WO2024027000A1

WO2024027000A1 - Method for realizing flame retardation of flame retardant on basis of blending modification of thermoplastic high polymer material

Info

Publication number: WO2024027000A1
Application number: PCT/CN2022/121207
Authority: WO
Inventors: 翁永华
Original assignee: 江苏卡续曼新材料科技有限公司
Priority date: 2022-08-03
Filing date: 2022-09-26
Publication date: 2024-02-08
Also published as: CN115141459A

Abstract

Disclosed in the present invention is a method for realizing flame retardation of a flame retardant on the basis of blending modification of a thermoplastic high polymer material, which method comprises the following steps: S1, selecting a non-oxide and a metal compound, and subjecting same to a complexation reaction with an anionic compound having an aryl group or a long carbon aliphatic chain to produce a porcelainizable metal complex; S2, adding an additive to the porcelainizable metal complex, and then blending same with a high polymer resin; and S3, burning the blended material into porcelain to dehydrate the metal complex, thereby forming a technical oxide scaled layer. In the present invention, in order to ensure that the introduction of the flame retardant that can realize porcelainization by means of sintering does not affect or slightly affect the properties of a thermoplastic plastic, an anionic ligand for the flame retardant that can realize porcelainization by means of sintering must be selected according to different molecular structures of thermoplastic plastics. The second inventive point of the present invention lies in that by selecting anionic ligands having certain affinity with the molecular structures of different thermoplastic plastics, the porcelainizable flame retardant added to different thermoplastic plastics can make same become flame retardant materials with good comprehensive performance.

Description

Flame retardant method based on blending modification of thermoplastic polymer materials

Technical field

The present invention relates to the field of flame retardant preparation, and in particular to a flame retardant method based on blending and modification of thermoplastic polymer materials.

Background technique

As an important basic raw material in the current modern industry, flame-retardant thermoplastic composite materials play an increasingly important role in all walks of life in my country. From the comprehensive characteristics of environmental protection, safety, cost-effectiveness of materials and retention of basic resin properties, etc. Generally speaking, all current flame retardant systems have obvious shortcomings.

Halogen flame retardants have developed into mainstream products in the flame retardant market due to their low dosage, high flame retardant efficiency and wide adaptability. However, the serious disadvantage of halogen flame retardants is that they generate a large amount of smoke and toxic and corrosive gases when burned, which can lead to corrosion of circuit system switches and other metal objects and pollution to the environment that cannot be caused by fire alone; to the human body Harm to the respiratory tract and other organs may even threaten life due to suffocation. In recent years, the United States, the United Kingdom, Norway, and Australia have formulated or promulgated laws to conduct combustion toxicity tests on certain products or regulate acid gases released by the use of certain products, and develop halogen-free flame retardants to replace halogen flame retardants. Agents have become a trend in the world's flame retardant field.

Inorganic flame retardants (Al(OH) ₃ , Mg(OH) ₂ , etc.) are abundant in sources and low in price, but their flame retardant effects are poor, the amount of addition is large, and they have a great impact on the performance of the product. Therefore, efforts are made at home and abroad to surpass Conduct technological development in terms of refinement, microencapsulation, surface treatment, and synergistic compounding.

Red phosphorus has high flame retardant efficiency, low dosage, and wide application range. Microencapsulated red phosphorus overcomes the shortcomings of red phosphorus such as moisture absorption, easy coloration, and easy explosion. Phosphorus stabilization-microencapsulation technology has received much attention in the field of flame retardancy.

Intumescent flame retardants are considered to be one of the promising ways to achieve halogen-free because they produce less smoke and no toxic gases during combustion.

According to statistics, 80% of fatal accidents in fires are caused by suffocation by smoke and toxic gases released by combustion. Research and development of new flame retardants to reduce the amount of smoke and toxic gases when materials burn has become a trend in recent years. One of the key research topics in the field, the currently used smoke suppressants are mainly metal oxides and transition metal oxides, mainly including zinc borate, molybdenum compounds (molybdenum trioxide, ammonium molybdate) and their compounds, Magnesium-zinc complex, ferrocene, tin oxide, copper oxide, etc. In addition, some inorganic fillers (Al(OH) ₃ , Mg(OH) _2, etc.) also have the effect of flame retardant and smoke suppression. Intumescent flame retardant The porous carbon layer of the agent also has the dual functions of flame retardant and smoke suppression.

At present, thermoplastic flame-retardant materials can usually only extinguish immediately after leaving the fire or within a short time after leaving the fire, but they cannot achieve the function of the component material itself not burning through or collapsing, which still cannot meet the current requirements of many emerging industries on material resistance. Flammability requirements, such as: new energy battery shells, building exterior panels, etc. For application fields like new energy battery shells, the ideal material flame retardant performance should be such that after a fire occurs, the component material forms a dense sintered layer, thereby inhibiting the spread of fire from one battery pack to other surrounding battery packs. Since new energy batteries are composed of a large number of battery pack units in many applications, if the battery pack shell material can achieve this flame retardant property , which is of great significance to the safe use of new energy.

Contents of the invention

The invention overcomes the shortcomings of the prior art and provides a flame retardant method based on blending and modification of thermoplastic polymer materials.

In order to achieve the above objectives, the technical solution adopted by the present invention is: a flame retardant method based on blending and modification of thermoplastic polymer materials, which is characterized by including the following steps: S1: Select non-oxide and metal compounds and aromatic compounds. The complex reaction of anionic compounds with base or long carbon aliphatic chain produces metal complexes that can be porcelain-formed; S2: The metal complexes that can be porcelain-formed are blended with polymer resin after adding additives; S3: Blending The material burns into porcelain, the metal complex dehydrates, and a technical oxide scale layer is formed.

In a preferred embodiment of the present invention, the additive at least includes a stabilizer, and the stabilizer is 3,5-di-tert-butyl-4-hydroxybenzyl diethyl phosphate.

In a preferred embodiment of the present invention, hexachlorobenzene is selected as the non-oxide.

In a preferred embodiment of the present invention, the metal compound is a potassium metal compound.

In a preferred embodiment of the present invention, the polymer resin is furfuryl alcohol resin.

In a preferred embodiment of the present invention, it is applied to battery pack shells, building hanging boards or cables.

The present invention solves the defects existing in the background technology and has the following beneficial effects:

Based on the flame retardant mechanism of traditional thermoplastic materials and the blending modification theory of thermoplastic materials, the present invention expands the conceptual scope of carbon formation during the flame retardant process of thermoplastic materials and creatively introduces an inorganic mineral combination that can be porcelain-formed at low temperature. When thermoplastic polymer materials encounter fire and generate high temperatures, one component of this inorganic mineral combination begins to melt and decompose, and its decomposition products combine with another component of the composition to form a compound with a higher melting point, thereby sintering into a layer The dense protective layer prevents the further spread of flames and achieves the flame retardant effect of the material.

The invention is completely environmentally friendly and will not produce toxic by-products due to combustion and decomposition due to the introduction of flame retardants. The introduced inorganic mineral compositions and polymer materials have a certain affinity and will not damage the performance of the materials; and are extremely cost-effective. High, the inorganic mineral composition involved is not a product of current resource scarcity, and the cost is extremely low. While the properties are basically consistent with current traditional flame retardant materials, the cost is 10 to 15% lower than current traditional flame retardant materials.

Detailed ways

The technical solutions in the embodiments of the present invention will be described clearly and completely below. In the description of the present invention, references to "embodiment", "one embodiment" or "other embodiments" indicate specific features described in conjunction with the embodiments. , structures or characteristics are included in at least some embodiments, but not necessarily all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to protection scope of the present invention.

The flame retardant method based on the blending modification of thermoplastic polymer materials includes the following steps: S1: Select non-oxide and metal compounds to react with anionic compounds with aryl groups or long carbon aliphatic chains, and the output can be Porcelain metal complex; S2: The metal complex that can be porcelain is blended with polymer resin after adding additives; S3: The blended material is burned into porcelain, the metal complex is dehydrated, and technical oxide scaling is formed. layer.

In one embodiment, the present invention can prepare flame-retardant PS. Specifically, the additive is 3,5-di-tert-butyl-4-hydroxybenzyl diethyl phosphate, the non-oxide is hexachlorobenzene, and the metal compound is metal Potassium compound, polymer resin uses furfuryl alcohol resin. On the basis of meeting the mechanical properties, formability and flame retardancy of equivalent flame-retardant PS in the existing market, the products of this project have better cost performance, with costs 10-15% lower than existing products. The products are mainly used in home appliances , office equipment, etc.

In other embodiments, the present invention can also prepare flame-retardant ABS. On the basis of meeting the mechanical properties, formability and flame retardancy of equivalent flame-retardant ABS in the existing market, the products of this project type have better cost performance and lower cost. The price of existing products is 10 to 15% lower, and the products are mainly used in electronic appliances, home appliances, office equipment, etc.

In other embodiments, the present invention can also prepare flame-retardant nylon. On the basis of meeting the mechanical properties, formability and flame retardancy of equivalent flame-retardant nylons in the existing market, the products of this project type have better cost performance and lower cost. Existing types of products are 10 to 15% lower. Products are mainly used in electrical, electromechanical equipment, new energy, etc.

In other embodiments, the present invention can also prepare flame-retardant polyolefins. On the basis of meeting the mechanical properties, formability and flame retardancy of equivalent flame-retardant polyolefins in the existing market, the products of this project type have better cost performance. The cost is 10 to 15% lower than existing products. The products are mainly used in home decoration, mechanical and electrical equipment, etc.

In other embodiments, the present invention can also prepare flame-retardant polyester. On the basis of meeting the mechanical properties, formability and flame retardancy of equivalent flame-retardant polyesters in the existing market, the products of this project type have better cost performance. The cost is 10 to 15% lower than existing products. The products are mainly used in electrical, electromechanical equipment, new energy, etc.

In other embodiments, the present invention can also prepare flame-retardant plastic alloys. On the basis of meeting the mechanical properties, formability and flame retardancy of equivalent flame-retardant plastic alloys in the existing market, the products of this project have better cost performance. The cost is 10 to 15% lower than existing products. Products are mainly used in home appliances, office equipment, electronic and electrical equipment, electromechanical equipment, new energy, etc.

In the above embodiments, the present invention can be applied to various industries that have flame retardant requirements for plastic parts, including at least:

New energy: new energy battery casing, charging pile, junction box casing, etc.

Communication: such as router shell, base station transmitter shell, etc.

Home appliances: such as monitor backplanes and home appliance casings.

Electrical: low-voltage switches, coil bobbins, wires and cables.

Construction: exterior wall hanging panels, interior decorative panels, floors.

Office equipment: printer casing, fax machine casing, computer monitor casing, etc.

The various index data of the present invention are shown in Table 1:

Table I

The key to realizing the flame retardant material of the present invention lies in the introduction of inorganic flame retardants that are efficient and can be sintered into porcelain. This kind of flame retardant is a metal complex designed according to the different molecular structures of the thermoplastic materials required to be flame retardant. The decomposition temperature of this metal complex is between 300-400°C. When the project material heats up during combustion , this metal complex dehydrates to form a metal oxide with an extremely high melting point (>1500°C), thereby forming a dense porcelain layer on the surface of the burning material. During this process, the flame retardant effect of the material is reflected in: on the one hand, the endothermic dehydration of the metal complex plays a role in cooling and suppressing the polymer; on the other hand, the dense porcelain layer formed also serves to insulate the air , the effect of preventing burning.

Unlike inorganic flame retardants such as molybdate or aluminum/magnesium hydroxide used to form a solid coating in traditional flame retardant systems, this porcelain flame retardant is based on and the required flame retardant thermoplastic material Metal complexes with a certain affinity are added in the form of metal oxides that can be porcelain-formed through molecular-level reactions during the combustion process of the material. Therefore, the efficiency is extremely high and the impact on the material properties is minimized.

Compatibility between sinterable porcelain flame retardants and thermoplastics: In order to ensure that the introduction of sinterable porcelain flame retardants has no impact or a slight impact on the properties of thermoplastic plastics, sinterable porcelain flame retardants can be sintered into porcelain flame retardants. The negative ligand of the material must be selected according to the different molecular structures of the thermoplastics. By selecting negative ligands that have a certain affinity with the molecular structures of different thermoplastic plastics, the present invention enables porcelain-able flame retardants to be used in different thermoplastic plastics to achieve flame retardant materials with excellent comprehensive properties.

Advantages of this invention compared with traditional technology:

Compared with halogen flame retardant: it has similar flame retardant effect as halogen flame retardant, but also overcomes the problems of high pollution in the production process, large amount of smoke and toxicity when burning.

Compared with intumescent flame retardant: it has the same environmental protection and low toxicity characteristics as intumescent flame retardant, but also overcomes the disadvantage of high addition amount and great impact on other physical and mechanical properties of the material.

Compared with AL(OH)3 and Mg(OH)2 flame retardant: it has similar advantages of low price, non-toxic, non-corrosive, good stability, non-volatile, and does not produce toxic gases at high temperatures, but also overcomes the This overcomes the shortcomings of large filling volume, reduced mechanical properties and poor processability.

Compared with phosphate ester flame retardant: it has similar advantages of environmental protection and high efficiency, but also overcomes its shortcomings of high volatility and low heat resistance.

The above is based on the ideal embodiment of the present invention. Through the above description, relevant personnel can make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the content in the description, and must be determined based on the scope of the claims.

Claims

The flame retardant method for flame retardants based on blending modification of thermoplastic polymer materials is characterized by including the following steps:

S1: Select non-oxide and metal compounds to react with anionic compounds with aryl groups or long carbon aliphatic chains to produce metal complexes that can be transformed into porcelain;

S2: Porcelain-forming metal complexes are added with additives and blended with polymer resin;

S3: The blended material is burned into porcelain, the metal complex is dehydrated, and a technical oxide scaling layer is formed.
The flame retardant method for flame retardants based on blending modification of thermoplastic polymer materials according to claim 1, characterized in that: the additive at least includes a stabilizer, and the stabilizer is 3,5-di-tert-butyl- 4-Hydroxybenzyldiethylphosphate.
The flame retardant method for flame retardants based on blending and modification of thermoplastic polymer materials according to claim 1, characterized in that: the non-oxide is selected from hexachlorobenzene.
The flame retardant method for flame retardants based on blending and modification of thermoplastic polymer materials according to claim 1, wherein the metal compound is a potassium metal compound.
The flame retardant method for flame retardants based on blending modification of thermoplastic polymer materials according to claim 1, characterized in that: the polymer resin adopts furfuryl alcohol resin.
The flame retardant method based on the blending and modification of thermoplastic polymer materials according to claim 1, characterized in that it is applied to battery pack shells or building hanging boards or cables.