KR920001791B1 - Polyoleffin heat-resistant resin composition and method for the thereof - Google Patents

Abstract

A fire retardant polyolefin resin composition comprises 100 wt. pts of polypropylene having a melt index of 8-10g/10min at 230 deg.C, 18- 50 wt. pts. of fire retardant composition, 10-60 wt. pts. of reinforcing agent, 0.2-3.4 wt. pts. of sodium methoxide reaction initiator, and 0.5-30 wt. pts. of Maleic anhydride modifier. The Fire retardant composition is composed of decabromophenyloxide (DBDPO), antimony anhybride and vinyl tri-B-methoxy ethoxy silane. The resin composition has good mechanical and thermal properties.

Description

Polyolefin flame retardant composite resin composition and method for producing same

The present invention relates to a polyolefin flame-retardant composite resin composition and a method for manufacturing the same that can be usefully used in electrical and electronic products, in particular, it is suitable for electrical and electronic parts that require mechanical and thermal properties due to improved rigidity and heat resistance than general polypropylene. A flame retardant composite resin composition using a composite polypropylene.

In general, polymer composite materials are mechanically compounded with polymers having different physical and chemical properties in a polymer substrate to impart new functionality. Until now, many studies have been conducted and many parts have been put into practical use.

The properties of these composite materials depend on the composition and content of the matrix and filler and are also determined by the shape, size, arrangement, cohesion or workability of the filler.

In addition to the above conditions, not only the properties of the base material and the filler two components but also the properties at the interface are greatly affected.

That is, if there is no interaction between the base material and the filler, most of the fillers do not exhibit the reinforcing effect, but only the effect of the heavy material.

Glass fiber, carbon fiber, or many other polymeric fiber reinforcements generally exhibit a design reinforcement effect, except for very short short fibers, but calcium carbonate, silica, mica, carbon black, talc, metal powder or metal Plate-like or granular fillers, such as thin plates, act as a limiting factor to reduce intrinsic properties such as tensile, impact, and bending due to the occurrence of interfacial cracks or dispersibility between polymer substrates and fillers. .

In particular, when the polymer base material is a non-polar polyolefin type (LDPE, HDPE, PP, etc.), the interface adhesion between the base material and the filler is weak, so that effective stress transfer does not occur, thereby causing a significant decrease in physical properties.

Therefore, it is cheaper than other polymer materials and has excellent chemical resistance, impact resistance, processability, and reproducibility. Therefore, it maintains the inherent properties of polyolefin resins widely used in industrial products and household goods, and reduces physical properties as composite materials. Inhibiting and enhancing the reinforcing effect are the most important elements of functional composite materials.

In recent years, polypropylene of polyolefins has been compounded and applied to electric, electronic goods, and automobile parts.

In particular, when used for electric and electronic parts, self-extinguishing performance is required, that is, it is required to be used within the range of 94-V-0 among UL recognized UL standards. In addition to sex, flame retardancy is required.

In general, in order to form rigidity of the composite polypropylene, a method of improving interfacial adhesion between the polypropylene and the filler is used, and a method of treating a coupling agent having a functional group on the surface of the filler is mainly used.

There are various binders such as titanium, silane, and zirconium, but propylene is commercially available for polypropylene. The structure of the silane-based binder is composed of a hydroxyl group or silanol group capable of bonding with an inorganic filler and an organic functional group that reacts with the polymer resin.

Japanese Patent Laid-Open Nos. 50-59586, 50-59587, 51-67492, etc. are inventions having the above-described structure. Japanese Patent Laid-Open Nos. 51-16066, 51-7702, etc., before the invention or treatment in which some of the silane systems have introduced a function. However, it does not exceed the limits of stiffness and heat resistance after treatment, and there is no mention of flame retardancy.

Unlike chemisorption of the silane-based binder, the organic monomer or polymer may be grafted to the filler to induce a reinforcing effect by increasing chain binding and compatibility with the base polymer, and polar bonding.

Most of the fillers are hydrophilic having hydroxyl groups on their surfaces, and can be grafted directly to the inorganic surface.

Recently, the surface of the inorganic material is grafted and then grafted to the active point, but due to the heterogeneity of the object, it is not easy and there is no practical example of the method.

There is also an example of attempting to mix the reinforcing material for the fiber in order to overcome the limitation of rigidity or heat-resistant bushing. Japanese Patent Laid-Open Nos. 51-73042 and 51-73043 are examples of this, but can only be seen as an effect of fibrous reinforcement.

Japan's special office 51-35419, 51-5676, 51-858, 51-68678, etc., may be referred to as a synergistic effect by modifying the lobster polymer instead of the filler, but in the form of a copolymer. There are many problems in the polymerization method and there is no mention of flame retardant and reinforcing effect.

An object of the present invention is to produce a composite polypropylene in which a flame retardancy using a binder is imparted to a filler while forming a heterogeneous polymer through a reactive agent in a polypropylene chain which is a nonpolar polymer. As a method of introducing a polar group into the non-polar polypropylene, a solution reaction method is generally used, but other radiation and photoreaction methods are also known. In the present invention, a melt kneading method is used in terms of practical use, that is, productivity.

That is, sodium methoxide (CH ₃ ONa) was selected to give an active point to polypropylene, and maleic anhydride was selected as a fundamental modifier.

The polypropylene is added to the initial inlet of the extruder together with sodium methoxide, and then maleic anhydride is added to the mid portion after the reaction is produced, but the three compositions may be added together at the beginning. The heat source by melting and kneading acts as a reaction medium, and was melted and kneaded in a twin extruder having a dispersing and pulverizing function to introduce an appropriate and sufficient polar group. In addition to introducing the reactor of the matrix (Matrix), the introduction of the reactor (flame retardant, synergist, reinforcing material) to the reactor at the same time to maximize the physical properties, the dualization of the flame retardant composition by the binder treatment and the binder treatment of the reinforcing material is also an achievement of the present invention. .

Si(OCH₃)₃(r-Methacryloxy propyl trimethoxy silane)을 사용하였고, 보강재의 처리방법은 난연조성물의 처리방법과 동일하였으며 폴리프로필렌 100중량부를 기준으로 난연조성물(DBDP0+Sb₂0₃+결합제)은 18-50중량부가 투입되며, 보강재(Talc+결합제)는 10-60중량부가 투입된다.The flame retardant composition was kneaded with decabromodiphenyl oxide (DBDPO) powder and antimony trioxide (Sb ₂ 0 ₃ ), which is 30 / 100-35 / 100 of the DBDPO input weight, using a Henschel mixer for 3-5 minutes. , CH ₂ = CHSi (OC ₂ H ₄ OCH ₃ ) ₃ (Vinyl trisβ-methoxy ethoxy silane) with vinyl group was kneaded with a solvent and kneaded together for 5-10 minutes. After completion of the kneading, the solvent was dried in a drier at 90-110 ° C. × 2 hr to complete the treatment. In addition, the bonding treatment of the reinforcing material is a silane binder having a propyl group similar to polypropylene.

Si (OCH ₃ ) ₃ (r-Methacryloxy propyl trimethoxy silane) was used, and the treatment method of the reinforcing material was the same as that of the flame retardant composition, and the flame retardant composition (DBDP0 + Sb ₂ 0 ₃ + binder) based on 100 parts by weight of polypropylene. 18-50 parts by weight of silver is added, and 10-60 parts by weight of reinforcing material (Talc + binder).

The reinforcement is limited to talc with an average particle diameter of 2.2μ. Polypropylene used as a base material for the composite resin composition of the present invention has a melt index of 8-10 (g / 10min) at 230 ° C. and 2.16 kg pressure due to its melting characteristics. Reached. A twin screw extruder was used to melt and knead the polypropylene, flame retardant composition, reinforcing material, reactant (initiator), reactor material (modifier), and the reaction residence time was set to 2-4 minutes. In unreacted state, property degradation by thermal history occurs for more than 5 minutes.

Preferably, 2.5 minutes-3 minutes is suitable, and the temperature is in the range of 180 ° C-210 ° C.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

EXAMPLE 1, 2, 3

To evaluate the physical properties of the composition having the composition ratio as shown in Table 1 after the extrusion molded in a twin screw extruder excellent in grinding and dispersing function, the results are shown in Table 3. The extrusion conditions were the temperature of 180 ℃ -210 ℃, the total discharge amount at 25 rpm was 25kg per hour and the diameter of the extruder was used 30mm.

TABLE 1

Composition and preparation method of the flame retardant composition and reinforcement of Table 1 are as follows.

Flame retardant composition

Decabromodiphenyl oxide

74.4 wt%, Sb ₂ O ₃ , 24.8 wt% were kneaded in a Henschel mixer for 3-5 minutes, and 0.8 wt% of Vinyitris β-methoxy ethoxy silane, a vinyl-containing binder, was diluted to 100: 1 in toluene. A flame retardant composition was prepared by kneading for 10 minutes and drying at 90 ° C. for 2 hours in a drier.

[Production of reinforcement]

A reinforcing material was prepared in the same manner as the method for preparing a flame retardant composition using 99.1 wt% of talc and 0.9 wt% of r-Methacryloxy propyl trimethoxysilane, a vinyl group binder having a propyl group as a binder.

The specification of the raw member used in the Example is as follows.

ㆍ Polypropylene: homopolymer for molding with melt index 8-10 (g / min) under 230 ℃, 2.16kg pressure

DBDPO DE-83R from Great Lakes

ㆍ Sb ₂ 0 ₃ : Ilsung antimony

ㆍ Flame retardant composition binder: Union Carbide Co. AT172

ㆍ Talc ÷ Intrinsic Firm D-600

ㆍ Reinforcement binder ÷ Union carbide AT174

ㆍ Reactant (Sodium methoxide): -Aldrich Chemical Company, Inc. # 16. 499-2

ㆍ Modifier (maleic anhydride)-: Aldrich Chemical Company, Inc. #M 18-8

Comparative Example 1, 2, 3, 4, 5, 6

To evaluate the physical properties of the composition having a composition ratio as shown in Table 2 after the extrusion molded in a twin screw extruder excellent in grinding and dispersing function, the results are shown in Table 3. In addition, the extrusion conditions are the same as in Example, but there is no binder in the flame retardant composition, ① in the reinforcement was used untreated powder, ② used talc treated in the same manner as in Example.

TABLE 2

The composition of the flame retardant composition was 75 wt% DBDPO, 25 wt% Sb ₂ O ₃ . The extrudate was injected for the evaluation of the examples and comparative examples carried out as described above and the injection conditions are as follows.

Injection Machine, Ostriase Engel 240/75, 50Z

Molding temperature 195 ℃ -2OO ℃ (injection temperature)

Mold temperature 40 ℃

Drying condition before molding: Dehumidification dryer 90 ℃ × 2hr Evaluation items include tensile strength (ASTM D638), flexural strength (ASTM D 790), impact strength (ASTM D 256), heat deflection temperature (ASTM D 648), flame retardancy (UL 94V -0).

TABLE 3

Evaluation result table

Claims (4)

100 parts by weight of polypropylene with a melt index of 8-10 (g / 10min) at a temperature of 230 ° C and a pressure of 2.16 kg as a basic resin, 18-50 parts by weight of flame retardant composition, 10-60 parts by weight of reinforcement, sodium methoxide (Sodium Methoxide, CH ₃ ONa) 0.2-3.4 parts by weight of reactant, Maleic Anhydride (Maleic Anhydride,

A method of producing a flame retardant composite resin composition comprising 0.5-30 parts by weight of a modifier of kneading and extruding in a twin extruder having a dispersion and grinding function. The flame retardant composition according to claim 1, wherein the flame retardant composition comprises 30 / 100-35 / 100 parts by weight of decabromodiphenyl oxide (DBDPO) powder and antimony trioxide (Sb ₂ 0 ₃ ) based on DBDPO content by weight, and vinyl trissilane (Vinyl tris). β-methoxy ethoxy silane) is a composition of the flame retardant composite resin composition, characterized in that the mixture of 0.5 / 100-1 / 100 parts by weight based on the combined weight of the DBDPO and Sb ₂ 0 ₃ combined. According to claim 1, the reinforcement is a talc powder and the average particle diameter of 2.2μ and 90% by weight of silicon dioxide (SiO ₂ ) and magnesium oxide (MgO) and silane (r-Methacryloxy propyl trimethoxy silan) A method for producing a flame retardant composite resin composition, characterized in that the composition is mixed 0.5 / 100-1 / 100 parts by weight relative to the weight of the talc powder. Resin composition consisting of the method of claim 1, 2, 3.