CN103333382A - Polycyclotriphosphazene-sulfone microsphere-containing composite fire retardation cable material and preparation method thereof - Google Patents

Abstract

The present invention relates to a polycyclotriphosphazene-sulfone microsphere-containing composite fire retardation cable material and a preparation method thereof. According to the cable material, high cross-linking degree polycyclotriphosphazene-sulfone microspheres, magnesium hydroxide and aluminum hydroxide are adopted as fire retardation agents, such that a residual rate of the cable material at a high temperature can be increased, and thermal stability and fire retardation of the cable material can be increased. The cable material has a characteristic of low smoking, and does not contain lead, antimony and other toxic substances, such that the cable material is a green environmental protection type material. With polyphosphazene microsphere addition, filling amounts of magnesium hydroxide and aluminum hydroxide can be reduced, and mechanical property of the material can be increased while fire retardation of the material is improved. With lubricant addition, a processing performance of the material can be increased. In addition, the cable material is a novel efficient fire retardation cable material.

Description

Contain composite fire resistance cable material of poly-ring three phosphonitriles-sulfone microballoon and preparation method thereof

Technical field

The present invention relates to a kind of fire-resistant cable material and preparation method thereof, particularly a kind of polymeric material field that belongs to relates to polymkeric substance cable material, especially a kind of composite fire resistance cable material that contains poly-ring three phosphonitriles-sulfone microballoon and preparation method thereof.

Background technology

Electric wire has the effect of power transmission and information conveyance, plays an important role in people's life with in producing.The low cigarette of design and preparation, low toxicity, the while possesses the CABLE MATERIALS of excellent fire-retardancy and insulating property again, becomes the focus of current fire-retardant research.

Traditional magnesium hydroxide and aluminium hydroxide based flame retardant, though can give the material good flame retardancy, but, because the matrix resin of most of CABLE MATERIALS is nonpolar polyolefins polymer, relatively poor with the consistency of the magnesium hydroxide of polarity, aluminium hydroxide, tend to reduce mechanical property and the processing characteristics of material.

The phosphonitrile compounds is alternately arranging with the phosphorus nitrogen-atoms on the main chain, and side chain is a class novel organic-inorganic compound of different organic substituents, and it has the incomparable superiority of traditional polymer.And by poly-ring three phosphonitriles-sulfone microballoon that precipitation polymerization method obtains, owing to highly cross-linked chemical structure, having excellent thermostability, the residual rate in air under 600 ℃ reaches more than 50%; The phosphorus nitrogen of high-content constitutes collaboration system simultaneously, has superior flame retardant effect, is a kind of BACN efficiently.

Summary of the invention

One of purpose of the present invention is to provide a kind of composite fire resistance cable material that contains poly-ring three phosphonitriles-sulfone microballoon.By adding poly-ring three phosphonitriles-sulfone microballoon, magnesium hydroxide and aluminium hydroxide simultaneously, give material excellent flame-retardant, favorable mechanical processibility, good insulation performance.

Two of purpose of the present invention is to provide the preparation method of this CABLE MATERIALS.

For achieving the above object, the present invention adopts following technical scheme:

A kind of composite fire resistance cable material that contains poly-ring three phosphonitriles-sulfone microballoon is characterized in that this CABLE MATERIALS mainly contains following component, and the mass percent of each component is:

Low Density Polyethylene 30% ~ 35%;

Ethylene-vinyl acetate copolymer 18% ~ 25%;

Poly-ring three phosphonitriles-sulfone microballoon 1% ~ 10%;

Magnesium hydroxide 25% ~ 35%;

Aluminium hydroxide 12% ~ 18%;

More than each constituent mass percentage composition sum be 100%.

Above-mentioned poly-ring three phosphonitriles-sulfone microballoon is ring three phosphonitriles-(4,4 '-dihydroxy diphenylsulphone) multipolymer, and its chemical structural formula is as follows:

。

Above-mentioned poly-ring three phosphonitriles-sulfone microballoon is median size 0.1 ~ 3 μ m of ring three phosphonitriles-(4,4 '-dihydroxy diphenylsulphone) multipolymer,

A kind of method for preparing the above-mentioned composite fire resistance cable material that contains poly-ring three phosphonitriles-sulfone microballoon is characterized in that the concrete steps of this method are:

(1) mixing of materials except magnesium hydroxide and aluminium hydroxide is even, obtain mixture A.

(2) magnesium hydroxide, aluminium hydroxide are evenly mixed, obtain mixture B;

(3) the mixture A adding Banbury mixer with step (1) carries out banburying, and the material temperature is made as 160 ~ 180 ℃; Behind banburying 5 ~ 10min, the mixture B adding Banbury mixer that step (2) obtains is proceeded banburying, the material temperature is made as 160 ~ 180 ℃, and banburying time 5 ~ 12min makes blend.

(4) blend that step (3) is made is put into open type plastic purificating set and is opened refining, and the material temperature is made as 170 ~ 190 ℃, carry out 5 ~ 20 times mixing, namely obtain containing the composite fire resistance cable material of poly-ring three phosphonitriles-sulfone microballoon.

Can be according to actual needs in the fire-resistant cable material of the present invention, add various additives, antioxidant for example: four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), three (2,4-di-tert-butyl-phenyl) phosphorous acid ester (oxidation inhibitor 168) etc.; Lubricant comprises PE wax, calcium stearate, Zinic stearas etc.

Compare with existing technology, product of the present invention has the following advantages:

1. high flame retardant, because poly-ring three phosphonitriles-sulfone microballoon height chemically crosslinked, has higher carbon yield, contain in the structure alternately arrange-the P=N-structure, composite with magnesium hydroxide, aluminium hydroxide, can improve the residual rate under the CABLE MATERIALS high temperature, obtain the good CABLE MATERIALS of flame retardant properties.

2. environmental protection, this CABLE MATERIALS is burnt under comparatively high temps, no matter is flaming combustion or flameless combustion, has the little advantage of the amount of being fuming, and toxicants such as simultaneously, cable is not leaded, antimony are a kind of environmental type CABLE MATERIALS.

3. long service life, selecting for use of oxidation inhibitor gives heat resistanceheat resistant, the ageing resistance of material excellence, and the CABLE MATERIALS of preparation has long work-ing life.

4. good machinery and processing characteristics, because poly-ring three phosphonitriles-sulfone microballoon and magnesium hydroxide, aluminium hydroxide have the cooperative flame retardant effect, can reduce the add-on of magnesium hydroxide, aluminium hydroxide, improve mechanical property and the processing characteristics of CABLE MATERIALS.Simultaneously, the lubricant in the prescription can increase the flowability of material, improves the processing characteristics of CABLE MATERIALS.

Embodiment

Embodiment one: each component and mass percent thereof are as follows:

The sheet material of above-mentioned CABLE MATERIALS or plate moulding preparation method, its preparation methods steps is as follows:

200g prepares burden by gross weight, with 60gLDPE, 40g ethylene-vinyl acetate copolymer, the poly-ring of 2g three phosphonitriles-sulfone microballoon, obtains mixture A.

Magnesium hydroxide 66g and aluminium hydroxide 32g are mixed, obtain mixture B.

Mixture A is added Banbury mixer carry out banburying, the material temperature is made as 160 ℃; Behind the banburying 5min, mixture B is added Banbury mixer proceed banburying, the material temperature is made as 160 ℃, and banburying time 10min makes blend.

The above-mentioned blend that makes is put into open type plastic purificating set opens refining, the material temperature be made as 180 ℃, carry out 20 times mixing, slice.

Sheet material after mixing is shredded, get and put into mould in right amount, the mould that sample is housed is put into vulcanizing press heat 4min down at 180 ℃, maintain the temperature at 180 ℃ then, with 15MPa pressure hot pressing 6min.Remove pressure, the mould that sample is housed is transferred to the vulcanizing press that temperature is room temperature rapidly, with the 15MPa pressure 5min that colds pressing, depanning obtains the poly-ring of LDPE/ three phosphonitriles-sulfone microballoon CABLE MATERIALS sheet material or sheet material.Then, this CABLE MATERIALS sheet material or sheet material are carried out the Performance Detection test, the results are shown in Table 1.

Embodiment two: contained component and mass percent thereof are as follows:

The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1, carries out the Performance Detection test, the results are shown in Table 1.

Embodiment three: contained component and mass percent thereof are as follows:

The preparation method of above-mentioned CABLE MATERIALS is identical with embodiment 1, carries out the Performance Detection test, the results are shown in Table 1.

Table 1:

。

Claims (4)

1. a composite fire resistance cable material that contains poly-ring three phosphonitriles-sulfone microballoon is characterized in that this CABLE MATERIALS mainly contains following component, and the mass percent of each component is:

Low Density Polyethylene 30% ~ 35%;

Ethylene-vinyl acetate copolymer 18% ~ 25%;

Poly-ring three phosphonitriles-sulfone microballoon 1% ~ 10%;

Magnesium hydroxide 25% ~ 35%;

Aluminium hydroxide 12% ~ 18%;

More than each constituent mass percentage composition sum be 100%.

2. the composite fire resistance cable material that contains poly-ring three phosphonitriles-sulfone microballoon according to claim 1 is characterized in that described poly-ring three phosphonitriles-sulfone microballoon is ring three phosphonitriles-(4,4 '-dihydroxy diphenylsulphone) multipolymer, and its chemical structural formula is as follows:

。

3. the composite fire resistance cable material that contains poly-ring three phosphonitriles-sulfone microballoon according to claim 2 is characterized in that described poly-ring three phosphonitriles-sulfone microballoon is median size 0.1 ~ 3 μ m of ring three phosphonitriles-(4,4 '-dihydroxy diphenylsulphone) multipolymer.

4. one kind prepares according to claim 1, the 2 or 3 described methods that contain the composite fire resistance cable material of poly-ring three phosphonitriles-sulfone microballoon, it is characterized in that the concrete steps of this method are:

(1) mixing of materials except magnesium hydroxide and aluminium hydroxide is even, obtain mixture A;

(2) magnesium hydroxide, aluminium hydroxide are evenly mixed, obtain mixture B;

(3) the mixture A adding Banbury mixer with step (1) carries out banburying, and the material temperature is made as 160 ~ 180 ℃; Behind banburying 5 ~ 10min, the mixture B adding Banbury mixer that step (2) obtains is proceeded banburying, the material temperature is made as 160 ~ 180 ℃, and banburying time 5 ~ 12min makes blend;

(4) blend that step (3) is made is put into open type plastic purificating set and is opened refining, and the material temperature is made as 170 ~ 190 ℃, carry out 5 ~ 20 times mixing, namely obtain containing the composite fire resistance cable material of poly-ring three phosphonitriles-sulfone microballoon.