CN106317627A - Method for preparing bio-based intumescent flame retardant - Google Patents

Abstract

The invention discloses a method for preparing a bio-based intumescent flame retardant, and belongs to the technical field of flame retardant materials. The method includes the steps that tea seeds are smashed to be puffed, the puffed tea seeds are subjected to enzymolysis, enzymolysis is completed, the temperature is increased, enzyme deactivation is carried out, then hydrochloric acid is added, tea saponin is precipitated accordingly, centrifugal separation is carried out, lower precipitation is dissolved in alcohol liquid and filtered, the filtered liquid is subjected to reduced pressure distillation, and tea saponin is obtained; the tea saponin is dissolved in an ethanol solution, the mixture and thionyl chloride are reacted to generate amide, then the amide, tripolycyanamide and urea are reacted, and the product is obtained; the product is modified and dried with a silane coupling agent, and the product and magnesium hydrate and the like are jointly subjected to ball milling, and the bio-based intumescent flame retardant can be obtained. The amide substance generated in the tea saponin reaction can be mixed with ammonium polyphosphate and can also be reacted with the urea; as a cross-linked polymer which is of a three-dimensional structure is obtained through reacting between molecules, the polymer flame retardant and a high polymer material have the quite good compatibility, and the moisture absorption phenomenon cannot be generated.

Description

A kind of preparation method of bio-based expanding fire retardant

Technical field

The invention discloses the preparation method of a kind of bio-based expanding fire retardant, belong to fire proofing technical field.

Background technology

Fire proofing is as concerning social safety and the material of people's security of the lives and property, and its research and production are to closing weight Want.In numerous fire retardant kinds, it is few that halogen flame has good flame retardation effect, consumption, the Effect on Mechanical Properties to material The advantage such as little, uses as main organic fire-retardant kind the most always, but due to halogenated flame retardant self defect, The promotion of industrial quarters and cost factor, the application of halogen-containing flame retardant will reduce.Inorganic combustion inhibitor such as metal-oxide, Silicate etc. have the advantage that the amount of being fuming is few, do not produce poison, but the addition that this based flame retardant needs is big, commonly greater than 60%, this will greatly affect the mechanical property of material.Nowadays, the expansion type flame retardant with P, N, C as essential core is Receive more and more attention.It has cigarette efficient, low, low toxicity, addition few, without advantages such as molten drops, have in some material There is the fire-retardant performance more excellent than other fire retardants, the most just by increasing application and various composites.And And expansion type flame retardant technology has become as one of the most most active fire-retardant research field, its research has a extensive future.

Expansion type flame retardant is commonly divided into organic phosphorous expansion type flame retardant and inorganic expansion type graphite fire retardant two is big Class.Expanding fire retardant system is typically made up of acid source, charcoal source and source of the gas 3 part.Wherein the function of acid source is, with charcoal source, ester occurs Change reaction, be allowed to be dehydrated.Source of the gas refers to discharge the most nontoxic and compound of nonflammable gas when decomposes.Charcoal source The very important part of expansion type flame retardant, refer in combustion can dehydrated dose seize moisture and by the thing of carbonization Matter.Expansion type flame retardant is the most sensitive to humidity, and the required addition of each component is big, causes certain wasting of resources, and becomes Charcoal is unstable, and these factors all can cause fire resistance or the mechanical properties decrease of material, thus limit expansion type flame retardant Application.

Summary of the invention

The technical problem that present invention mainly solves: exist for the most traditional expansion type flame retardant and affected relatively by moisture Greatly, becoming the defect that charcoal is unstable, cause the fire resistance of material and the phenomenon of mechanical properties decrease, the present invention is first by tea-seed Carrying out expanding treatment after pulverizing, make part tea-seed oil discharge, then the tea-seed after expanded is carried out enzymolysis, enzymolysis is tied Intensification enzyme denaturing after bundle, adds hydrochloric acid, makes tea saponin precipitate, after being then centrifuged for separating, after lower sediment is dissolved in ethanol solution Filter, filtrate decompression distilled, obtains tea saponin, after tea saponin is dissolved in ethanol solution, react generation amide with thionyl chloride, The most again with tripolycyanamide, urea reaction, obtaining product, recycle silicon alkane coupling agent is to product modification, dried and magnesium hydroxide Etc. common ball milling, i.e. can get bio-based expanding fire retardant.The amide material that in the present invention, tea saponin reaction generates both can be with APP reaction can also be with urea reaction, due to the cross linked polymer obtaining stereochemical structure that reacts to each other between molecule, this Base polymer fire retardant and macromolecular material have the good compatibility, and will not produce hygroscopic effect.

In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is:

(1) weigh 200～300g tea-seed, be placed in pulverizer pulverizing, be subsequently added in screw extrusion machine, Under 110～120 DEG C, 0.03～0.05MPa expanded 30～40min, obtain expanded after tea-seed powder, wherein screw speed It is 130～140r/min；

(2) by above-mentioned expanded after tea-seed powder join in enzymatic vessel, add 600～700mL deionized waters, stir 10 ～after 20min, add 0.3～0.5g neutral protease, and enzymolysis 2～3h at 35～45 DEG C, after enzymolysis terminates, it is warming up to 100～110 DEG C, stirring 10～20min, adding 50～60mL mass fractions is 10% hydrochloric acid, stirs 5～10min, then will Enzymolysis solution is placed in a centrifuge, and is centrifuged 30～40min, removes supernatant, obtain lower sediment under 5000～6000r/min；

(3) lower sediment is joined that to add 300～400mL mass fractions in beaker be 75% ethanol solution, stirring 10～ 20min, filters, obtains filtrate, filtrate decompression is distilled, obtains tea saponin, take 10～20g tea saponin solution and join with temperature In the there-necked flask of degree meter and reflux, flask is placed in water-bath, is warming up to 80～90 DEG C, add 100～200mL Mass fraction is 75% ethanol solution, stirs 10～20min, adds 5～8mL thionyl chlorides, is stirred at reflux reaction 3～4h, then Add 8～12g APPs, stirring reaction 2～3h, sequentially add 1～3g carbamide, 0.3～0.5g iron chloride, stirring reaction 1～2h, obtain product；

(4) in above-mentioned product, add 1～3g γ-aminopropyl triethoxysilane, stir 2～3h, be subsequently placed in baking oven In, it is dried 5～6h at 50～60 DEG C, then naturally cools to room temperature, be subsequently transferred in ball mill, add 2～4g hydrogen-oxygens Change magnesium, 3～5g aluminium hydroxide, 1～3g ferrocene, ball milling 3～4h, obtain mixed-powder, i.e. bio-based expanding fire retardant.

The application process of the present invention is: take the bio-based expanding fire retardant that the 20～25g present invention prepare, 70～75g poly-third Alkene is placed in twin-roll plastic mixing mill, temperature 170～180 DEG C mixing 10～12min, on vulcanizing press at a temperature of 150 DEG C Carrying out hot pressing, room temperature cold moudling, 60～70 DEG C aging 7～8h, sample preparation in universal sampling machine, the hot strength of sample 26.5～28.5MPa, fire resistance is preferable.

The invention has the beneficial effects as follows:

(1) preparation condition of the present invention is gentle, easily controllable, reproducible, productivity is high, low cost, and heat stability improves, carbon left Also increase；

(2) the bio-based expanding fire retardant present invention prepared is applied to polypropylene fire retardant system, and the compatibility improves, flame-retardant polypropylene Alkene mechanical property, fire resistance etc. are effectively improved and are suitable for large-scale production and application.

Detailed description of the invention

First weigh 200～300g tea-seed, be placed in pulverizer pulverizing, be subsequently added to screw extrusion In machine, under 110～120 DEG C, 0.03～0.05MPa expanded 30～40min, obtain expanded after tea-seed powder, wherein spiral shell Bar rotating speed is 130～140r/min；By above-mentioned expanded after tea-seed powder join in enzymatic vessel, add 600～700mL Deionized water, after stirring 10～20min, adds 0.3～0.5g neutral protease, enzymolysis 2～3h, enzymolysis at 35～45 DEG C After end, be warming up to 100～110 DEG C, stir 10～20min, adding 50～60mL mass fractions is 10% hydrochloric acid, stirring 5～ 10min, is then placed in a centrifuge enzymolysis solution, is centrifuged 30～40min, removes supernatant under 5000～6000r/min, To lower sediment；Lower sediment being joined in beaker and adding 300～400mL mass fractions is 75% ethanol solution, stirs 10 ～20min, filter, obtain filtrate, by filtrate decompression distill, obtain tea saponin, take 10～20g tea saponin solution join with In the there-necked flask of thermometer and reflux, flask is placed in water-bath, is warming up to 80～90 DEG C, add 100～ 200mL mass fraction is 75% ethanol solution, stir 10～20min, add 5～8mL thionyl chlorides, be stirred at reflux reaction 3～ 4h, adds 8～12g APPs, stirring reaction 2～3h, sequentially adds 1～3g carbamide, 0.3～0.5g iron chloride, stir Mix reaction 1～2h, obtain product；In above-mentioned product, add 1～3g γ-aminopropyl triethoxysilane, stir 2～3h, It is subsequently placed in baking oven, is dried 5～6h at 50～60 DEG C, then naturally cools to room temperature, be subsequently transferred in ball mill, then add Enter 2～4g magnesium hydroxide, 3～5g aluminium hydroxide, 1～3g ferrocene, ball milling 3～4h, obtain mixed-powder, i.e. bio-based expands Fire retardant.

Example 1

First weigh 200g tea-seed, be placed in pulverizer pulverizing, be subsequently added in screw extrusion machine, 110 DEG C, expanded 30min under 0.03MPa, obtain expanded after tea-seed powder, wherein screw speed is 130r/min；By above-mentioned Tea-seed powder after expanded joins in enzymatic vessel, adds 600mL deionized water, after stirring 10min, adds in 0.3g Property protease, enzymolysis 2h at 35 DEG C, after enzymolysis terminates, be warming up to 100 DEG C, stir 10min, adding 50mL mass fraction is 10% hydrochloric acid, stirs 5min, is then placed in a centrifuge by enzymolysis solution, and under 5000r/min, centrifugal 30min, removes supernatant, Obtain lower sediment；Lower sediment being joined in beaker and adding 300mL mass fraction is 75% ethanol solution, stirring 10min, filters, obtains filtrate, filtrate decompression is distilled, obtains tea saponin, take 10g tea saponin solution and join with thermometer With in the there-necked flask of reflux, being placed in water-bath by flask, be warming up to 80 DEG C, adding 100mL mass fraction is 75% Ethanol solution, stirs 10min, adds 5mL thionyl chloride, is stirred at reflux reaction 3h, adds 8g APP, stirring reaction 2h, sequentially adds 1g carbamide, 0.3g iron chloride, stirring reaction 1h, obtains product；1g γ-ammonia is added in above-mentioned product Propyl-triethoxysilicane, stirs 2h, is subsequently placed in baking oven, at 50 DEG C of dry 5h, then naturally cools to room temperature, turn subsequently Move on in ball mill, add 2g magnesium hydroxide, 3g aluminium hydroxide, 1g ferrocene, ball milling 3h, obtain mixed-powder, i.e. biological Base expanding fire retardant.

The application process of the present invention is: take the bio-based expanding fire retardant that the 20g present invention prepares, and 70g polypropylene is placed in double In roller plasticator, at 170 DEG C of mixing 10min of temperature, carrying out hot pressing on vulcanizing press at a temperature of 150 DEG C, room temperature is colded pressing Molding, in 60 DEG C of aging 7h, sample preparation in universal sampling machine, hot strength 26.5MPa of sample, fire resistance is preferable.

Example 2

First weigh 250g tea-seed, be placed in pulverizer pulverizing, be subsequently added in screw extrusion machine, 115 DEG C, expanded 35min under 0.04MPa, obtain expanded after tea-seed powder, wherein screw speed is 135r/min；By above-mentioned Tea-seed powder after expanded joins in enzymatic vessel, adds 650mL deionized water, after stirring 15min, adds in 0.4g Property protease, enzymolysis 2.5h at 40 DEG C, after enzymolysis terminates, be warming up to 105 DEG C, stir 15min, add 55mL mass fraction Being 10% hydrochloric acid, stir 7min, be then placed in a centrifuge by enzymolysis solution, under 5500r/min, centrifugal 35min, removes supernatant Liquid, obtains lower sediment；Lower sediment being joined in beaker and adding 350mL mass fraction is 75% ethanol solution, stirring 15min, filters, obtains filtrate, filtrate decompression is distilled, obtains tea saponin, take 15g tea saponin solution and join with thermometer With in the there-necked flask of reflux, being placed in water-bath by flask, be warming up to 85 DEG C, adding 150mL mass fraction is 75% Ethanol solution, stirs 15min, adds 7mL thionyl chloride, is stirred at reflux reaction 3.5h, adds 10g APP, stirring Reaction 2.5h, sequentially adds 2g carbamide, 0.4g iron chloride, stirring reaction 1.5h, obtains product；2g is added in above-mentioned product γ-aminopropyl triethoxysilane, stirs 2.5h, is subsequently placed in baking oven, at 55 DEG C of dry 5.5h, then naturally cools to Room temperature, is subsequently transferred in ball mill, adds 3g magnesium hydroxide, 4g aluminium hydroxide, 2g ferrocene, ball milling 3.5h, is mixed Close powder, i.e. bio-based expanding fire retardant.

The application process of the present invention is: take the bio-based expanding fire retardant that the 23g present invention prepares, and 73g polypropylene is placed in double In roller plasticator, at 175 DEG C of mixing 11min of temperature, carrying out hot pressing on vulcanizing press at a temperature of 150 DEG C, room temperature is colded pressing Molding, in 65 DEG C of aging 7.5h, sample preparation in universal sampling machine, sample hot strength 27.5MPa, fire resistance is preferable.

Example 3

First weigh 300g tea-seed, be placed in pulverizer pulverizing, be subsequently added in screw extrusion machine, 120 DEG C, expanded 40min under 0.05MPa, obtain expanded after tea-seed powder, wherein screw speed is 140r/min；By above-mentioned Tea-seed powder after expanded joins in enzymatic vessel, adds 700mL deionized water, after stirring 20min, adds in 0.5g Property protease, enzymolysis 3h at 45 DEG C, after enzymolysis terminates, be warming up to 110 DEG C, stir 20min, adding 60mL mass fraction is 10% hydrochloric acid, stirs 10min, is then placed in a centrifuge by enzymolysis solution, and under 6000r/min, centrifugal 40min, removes supernatant, Obtain lower sediment；Lower sediment being joined in beaker and adding 400mL mass fraction is 75% ethanol solution, stirring 20min, filters, obtains filtrate, filtrate decompression is distilled, obtains tea saponin, take 20g tea saponin solution and join with thermometer With in the there-necked flask of reflux, being placed in water-bath by flask, be warming up to 90 DEG C, adding 200mL mass fraction is 75% Ethanol solution, stirs 20min, adds 8mL thionyl chloride, is stirred at reflux reaction 4h, adds 12g APP, and stirring is anti- Answer 3h, sequentially add 3g carbamide, 0.5g iron chloride, stirring reaction 2h, obtain product；In above-mentioned product add 3g γ- Aminopropyl triethoxysilane, stirs 3h, is subsequently placed in baking oven, at 60 DEG C of dry 6h, then naturally cools to room temperature, subsequently Transfer in ball mill, add 4g magnesium hydroxide, 5g aluminium hydroxide, 3g ferrocene, ball milling 4h, obtain mixed-powder, the most raw Thing base expanding fire retardant.

The application process of the present invention is: take the bio-based expanding fire retardant that the 25g present invention prepares, and 75g polypropylene is placed in double In roller plasticator, at 180 DEG C of mixing 12min of temperature, carrying out hot pressing on vulcanizing press at a temperature of 150 DEG C, room temperature is colded pressing Molding, in 70 DEG C of aging 8h, sample preparation in universal sampling machine, sample hot strength 28.5MPa, fire resistance is preferable.

Claims (1)

1. the preparation method of a bio-based expanding fire retardant, it is characterised in that concrete preparation process is:

(1) weigh 200～300g tea-seed, be placed in pulverizer pulverizing, be subsequently added in screw extrusion machine, Under 110～120 DEG C, 0.03～0.05MPa expanded 30～40min, obtain expanded after tea-seed powder, wherein screw speed It is 130～140r/min；

(2) by above-mentioned expanded after tea-seed powder join in enzymatic vessel, add 600～700mL deionized waters, stir 10 ～after 20min, add 0.3～0.5g neutral protease, and enzymolysis 2～3h at 35～45 DEG C, after enzymolysis terminates, it is warming up to 100～110 DEG C, stirring 10～20min, adding 50～60mL mass fractions is 10% hydrochloric acid, stirs 5～10min, then will Enzymolysis solution is placed in a centrifuge, and is centrifuged 30～40min, removes supernatant, obtain lower sediment under 5000～6000r/min；

(3) lower sediment is joined that to add 300～400mL mass fractions in beaker be 75% ethanol solution, stirring 10～ 20min, filters, obtains filtrate, filtrate decompression is distilled, obtains tea saponin, take 10～20g tea saponin solution and join with temperature In the there-necked flask of degree meter and reflux, flask is placed in water-bath, is warming up to 80～90 DEG C, add 100～200mL Mass fraction is 75% ethanol solution, stirs 10～20min, adds 5～8mL thionyl chlorides, is stirred at reflux reaction 3～4h, then Add 8～12g APPs, stirring reaction 2～3h, sequentially add 1～3g carbamide, 0.3～0.5g iron chloride, stirring reaction 1～2h, obtain product；

(4) in above-mentioned product, add 1～3g γ-aminopropyl triethoxysilane, stir 2～3h, be subsequently placed in baking oven In, it is dried 5～6h at 50～60 DEG C, then naturally cools to room temperature, be subsequently transferred in ball mill, add 2～4g hydrogen-oxygens Change magnesium, 3～5g aluminium hydroxide, 1～3g ferrocene, ball milling 3～4h, obtain mixed-powder, i.e. bio-based expanding fire retardant.