CN104119614B - The Synthesis and applications of zinc hydroxyl stannate-polygorskite-trithiocyanuric acid compound smoke inhibition fire retardant - Google Patents

Abstract

Does is the invention provides a kind of zinc hydroxyl stannate-polygorskite-trithiocyanuric acid compound smoke inhibition fire retardant with good smoke-inhibiting flame retardant performance, that (its properity is see CN102515185 by zinc hydroxyl stannate-palygorskite mixture? A) carry out composite with the mass ratio of 20:1 ~ 1:1 with trithiocyanuric acid and obtain.Experiment shows, trithiocyanuric acid and zinc hydroxyl stannate-palygorskite mixture have good synergy, with it for fire retardant material prepared by additive becomes carbon respond well, can be widely used in the modification of plastics and all kinds of rubber.

Description

Preparation and application of zinc hydroxystannate-palygorskite-trithiocyanuric acid composite smoke suppressant flame retardant

technical field

The invention relates to a composite flame retardant, in particular to a preparation method of a zinc hydroxystannate-palygorskite-trimeric thiocyanate composite smoke-suppressing flame retardant; the present invention also relates to the composite smoke-suppressing flame retardant The application in the preparation of flame-retardant polymer materials.

Background technique

In recent decades, plastics, rubber, synthetic fibers and other polymer materials and their products have been vigorously developed. They are rapidly replacing traditional steel, metal products, cement and natural polymers such as wood and cotton, and are widely used in industries. , agriculture, military and other sectors of the national economy. In 2013, the production of plastic alone reached 299 million tons, and its volume was much larger than the volume of steel produced in the same year, which has become necessary for people's daily life. However, since most polymer materials are flammable, more and more polymer materials are used, and the fire situation caused by their application is very serious around the world. Moreover, when polymers burn, they not only release a lot of heat, but are often accompanied by A large amount of smoke and toxic gas are produced, causing serious damage to people's lives and property. Therefore, the preparation of high-performance flame-retardant materials has become an urgent problem to be solved by the society.

At present, the method of preparing polymer materials with high flame retardancy is to modify them by adding flame retardants. Among the many halogen-free flame retardant additives, zinc hydroxystannate [ZnSn(OH) ₆ , ZHS] has the advantages of non-toxicity, flame retardancy, and smoke suppression, and meets the requirements of today's green flame retardants. Research is progressing very rapidly into a possible alternative to antimony trioxide. Due to its special crystal structure and properties, palygorskite clay, as a nano-inorganic filler, can play a good role in flame retardancy and smoke suppression, and has been widely studied by scientific researchers. CN102515185A provides a zinc hydroxystannate-palygorskite clay composite, which is prepared by co-precipitation method using zinc chloride trihydrate, tin chloride and palygorskite clay as raw materials. The compound has high flame retardant performance and high smoke suppression performance. It is used to prepare flame retardant polyvinyl chloride material, which can replace the current antimony series flame retardant and smoke suppression agent, and obtain a compound with good flame retardant performance, smoke suppression performance and mechanical properties. Polymer Materials. However, the crystal form of the zinc hydroxystannate prepared by this method is complete, but the crystal particle size is large, and there are problems such as large dosage as a flame retardant and smoke suppressant, and serious damage to the mechanical properties of the material.

Due to the extremely high nitrogen content (51.83%), triazine compounds have the advantages of high density and good thermal stability. They can be used as gas generating agents and excellent charring agents for flame retardant materials. Among the numerous triazine compounds, thiocyanic acid (chemically named as 1,3,5-triazine-2,4,6-(1H.3H.5H)trithiol) is non-toxic and easy to disperse It is widely used in polymer modification due to its small dosage and safe process operation, but its single use does not contribute to the flame retardancy of composite materials. Therefore, there is no literature about thiocyanate. Report on flame retardant performance research.

Contents of the invention

The purpose of the present invention is to address the problems existing in the prior art and utilize the characteristics of thiocyanic acid to provide a zinc hydroxystannate-palygorskite-thiocyanic acid compound with good smoke suppression and flame retardant properties. The preparation method of smoke suppression flame retardant;

Another object of the present invention is to provide the application of a zinc hydroxystannate-palygorskite-thiocyanuric acid composite smoke suppression flame retardant in the preparation of flame-retardant polymer materials.

(1) Preparation of composite smoke suppressing flame retardant

1. Preparation of zinc hydroxystannate-palygorskite clay composite: dissolve ZnCl ₂ 3H ₂ O in water, add palygorskite clay 5-20 times the mass of ZnCl ₂ 3H ₂ O, heat to 80-95 ℃, stir for 20-40min; adjust the pH of the system to 5.0-6.4; add SnCl ₄ 5H ₂ O that is 2-5 times the mass of ZnCl ₂ 3H ₂ O, and stir for 10-25min; adjust the final pH of the reaction system to 9.0- 9.4, crystallize at room temperature for 3-5 hours, filter the precipitate, wash, dry, and grind to obtain the zinc hydroxystannate-palygorskite clay composite. For its structure and properties, refer to CN102515185A.

2. Preparation of composite smoke-suppressing flame retardant: Compound zinc hydroxystannate-palygorskite clay and thiocyanic acid at a mass ratio of 20:1 to 1:1.

Among the composite smoke suppressing flame retardants, zinc hydroxystannate-palygorskite clay mainly acts as a smoke suppressing agent, and thiocyanate mainly acts as a carbon forming agent, and the combination of the two produces a good synergistic effect. The flame retardant performance and smoke suppression effect of the composite smoke suppression flame retardant are greatly improved; moreover, the carbonization effect of the flame retardant material is good, and can be widely used in plastics such as polypropylene (PP), polyethylene (PE) , polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene copolymer (ABS), polystyrene (PS), polyethylene terephthalate (PET), polyamide (PA), poly In the modification of general plastics such as carbonate (PC), it can also be widely used in various types of rubber, such as natural rubber (NR), styrene-butadiene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), In the modification of nitrile rubber (NBR), butyl rubber (IIR), chloroprene rubber (CR), ethylene propylene rubber (EPDM) and acrylic rubber (ACM), etc.

(2) Preparation and performance testing of flame-retardant polymer materials

1. Preparation of flame-retardant polymer materials: adding zinc hydroxystannate-palygorskite-trithiocyanuric acid composite smoke-suppressing flame retardant to the polymer material matrix, and preparing flame-retardant materials by melting and kneading type polymer material; the matrix of the polymer material is plastic or rubber; the addition amount of the zinc hydroxystannate-palygorskite-mercaptan composite flame retardant is 20% to 45% of the mass of the polymer material matrix.

2. Test of performance indicators: Taking modified polypropylene as an example, the flame retardant properties of flame retardant polymer materials prepared with hydroxyzinc stannate-palygorskite-trithiocyanate composite flame retardant as additives, The smoke suppression performance and mechanical properties will be described.

(1) Flame retardant performance: test the limiting oxygen index of the sample according to GB/T2406.2-2009; test the horizontal and vertical combustion performance of the sample according to GB/T2408-2008. The results are as follows: more than 34, the horizontal combustion reaches the HB-a level, and the vertical combustion reaches the UL94V-0 level. Fully meet the requirements of GB/T8624-1997 on the combustion level of building materials reaching B ₁ and the regulations on the combustion of wire and cable sheath materials in YD/T1113-2001.

(2) Smoke density: test the smoke density of the sample according to GB/T8323.2-2008. The smoke density is less than 120 under flameless conditions.

(3) Mechanical properties: The tensile strength and elongation at break are tested according to GB1040. The test results are: the tensile strength is above 11.5MPa, and the elongation at break is above 125%. The properties of the material conform to the provisions of the industry standard YD/T1113-2001 on the mechanical properties of wire and cable sheathing materials.

In summary, the composite flame retardant prepared by the present invention has better flame retardant performance and smoke suppression performance than the prior art. Using it as an additive, the prepared modified polymer material has good flame retardancy, smoke suppression performance and mechanical performance.

detailed description

The preparation and performance of the composite flame retardant and the flame retardant polymer material of the present invention will be further described through specific examples below.

Example 1

(1) Preparation of zinc hydroxystannate-palygorskite composite: Dissolve 10g of ZnCl ₂ 3H ₂ O in 100ml of distilled water, add 50g of palygorskite clay (attapulgite), heat to 80°C, and stir for 20min . Use HCl to adjust the pH of the system to 5.0; add 20g of SnCl ₄ 5H ₂ O, stir vigorously for 10 minutes, use NaOH to adjust the final pH of the reaction system to 9.0, crystallize at room temperature for 3 hours, filter the precipitate, wash it, and then dry it in an oven , and ground through a 300m sieve to obtain zinc hydroxystannate-palygorskite composite;

(2) Preparation of composite flame retardant: compound zinc hydroxystannate-palygorskite composite with thiocyanic acid at a mass ratio of 1:1;

(3) Preparation of modified polypropylene: Add the above-mentioned hydroxyl composite flame retardant to the polypropylene matrix (the amount added is 20% of the polypropylene mass), and the flame retardant is prepared by the conventional process of melt mixing and additives. Combustible polypropylene material;

(4) Performance indicators of flame-retardant polypropylene: oxygen index is 38, horizontal combustion reaches HB-a level, vertical combustion reaches UL94V-0 level, smoke density is 110 under flameless conditions, tensile strength is 13MPa, elongation at break The length is 140%.

Example 2

(1) Preparation of zinc hydroxystannate-palygorskite composite: same as Example 1;

(2) Preparation of composite flame retardant: compound zinc hydroxystannate-palygorskite composite with thiocyanic acid at a mass ratio of 5:1;

(3) Preparation of modified polypropylene: add the above-mentioned hydroxyl composite flame retardant to the polypropylene matrix (the amount added is 30% of the polypropylene mass), and obtain the flame retardant through the conventional process of melt mixing and additives. Combustible polypropylene material;

(4) Performance indicators of flame-retardant polypropylene: oxygen index is 37, horizontal combustion reaches HB-a level, vertical combustion reaches UL94V-0 level, smoke density is 105 under flameless conditions, tensile strength is 12.3MPa, fracture The elongation was 141%.

Example 3

(1) Preparation of zinc hydroxystannate-palygorskite composite: same as Example 1;

(2) Preparation of composite flame retardant: compound zinc hydroxystannate-palygorskite composite with thiocyanuric acid at a mass ratio of 10:1;

(3) Preparation of modified polypropylene: add the hydroxyl composite flame retardant prepared above to the polypropylene matrix (the amount added is 40% of the polypropylene mass), and obtain the flame retardant through the conventional process of melt mixing and additives. Combustible polypropylene material;

(4) Performance indicators of flame-retardant polypropylene: oxygen index is 39, horizontal combustion reaches HB-a level, vertical combustion reaches UL94V-0 level, smoke density is 98 under flameless conditions, tensile strength is 12MPa, elongation at break The elongation rate is 135%.

Example 4

(1) Preparation of zinc hydroxystannate-palygorskite composite: same as Example 1;

(2) Preparation of composite flame retardant: compound the zinc hydroxystannate-palygorskite composite with thiocyanic acid at a mass ratio of 15:1;

(3) Preparation of modified polypropylene: Add the above-mentioned hydroxyl compound flame retardant to the polypropylene matrix (the amount added is 45% of the polypropylene mass), and the flame retardant is prepared by the conventional process of melt mixing and additives. Combustible polypropylene material;

(4) Performance indicators of flame-retardant polypropylene: oxygen index is 40, horizontal combustion reaches HB-a level, vertical combustion reaches UL94V-0 level, smoke density is 87 under flameless conditions, tensile strength is 11.5MPa, fracture The elongation is 125%.

Example 5

(1) Preparation of zinc hydroxystannate-palygorskite composite: same as Example 1;

(2) Preparation of composite flame retardant: compound zinc hydroxystannate-palygorskite composite with thiocyanic acid at a mass ratio of 20:1;

(3) Preparation of modified polypropylene: add the above-mentioned hydroxyl composite flame retardant to the polypropylene matrix (the amount added is 30% of the polypropylene mass), and obtain the flame retardant through the conventional process of melt mixing and additives. Combustible polypropylene material;

(4) Performance indicators of flame-retardant polypropylene: oxygen index is 34, horizontal combustion reaches HB-a level, vertical combustion reaches UL94V-0 level, smoke density is 120 under flameless conditions, tensile strength is 13.6MPa, fracture The elongation was 131%.

Claims (2)

1. a kind of preparation method of zinc hydroxystannate-palygorskite-thiocyanuric acid compound smoke suppression flame retardant is that zinc hydroxystannate-palygorskite clay compound and thiocyanic acid are mixed with 20: Compounded at a mass ratio of 1 to 1:1; The preparation process of the zinc hydroxystannate-palygorskite clay compound is as follows: dissolving ZnCl ₂ 3H ₂ O in water, adding palygorskite clay 5 to 20 times the mass of ZnCl ₂ 3H ₂ O, heating to 80 ~95°C, stir for 20-40min; adjust the pH of the system to 5.0-6.4; add SnCl ₄ 5H ₂ O 2-5 times the mass of ZnCl ₂ 3H ₂ O, stir for 10-25min; adjust the final pH of the reaction system= 9.0 to 9.4, crystallize at room temperature for 3 to 5 hours, filter the precipitate, wash, dry, and grind to obtain zinc hydroxystannate-palygorskite clay composite. 2. the application of zinc hydroxystannate-palygorskite-tripolythiocyanate composite smoke-suppressing flame retardant prepared by the method as claimed in claim 1 in the preparation of flame-retardant polymer materials is characterized in that: the hydroxytin Zinc acid-palygorskite-trimeric thiocyanate composite smoke-suppressing flame retardant is added to the polymer material matrix, and the flame-retardant polymer material is prepared by melting and mixing; The addition amount of the zinc hydroxystannate-palygorskite-thiocyanuric acid composite flame retardant is 20%-45% of the mass of the polymer material matrix; the polymer material matrix is plastic.