine pentamethylene phosphonic acid or an acid salt aqueous solution of diethylenetriamine pentamethylene phosphonic acid with an aqueous solution of an alkaline compound according to equivalent weight to obtain a diethylenetriamine pentamethylene phosphonic acid metal salt aqueous solution, and reacting with an aluminum metal compound or an aqueous solution thereof. The structure is characterized in that each diethylenetriamine pentamethylene phosphonic acid has 2 undissociated hydrogen ions to provide 8 univalent anions, and forms a stable chemical structure with trivalent metal aluminum ions.

Preferred embodiments of the flame retardant include at least one of the following (a) to (c):

(a) the particle size of the aluminum diethylenetriamine pentamethylene phosphonate is D50-5 mu m-100 mu m;

(b) the tap bulk density of the aluminum diethylenetriamine pentamethylene phosphonate is 0.4g/cm³～0.9g/cm³；

(c) The angle of repose of the aluminum diethylenetriamine pentamethylene phosphonate is 25-45 degrees.

The invention also aims to provide a preparation method of the flame retardant, which comprises the following steps:

(1) reacting diethylenetriamine pentamethylene phosphonic acid or an acid salt aqueous solution of diethylenetriamine pentamethylene phosphonic acid with an aqueous solution of an alkaline compound according to equivalent weight to obtain an alkali metal salt aqueous solution of diethylenetriamine pentamethylene phosphonic acid;

(2) reacting the aqueous solution of the alkali metal salt of diethylenetriamine pentamethylene phosphonic acid with the aluminum metal compound or the aqueous solution of the aluminum metal compound to prepare the aluminum diethylenetriamine pentamethylene phosphonic acid.

As a preferred embodiment of the method for producing the flame retardant of the present invention, at least one of the following (d) to (f):

(d) in the step (1), the alkaline compound is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acetate or potassium acetate;

(e) in the step (1), the acid salt of diethylenetriamine pentamethylene phosphonic acid is monosodium diethylenetriamine pentamethylene phosphonic acid, disodium diethylenetriamine pentamethylene phosphonic acid, trisodium diethylenetriamine pentamethylene phosphonic acid, tetrasodium diethylenetriamine pentamethylene phosphonic acid, pentasodium diethylenetriamine pentamethylene phosphonic acid, hexasodium diethylenetriamine pentamethylene phosphonic acid, heptasodium diethylenetriamine pentamethylene phosphonic acid, octasodium diethylenetriamine pentamethylene phosphonic acid, at least one of monopotassium diethylenetriamine pentamethylenephosphonic acid, dipotassium diethylenetriamine pentamethylenephosphonic acid, tripotassium diethylenetriamine pentamethylenephosphonic acid, tetrapotassium diethylenetriamine pentamethylenephosphonic acid, pentapotassium diethylenetriamine pentamethylenephosphonic acid, hexapotassium diethylenetriamine pentamethylenephosphonic acid, heptapotassium diethylenetriamine pentamethylenephosphonic acid, and octapotassium diethylenetriamine pentamethylenephosphonic acid;

(f) in the step (2), the aluminum metal compound is at least one of aluminum sulfate, aluminum chloride, aluminum acetate, aluminum nitrate, aluminum hydroxide and aluminum oxide.

The invention also aims to provide the application of the flame retardant in high polymer materials, wood or paper.

The invention also aims to provide a flame retardant composition which comprises the flame retardant.

As a preferred embodiment of the flame retardant composition, the flame retardant composition comprises the following components in percentage by weight: 10-99.9% of the flame retardant and 0.1-90% of the additive.

As a more preferred embodiment of the flame retardant composition of the present invention, the flame retardant composition comprises the following components in weight percent: 20-70% of the flame retardant and 30-80% of the additive.

As a preferred embodiment of the flame retardant composition of the present invention, the additive is at least one of aluminum diethylphosphinate, aluminum dipropylphosphinate, aluminum dibutylphosphinate, aluminum ethylbutylphosphinate, aluminum hypophosphite, piperazine pyrophosphate, piperazine polyphosphate, melamine pyrophosphate, melamine polyphosphate, melamine cyanurate, guanidine, and dicyandiamide.

The invention also aims to provide a flame-retardant polymer material which comprises the flame retardant composition.

As a preferred embodiment of the flame retardant polymer material of the present invention, the flame retardant polymer material comprises the following components in percentage by weight: 1-50% of the flame retardant composition, 30-99% of a polymer, 0-60% of an auxiliary agent and 0-60% of a filler.

As a more preferable embodiment of the flame retardant polymer material of the present invention, the flame retardant polymer material comprises the following components in percentage by weight: 5-30% of the flame retardant composition, 40-95% of a polymer, 0-40% of an auxiliary agent and 0-40% of a filler.

As a preferred embodiment of the flame retardant polymer material of the present invention, the polymer is a thermoplastic polymer and/or a thermosetting polymer.

As a preferred embodiment of the flame retardant polymer material of the present invention, the thermoplastic polymer is at least one of polyester, polyamide and polyolefin.

As a preferred embodiment of the flame retardant polymer material of the present invention, the thermoplastic polymer is at least one of nylon 66, polybutylene terephthalate and polypropylene.

The invention has the beneficial effects that: the invention provides an aluminum diethylenetriamine pentamethylene phosphonate flame retardant which has a stable molecular structure, each diethylenetriamine pentamethylene phosphonate provides 8 univalent anions to form salt with aluminum ions, and the aluminum diethylenetriamine pentamethylene phosphonate flame retardant has the advantages of high phosphorus content, good thermal stability, high flame retardant efficiency, high char yield, no halogen, environmental protection and the like, and can be widely applied to the fields of high polymer materials, wood, paper and the like as a phosphorus-nitrogen flame retardant. The invention also provides a preparation method of the aluminum diethylenetriamine pentamethylenephosphonate flame retardant, and the preparation method has the advantages of easily obtained raw materials, simple synthesis process, high yield and easy industrial production. The invention also provides the application of the flame retardant in high polymer materials, wood or paper. The invention also provides a flame retardant composition containing the flame retardant. The invention also provides a flame-retardant high polymer material containing the flame retardant composition.

Drawings

FIG. 1 shows the structure of formula (I).

Detailed Description

The raw materials of the invention are all from commercial products.

The method for testing the particle size of the aluminum diethylenetriamine pentamethylene phosphonate comprises the following steps:

the particle size distribution of aluminum diethylenetriamine pentamethylenephosphonate dispersed in the liquid phase was measured by a laser particle sizer. The specific operation is as follows: according to the particle size of the aluminum diethylenetriamine pentamethylene phosphonate, 0.05g to 1.0g of the aluminum diethylenetriamine pentamethylene phosphonate is put into a beaker, added with alcohol and water, dispersed by ultrasonic or stirring, and poured into a laser particle sizer to measure the particle size distribution of the aluminum diethylenetriamine pentamethylene phosphonate. The particle size of the aluminum diethylenetriamine pentamethylene phosphonate is evaluated according to D (10), D (50) and D (90) measured by a laser particle sizer.

The test method of the angle of repose of the aluminum diethylenetriamine pentamethylene phosphonate comprises the following steps:

and pouring the powder sample into a funnel, enabling the sample to fall on a round flat plate with the radius r below the round flat plate through the funnel, and gradually piling the powder until the powder cannot be piled up continuously. The powder bulk height h is measured and the angle of repose α is calculated according to the formula (1).

tgα＝h/r (1)。

The tapped bulk density test method of the aluminum diethylenetriamine pentamethylene phosphonate is determined by referring to GB/T20316.2-determination of bulk density.

The infrared absorption spectrum testing method of the aluminum diethylenetriamine pentamethylene phosphonate is determined by referring to the method of GB/T6040-2002 'general rule on infrared spectrum analysis methods'.

The performance test of the flame-retardant high polymer material is carried out according to the following standards:

tensile strength: GB/T1040 + 1992 test methods for tensile Properties of plastics;

bending strength: GB/T9341-2000 method for testing bending property of plastics;

deflection: GB/T9341-2000 method for testing bending property of plastics;

notched impact strength: GB/T16420 1996 test method for small samples of plastic impact properties;

the combustion performance is UL94 test for the combustion performance of plastics.

The performance test of the flame-retardant wood is carried out according to the following standards:

bonding strength: GB/T17657-1999 test method for physical and chemical properties of artificial boards and facing artificial boards;

limiting oxygen index: GB/T2406-2009 oxygen index method for testing the combustion performance of plastics, GB 50222-95 fire protection code for interior decoration design of buildings stipulates that the oxygen index of grade B1 is not less than 48%;

smoke density: GB/T8627 and 1999 Smoke Density test method for burning or decomposing building materials, the smoke Density level SDR is less than or equal to 75.

The performance test of the flame-retardant paper is carried out according to the following standards:

combustion performance: GB/T14656-2009 flame retardant paper and paperboard burning performance test method;

limiting oxygen index: GB/T2406 and 2009 'Plastic burning Performance test method oxygen index method', GB 50222-95 'architectural interior decoration design fire protection code' stipulates that the B1 grade oxygen index is not less than 48%.

To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.