CN102675691A

CN102675691A - Organosilicone modified aluminum hydroxide fire retardant and preparation method thereof

Info

Publication number: CN102675691A
Application number: CN2012101905238A
Authority: CN
Inventors: 楼芳彪
Original assignee: Individual
Current assignee: Individual
Priority date: 2012-06-05
Filing date: 2012-06-05
Publication date: 2012-09-19
Anticipated expiration: 2032-06-05
Also published as: CN102675691B

Abstract

The invention provides an organosilicone modified aluminum hydroxide fire retardant and a preparation method thereof. According to the fire retardant and the method, condensation reaction is performed on methyl trichlorosilane and relatively active hydroxyl in aluminum hydroxide, and silicon methyl is imported onto the aluminum hydroxide so that the organosilicone modified aluminum hydroxide fire retardant has good hydrophobicity, thereby enhancing the compatibility with high polymer substrates and exerting the synergistic flame retarding effect. The organosilicone modified aluminum hydroxide fire retardant prepared by using the method has good thermal stability and high decomposition temperature, and can remarkably improve the flame retardant property and the mechanical property of high polymers. The type of fire retardants can be widely applied to rubber and plastic high polymer materials such as poly flammable hydrocarbon, can be nontoxic and smokeless, and can meet the environmental requirements.

Description

A kind of organic-silicon-modified aluminium hydroxide fire retardant and preparation method thereof

Technical field

The invention belongs to the fire retardant synthesis technical field, relate to the halogen-free inorganic flame retardant technology of preparing, particularly the aluminium hydroxide fire retardant modification technology.

Background technology

Current high molecular synthetic material all is used widely in every field, but because of macromolecular material inflammable, so fire-retardant research focus that has become countries in the world of macromolecular material.The fire retardant of addition type is easy to use because of it, and application quantity is also increasing.Additive flame retardant is divided into inorganic and organic two big types.Inorganic combustion inhibitor mainly contains white lake, Marinco H, red phosphorus, ammonium polyphosphate, weisspiessglanz etc.White lake in the mineral-type fire retardant because of its have concurrently fire-retardant, fill, press down multiple function such as cigarette, the fire retardant material that uses white lake can not produce poisonous and corrosive gases when meeting high heat burning.So white lake has become the maximum environmental protection inorganic fire retardant of current usage quantity.

White lake is claimed hibbsite (ATH) again, and molecular formula is Al ₂O ₃3H ₂O or Al (OH) ₃The fire retardant mechanism of ATH it has been generally acknowledged that following four aspects: 1. fill and make polymer concentration decline; 2. decomposes heat absorption reduces polymer temperature; 3. decompose the water vapor dilution inflammable gas and the concentration of oxygen that discharge; 4. decompose the Al that generates ₂O ₃The overlie polymer surface, starvation.When using ATH to make fire retardant separately, addition will reach more than 60% just can play flame retardant effect preferably.Because of ATH is hydrophilic, bad with the superpolymer consistency, so big addition will have a strong impact on the processing characteristics and the mechanical property of fire-retardant superpolymer, therefore need make surface modification treatment to ATH.The surface-modifying agent of ATH is selected silane coupling agent, titanium (zirconium) acid esters coupling agent, hard ester acid (salt) etc. usually for use." aluminium hydroxide fire retardant of a kind of surface-treated and preparation method thereof " (CN200710069077.4) adopts (Asia) SULPHOSUCCINIC ACID ESTER and silane coupling agent to carry out surface treatment; " a kind of method of modifying of white lake/flame retardant of magnesium hydroxide " (CN20101028830.0) adopts elder generation to be adsorbed in powder surface with radical polymerization-type resin, re-uses radiation-initiated polymerization and carries out surface-treated in the method that powder surface forms the polymer coating film; " a kind of preparation method of silicone oil surface-treated aluminium hydroxide fire retardant " (CN20101053724.8) earlier with silicone oil with physical adsorption in the ATH surface, spray the method that the surface hydroxyl of functional group that catalyzer makes silicone oil and ATH reacts again and handle.The silane coupling agent price that aforesaid method is selected for use is more expensive, and the treatment process that has is comparatively complicated, and mass market is promoted has certain influence.

Summary of the invention

The present invention is directed to the deficiency of prior art, a kind of preparation method of organic-silicon-modified aluminium hydroxide fire retardant newly is provided.The present invention selects for use the METHYL TRICHLORO SILANE (being called for short a first) of the cheapness of by-product in the maximum an organosilane monomer methyl chlorosilane production of China's production capacity as organosilicon modifier; Make it with ATH on comparatively active-OH base chemical reaction takes place, generate organic-silicon-modified aluminium hydroxide fire retardant.

Al (OH) ₃Seen three-OH group from molecular formula, METHYL TRICHLORO SILANE has three active Si-Cl keys, can with active-OH base attack.But experiment be illustrated in only have an appointment among the ATH 1/3rd-OH can with a first attack, emit HCl gas, condensation forms an Al-O-Si key.See from the fire retardant mechanism of ATH, also can not make all-OH base all with a first dereaction, otherwise will lose flame retardant effect.Therefore see from molecular structure, METHYL TRICHLORO SILANE will with each one-OH radical reaction of three ATH, be condensed into a bigger molecule.Since on this molecule first line of a couplet the silicon methyl, therefore have better hydrophobic can, strengthened the consistency of this fire retardant and superpolymer base material, can obviously improve the processing characteristics and the mechanical property of fire-retardant superpolymer.Owing in flame retardant molecule, introduced element silicon, can bring into play the cooperative flame retardant effect preferably in addition.

The preparation method of the organic-silicon-modified white lake that the present invention proposes comprises two kinds of technologies of wet method and semidrying.

Wet processing: ATH is put into reaction system; Add an amount of diluting solvent as required and make it to be uniformly dispersed, add an amount of methyl three oxosilanes, the mol ratio of white lake and METHYL TRICHLORO SILANE is 1: 0.2-0.35; Control reaction temperature 40-120 ℃; Reaction 2-10h, the HCl gas of emitting absorbs with alkali lye, emits until no HCl.The upper strata thinner is poured out in cooling, and the evaporation of heating eliminates thinner (thinner is all reusable).Add water washing, filtration, being washed till does not have cl ions in the filtrating, and drying obtains the good organic-silicon-modified aluminium hydroxide fire retardant of hydrophobicity.

Semidry process: ATH is put into reaction system, add METHYL TRICHLORO SILANE,, can add an amount of thinner, stir and make it evenly moistening if be necessary.The same wet processing of other processing condition.

The thinner that wet processing adopts is at least a in hexanaphthene, the benzene,toluene,xylene.

The thinner that semidry process is selected for use can be a kind of in the thinner used in methylene dichloride, trichloroethane, acetone or the wet processing.

Embodiment

Following embodiment is to further explain of the present invention, but the present invention is not limited to the embodiment of following proposition.

Embodiment 1

Take by weighing 78g (1mol) Al (OH) ₃Be added in the there-necked flask that whisking appliance, cold doubtful pipe are housed, the prolong upper end connects gas absorbing device, and there-necked flask places temperature automatically controlled oil bath pan.Add the 250ml hexanaphthene, stir and make Al (OH) ₃Homodisperse.Add 30g (0.2mol) METHYL TRICHLORO SILANE again, 45 ℃ of stirring reaction 1h of temperature control, 60 ℃ of 3h, 85 ℃ of 5h, the HCl gas of emitting in the reaction process absorbs with alkali lye, detects and emits until no HCl gas.Leave standstill cooling, pour out the upper strata solvent, most solvent (recyclable use again) is taken off in reheat evaporation.Add 200ml zero(ppm) water again, stir 0.5h, filter, in filtrating, do not have cl ions with distilled water wash at 50-60 ℃.Be drying to obtain white hydrophobic powder 84g, yield 97%, the hydrophobic performance of product is fine, places in the water still not sink in a week.

Embodiment 2

Take by weighing 78g (1mol) Al (OH) ₃Be added in the reaction system like embodiment 1, add 250ml benzene, stir and make Al (OH) ₃Homodisperse.Add 37.5g (0.25mol) METHYL TRICHLORO SILANE again, 45 ℃ of stirring reaction 1h of temperature control, 60 ℃ of 3h, 85 ℃ of 5h, detecting has not had HCl gas and has emitted, and the subsequent disposal measure is with embodiment 1.Obtain white hydrophobic powder 85g, yield 95.8%.The hydrophobic performance of product is with embodiment 1.

Embodiment 3

Take by weighing 78g (1mol) Al (OH) ₃Be added in the reaction system like embodiment 1, add 250ml toluene, stir and make it homodisperse.Add 52.5g (0.35mol) METHYL TRICHLORO SILANE again, 45 ℃ of stirring reaction 1h of temperature control, 60 ℃ of 2h, 100 ℃ of 4h, detection has not had HCl gas and has emitted.The subsequent disposal measure is with embodiment 1.Obtain white hydrophobic powder 88.5g, yield 95.2%.The hydrophobic performance of product is the same.

Embodiment 4

Take by weighing 156g (2mol) Al (OH) ₃Be added in the reaction system like embodiment 1, add 60g (0.4mol) METHYL TRICHLORO SILANE that has diluted with the 40ml methylene dichloride again, stir and make it evenly moistening.45 ℃ of stirring reaction 1h of temperature control, 60 ℃ of 3h, 90 ℃ of 5h, detecting has not had HCl gas and has emitted, and steams diluting solvent to the greatest extent, and the subsequent disposal measure obtains white hydrophobic powder 168g with embodiment 1, yield 97.1%.The hydrophobic performance of product is the same.

Embodiment 5

Take by weighing 156g (2mol) Al (OH) ₃In the reaction system of adding with embodiment 1, add 90g (0.6mol) METHYL TRICHLORO SILANE of having used the 20ml acetone diluted again, stir and make it evenly moistening.45 ℃ of stirring reaction 1h of temperature control, 60 ℃ of 2h, 100 ℃ of 4h, detecting has not had HCl gas and has emitted, and steams diluting solvent to the greatest extent, and the subsequent disposal measure obtains white hydrophobic powder 175g with embodiment 1, yield 96.3%, the hydrophobic performance of product is the same.

Embodiment 6

Take by weighing 312g (4mol) Al (OH) ₃In the reaction system of adding with embodiment 1, add 210g (1.4mol) METHYL TRICHLORO SILANE again, stir and make it evenly moistening.45 ℃ of stirring reaction 1h of temperature control, 60 ℃ of 3h, 110 ℃ of 4h, detecting has not had HCl gas and has emitted, and the subsequent disposal measure obtains white hydrophobic powder 355g with embodiment 1, yield 95.4%, the hydrophobic performance of product is the same.With products obtained therefrom and undressed Al (OH) ₃Opposing complies the thermal weight loss test, and the result is as shown in table 1:

Table 1 thermal weight loss data

Can find out the Al that handled (OH) from last table ₃Heat resisting temperature is apparently higher than undressed control sample.

Application examples

The organic-silicon-modified aluminium hydroxide fire retardant that makes by embodiment 6 conditions and Vestolen PP 7052 (PP), oxidation inhibitor (0.2%), lubricant (0.8%) thorough mixing in high-speed mixer; Be transferred to twin screw again and extrude middle extruding pelletization; Fire-retardant pellet is at 90-95 ℃ of dry 2h; Be injection molded into various standard strips with injection moulding machine, by relevant criterion its flame retardant properties of test and mechanical property.With undressed aluminium hydroxide fire retardant with condition as control samples, its result sees table 2:

Table 2 different flame retardant and consumption fire Effect on Performance to flame-retardant polypropylene

Can find out that from last table the organic-silicon-modified aluminium hydroxide fire retardant that the present invention makes is applied to Vestolen PP 7052, its flame retardant properties and mechanical property all obviously are superior to undressed same based flame retardant.

Claims

1. an organic-silicon-modified aluminium hydroxide fire retardant is characterized in that, is formed by METHYL TRICHLORO SILANE and white lake reaction.

2. fire retardant according to claim 1 is characterized in that: the mol ratio of METHYL TRICHLORO SILANE and white lake is 0.2-0.35: 1.

3. the preparation method of the described fire retardant of claim 1 comprises two kinds of technologies of wet processing and semidry process.

4. preparation method according to claim 3; Wet processing is: white lake is put into reaction system, add an amount of thinner stirring and make it to be uniformly dispersed, add an amount of METHYL TRICHLORO SILANE again; At 40-120 ℃ of reaction 2-10h, reaction product is carried out purifying, drying.Semidry process is: white lake is put into reaction system, add an amount of METHYL TRICHLORO SILANE, if be necessary, can add the small diluted amount agent, stir and make it evenly moistening, the same wet processing of method for subsequent processing.

5. preparation method according to claim 4 is characterized in that, the described thinner of wet processing is at least a in hexanaphthene, the benzene,toluene,xylene; The described thinner of semidry process can be a kind of in the used thinner in methane dioxide, trichloroethane, acetone or the wet processing.

6. preparation method according to claim 4, its purification process is: evaporation eliminates the thinner in the reactant, and heated and stirred, filtration, washing do not have cl ions to filtrating.