CN102383210A - Phosphor nitrogen fire retardant dispersion and preparation method thereof - Google Patents

Abstract

The invention relates to a phosphorus-nitrogen flame retardant dispersion and a preparation method thereof, belonging to the field of fine chemicals. The present invention aims to solve the problem that the flame retardant dispersion made of viscose fiber flame retardant has poor stability and is difficult to realize large-scale industrial production in the prior art, and provides a phosphorus nitrogen flame retardant dispersion and its preparation method. In the method of the present invention, by adding a certain proportion of wetting agent, polymer dispersant and deflocculating dispersant, adding an appropriate defoamer, and performing high-speed dispersion and stirring in a cylinder, the phosphorus-nitrogen flame retardant is dispersed The liquid has uniform dispersion, good stability, good compatibility with viscose liquid, and good spinnability. It is an acid-resistant and alkali-resistant flame-retardant dispersion liquid with a wide range of applications; the phosphorus nitrogen prepared by the present invention It is a fiber made by mixing flame retardant dispersion and viscose, spinning and post-processing. The limiting oxygen index is above 30, and the fiber has good physical and mechanical properties.

Description

A kind of phosphorus nitrogen flame retardant dispersion liquid and preparation method thereof

technical field

The invention relates to a flame retardant dispersion and a preparation method thereof. More specifically, the invention relates to a phosphorus-nitrogen flame retardant dispersion and a preparation method thereof, belonging to the field of fine chemicals.

Background technique

Viscose fiber has a wide range of uses because of its excellent hygroscopicity, easy dyeing, antistatic, and easy textile processing. However, viscose fiber is a flammable fiber, and the textiles made of it are extremely flammable and cause fires, causing great harm to people's lives and property, thus limiting its wide application. With the improvement of people's consumption level and the enhancement of safety awareness , the demand for flame retardant viscose fiber has become stronger and stronger, which has effectively promoted the flame retardant research of viscose fiber at home and abroad.

At present, the flame retardants used in the production of flame-retardant viscose fibers are mainly the following: Austrian Lenzing Company and Japan Toyobo use chlorinated phosphonate flame retardants, which are not environmentally friendly because they contain halogens Requirements, applications are limited; France's Rhone Planck TF-80 fiber and American PER flame-retardant viscose fiber use organic ester flame retardants, and Finland's Kemiraoy company produces Visil series composite flame retardants with water glass flame retardants Viscose fiber, Danufi L flame retardant viscose fiber produced by German Hoechest company using halogen-free organophosphorus flame retardant, and Swiss Sandoz company using Sandoflam-5060 pyrophosphate flame retardant to produce flame retardant fiber by blending Flame retardant viscose fibers, although these flame retardant viscose fibers do not contain halogens, but because the effective flame retardant components in the flame retardants used are single, the addition of flame retardants is relatively large, which not only affects the physical properties of the fibers, And also increased the production cost.

The flame retardants used in China for the flame retardant of viscose fibers are mainly dithiopyrophosphate (DDPS) used by Cheng Bowen, etc., alkoxycyclotriphosphazene flame retardants used by Chen Sheng, etc., and silica gel-carbonic acid used by Tian Li. Potassium flame retardants have been studied on the flame retardancy of viscose fibers. At present, the flame retardant used in the Anfang flame-retardant fiber produced by Shandong Hailong Co., Ltd., the largest viscose fiber manufacturer in China, is a silicon-based flame retardant. Since it is a solution, it can be directly configured into a solution and added to the viscose during liquid preparation. Other solid flame retardants must be made into flame retardant dispersions in order to successfully produce flame retardant viscose fibers; at the same time, due to the large particle size, wide particle size distribution and flame retardant dispersion Due to problems such as poor stability and the high price of imported flame retardants, large-scale industrial production has not been realized in the end.

Contents of the invention

The invention aims to solve the problem that the flame retardant dispersion made of viscose fiber flame retardant has poor stability and is difficult to realize large-scale industrial production in the prior art, and provides a flame retardant dispersion and its preparation method More specifically, it provides a dispersion of phosphorus-nitrogen flame retardants and a preparation method and application of the dispersion of phosphorus-nitrogen flame retardants suitable for viscose fibers.

In order to realize the above-mentioned purpose of the invention, its concrete technical scheme is as follows:

A phosphorus-nitrogen flame retardant dispersion, characterized in that it comprises the following components in parts by weight:

25-30 parts of phosphorus nitrogen flame retardant, 1-2 parts of wetting agent, 3-5 parts of polymer dispersant, 1-2 parts of deflocculant and dispersant, 0.5-1 part of defoamer, 60 parts of deionized water -70 copies;

The phosphorus-nitrogen flame retardant is N, ^N' -bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl)ethylenediamine ;

The wetting agent is alcohols, such as: ethanol, propanol, ethylene glycol, propylene glycol, isopropanol. the

The polymer dispersant is a polycarboxylate sodium salt dispersant or polyacrylic acid ammonium with a pH value of 7-8 and an active ingredient of 43-47%.

The deflocculating dispersant is BYK-109, an alkoxyaminoamide deflocculating and dispersing agent with a molecular weight of 4000-6000.

The defoamer is a silicon-based defoamer, such as: simethicone, SXP defoamer, SG defoamer, GXP defoamer, OS defoamer, WH_1 defoamer or PGA defoamer.

A method for preparing a phosphorus-nitrogen flame retardant dispersion, characterized in that it comprises the following process steps:

A. Add 60-70 parts of deionized water and 1-2 parts of wetting agent into the tank and mix evenly under stirring at a speed of 100-150 r/min;

B. Put 3-5 parts of polymer dispersant and 1-2 parts of deflocculant into the pulling tank, and perform high-speed dispersion at a speed of 300-400 r/min for 10-20 min;

C. Reduce the stirring speed to 150-200 r/min, and add 0.5-1 parts of defoamer to the tank while stirring;

D. After the bubbles are eliminated, under stirring at a speed of 250-350 r/min, slowly add 25-30 parts of phosphorus-nitrogen flame retardant into the cylinder, and stir and disperse for 20-30 min;

E. Grind the obtained solution with a ball mill for 2-3 h until the particle size is 100-500 nm, and then obtain a phosphorus-nitrogen flame retardant dispersion suitable for viscose fiber according to the present invention.

The phosphorus-nitrogen flame retardant dispersion provided by the invention can be well applied in the production of flame-retardant viscose fibers.

The flame retardant dispersion liquid that the present invention makes has following advantage:

1. In the production process of viscose fiber, the viscose liquid enters the coagulation bath through the spinneret for regeneration and forming; since the spinneret hole diameter is only about 0.6mm, the requirement for the particle size of the added ingredients is very high. Reach below 500nm, and the dispersion liquid is required to have good dispersibility and stability, without flocculation and delamination, otherwise it will affect the production of viscose fiber, and will seriously affect the physical and mechanical properties and resistance of the finished fiber. flammability. Phosphorus-nitrogen flame retardant N, ^N' -bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl)ethylenediamine in the present invention It is a needle-like white crystal, containing phosphorus and nitrogen flame retardant ingredients, insoluble in water, the original particle size is about 30um, and cannot be directly applied to flame retardant materials. After dispersion and grinding, its particle size meets the application requirements, and it is added to In the material, it will basically not affect the mechanical properties of the material itself, and will endow the material with excellent flame retardant effect. The above-mentioned problems are solved by adding various additives to make the particle size of the flame retardant reach the range of 100-500nm after grinding.

2. By adding a certain proportion of wetting agent, polymer dispersing agent and deflocculating dispersing agent, the prepared dispersion liquid is not only dispersed evenly, but also not easy to precipitate and layer after long-term storage, and can be mixed with viscose collagen solution Even without agglomeration.

3. Add appropriate defoaming agent to reduce the air bubbles in the dispersion, so that the air bubbles produced after mixing with the viscose collagen solution will affect the forming effect of the fiber, and at the same time, it can effectively reduce the foam in the post-processing process, so that the production can go smoothly.

4. Perform high-speed dispersion and stirring in the pulling cylinder to reduce the problem of flame retardants sinking to the bottom, so that all flame retardants can go through basically similar grinding and dispersion processes to ensure the flame retardant in the final dispersion The particle size distribution of the agent is uniform, which reduces the occurrence of defects in the spinning process.

5. The phosphorus-nitrogen flame retardant dispersion produced by the present invention is evenly dispersed, has good stability, good compatibility with viscose, and has good spinnability. It is an acid-resistant and alkali-resistant flame-retardant dispersion with Wide range of application fields; after mixing the phosphorus-nitrogen flame retardant dispersion liquid and viscose solution prepared by the present invention, the fibers obtained by spinning and post-processing have a limiting oxygen index of more than 30, and the fibers have good physical and mechanical properties.

Detailed ways

Example 1

A phosphorus nitrogen flame retardant dispersion, comprising the following components in parts by weight:

25 parts of phosphorus nitrogen flame retardant, 1 part of wetting agent, 3 parts of polymer dispersant, 1 part of deflocculant dispersant, 0.5 part of defoamer, 60 parts of deionized water;

The phosphorus-nitrogen flame retardant is N, ^N' -bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl)ethylenediamine ;

Described macromolecular dispersant is pH value 7, and active ingredient is in the polycarboxylate sodium salt dispersant of 43%;

The deflocculating and dispersing agent is BYK-109, an alkoxyaminoamide deflocculating and dispersing agent with a molecular weight of 4000.

Example 2

A phosphorus nitrogen flame retardant dispersion, comprising the following components in parts by weight:

30 parts of phosphorus nitrogen flame retardant, 2 parts of wetting agent, 5 parts of polymer dispersant, 2 parts of deflocculant and dispersant, 1 part of defoamer, 70 parts of deionized water;

The phosphorus-nitrogen flame retardant is N, ^N' -bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl)ethylenediamine ;

Described macromolecular dispersant is pH value 8, and active ingredient is in the polycarboxylate sodium salt dispersant of 47%;

The deflocculating dispersant is BYK-109, an alkoxyaminoamide deflocculating and dispersing agent with a molecular weight of 6000.

Example 3

A phosphorus nitrogen flame retardant dispersion, comprising the following components in parts by weight:

27.5 parts of phosphorus nitrogen flame retardant, 1.5 parts of wetting agent, 4 parts of polymer dispersant, 1.5 parts of deflocculant and dispersant, 0.75 parts of defoamer, 65 parts of deionized water;

The phosphorus-nitrogen flame retardant is N, ^N' -bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl)ethylenediamine ;

Described macromolecule dispersant is pH value 7.5, and active ingredient is ammonium polyacrylate at 45%;

The deflocculating dispersant is BYK-109, alkylhydroxyaminoamide deflocculating and dispersing agent with a molecular weight of 5000.

Example 4

A phosphorus nitrogen flame retardant dispersion, comprising the following components in parts by weight:

29 parts of phosphorus nitrogen flame retardant, 1.1 parts of wetting agent, 4.5 parts of polymer dispersant, 1.7 parts of deflocculant and dispersant, 0.6 part of defoamer, 66 parts of deionized water;

The phosphorus-nitrogen flame retardant is N, ^N' -bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl)ethylenediamine ;

Described macromolecule dispersant is pH value 7.9, and active ingredient is ammonium polyacrylate at 44%;

The deflocculating dispersant is BYK-109, an alkoxyaminoamide deflocculating and dispersing agent with a molecular weight of 5500.

Example 5

On the basis of embodiment 1-4, described wetting agent and defoamer have following preferred scheme:

1. The wetting agent is ethanol, propanol, ethylene glycol, propylene glycol or isopropanol. the

2. The defoamer is simethicone, SXP defoamer, SG defoamer, GXP defoamer, OS defoamer, WH_1 defoamer or PGA defoamer.

Example 6

A method for preparing a phosphorus-nitrogen flame retardant dispersion, comprising the following process steps:

A. Add 60 parts of deionized water and 1 part of wetting agent into the tank and stir, and mix evenly at 100 r/min;

B. Put 3 parts of polymer dispersant and 1 part of deflocculant into the cylinder, and disperse at a high speed of 300 r/min for 10 min;

C. Reduce the stirring speed to 150 r/min, and add 0.5 parts of defoamer to the tank while stirring;

D. After the bubbles are eliminated, under stirring at a rotating speed of 250 r/min, slowly add 25 parts of phosphorus-nitrogen flame retardant into the cylinder, and stir and disperse for 20 minutes;

E. Use a ball mill to grind the obtained solution for 2 hours until the particle size is 100 nm, and obtain a phosphorus nitrogen flame retardant dispersion suitable for viscose fiber according to the present invention.

Example 7

A method for preparing a phosphorus-nitrogen flame retardant dispersion, comprising the following process steps:

A. Add 70 parts of deionized water and 2 parts of wetting agent into the tank and stir, and mix evenly at 150 r/min;

B. Put 5 parts of polymer dispersant and 2 parts of deflocculant into the cylinder, and disperse at a high speed of 400 r/min for 20 min;

C. Reduce the stirring speed to 200 r/min, and add 1 part of defoamer to the tank while stirring;

D. After the air bubbles disappear, slowly add 30 parts of phosphorus-nitrogen flame retardant into the tank at the same time under stirring at a rotating speed of 350 r/min, and stir to disperse for 30 minutes;

E. Grinding the obtained solution with a ball mill for 3 hours until the particle size is 500 nm, and then obtaining a phosphorus-nitrogen flame retardant dispersion suitable for viscose fiber according to the present invention.

Example 8

A method for preparing a phosphorus-nitrogen flame retardant dispersion, comprising the following process steps:

A. Add 65 parts of deionized water and 1.5 parts of wetting agent into the tank and stir, and mix evenly at 125 r/min;

B. Put 4 parts of polymer dispersant and 1.5 parts of deflocculant into the cylinder, and disperse at a high speed of 350 r/min for 15 min;

C. Reduce the stirring speed to 175 r/min, and add 0.75 parts of defoamer to the tank while stirring;

D. After the bubbles are eliminated, under stirring at a rotating speed of 300 r/min, slowly add 27.5 parts of phosphorus-nitrogen flame retardant into the cylinder, and stir and disperse for 25 minutes;

E. Grind the obtained solution by a ball mill for 2.5 hours until the particle size is 300 nm, and obtain a phosphorus-nitrogen flame retardant dispersion suitable for viscose fiber according to the present invention.

Example 9

A method for preparing a phosphorus-nitrogen flame retardant dispersion, comprising the following process steps:

A. Add 68 parts of deionized water and 1.1 parts of wetting agent into the tank and stir, and mix evenly at 110 r/min;

B. Put 4.8 parts of polymer dispersant and 1.7 parts of deflocculant into the cylinder, and disperse at a high speed of 370 r/min for 12 min;

C. Reduce the stirring speed to 180 r/min, and add 0.9 parts of defoamer to the tank while stirring;

D. After the bubbles are eliminated, under stirring at a rotating speed of 330 r/min, slowly add 26 parts of phosphorus-nitrogen flame retardant into the cylinder, and stir and disperse for 21 minutes;

E. Grinding the obtained solution with a ball mill for 2.5 hours until the particle size is 200nm, to obtain a phosphorus nitrogen flame retardant dispersion suitable for viscose fiber according to the present invention.

Example 10

Application examples of phosphorus nitrogen flame retardant dispersion liquid of the present invention in the preparation of flame retardant viscose fiber:

Each raw material is weighed according to the following parts by weight (hereinafter referred to as parts):

65 parts of deionized water, 1.5 parts of ethylene glycol, 4.5 parts of polycarboxylate sodium salt dispersant, 1.5 parts of high molecular weight alkoxyaminoamide, 0.7 parts of defoamer, N, ^N' -bis(5,5-dimethyl -2-phospha-2-thio-1,3-dioxan-2-yl)ethylenediamine flame retardant 26.8 parts

Production Process:

(1) Add 65 parts of deionized water and 1.5 parts of ethylene glycol into the tank and mix evenly at a speed of 120 r/min;

(2) Put 4.5 parts of polycarboxylate sodium salt dispersant and 1.5 parts of high-molecular-weight alkoxyaminoamide dispersant into the cylinder, and perform high-speed dispersion for 15 min at a speed of 350 r/min;

(3) Add 0.7 parts of organopolysiloxane defoamer into the tank until the bubbles disappear;

(4) Add 26.8 parts of N,N ^' -bis(5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl)ethylenediamine flame retardant Stir and disperse for 25 minutes at a speed of 300 r/min in the cylinder;

(5) Grind the obtained solution with a bead mill for 2.5 hours until the particle size is 250 nm, and then obtain the flame retardant dispersion of the present invention.

The flame retardant dispersion produced by this process has a particle size of 250 nm, good dispersion, and no flocculation and stratification. The dispersion is added to the viscose at 20% of the α-cellulose content, and the viscose filtration value is 165 ml, with a viscosity of 32 s, is a viscose spinning solution with good spinnability. The indicators of the viscose fiber spun are: dry breaking strength: 2.15 cN/dtex; wet breaking strength: 1.03 cN/dtex ; Dry elongation at break: 19%; Linear density deviation: -1.0%; Whiteness: 73%; Oil content: 2.5%; Moisture regain: 13%; Residual sulfur rate: 8 mg/100 g; Limiting oxygen index ( LOI) 31.

Example 11

Application examples of phosphorus nitrogen flame retardant dispersion liquid of the present invention in the preparation of flame retardant viscose fiber:

Weigh each raw material according to the following weight (unit: part):

60 parts of deionized water, 2 parts of ethylene glycol, 5 parts of polycarboxylate sodium salt dispersant, 2 parts of high molecular weight alkanolamide, 1 part of defoamer, N,N'-bis(5,5-dimethyl - 30 parts of 2-phospha-2-thio-1,3-dioxan-2-yl) ethylenediamine flame retardant.

Production Process:

1. Add 60 parts of deionized water and 2 parts of ethylene glycol into the tank and mix evenly at a speed of 150 r/min;

2. Put 5 parts of polycarboxylate sodium salt dispersant and 2 parts of high-molecular-weight alkoxyaminoamide dispersant into the cylinder, and perform high-speed dispersion at a speed of 400 r/min for 20 minutes;

3. Add 1 part of organopolysiloxane defoamer into the tank until the bubbles disappear;

4. Add 30 parts of N, ^N' -bis(5,5-dimethyl-2-phospha-2-thioxo-1,3-dioxan-2-yl)ethylenediamine flame retardant into the pulley Stir and disperse in the tank for 30 min at a speed of 350 r/min;

5. Grind the obtained solution with a bead mill for 3 hours until the particle size is 200 nm.

The flame retardant dispersion produced by this process has a particle size of 200 nm, good dispersion, and no flocculation and stratification. The dispersion is added to the viscose at 18% of the α-cellulose content, and the viscose filtration value is 170ml, viscosity 30s, is a kind of viscose spinning solution with good spinnability, the indicators of viscose fiber spun out are: dry breaking strength: 2.05cN/dtex; wet breaking strength: 1.13 cN/dtex; dry breaking strength: 1.13 cN/dtex; Elongation at break: 19.5%; linear density deviation: -2.0%; whiteness: 75%; oil content: 2.3%; moisture regain: 11%; residual sulfur rate: 10 mg/100 g; limiting oxygen index (LOI) 33.

Example 12

Application examples of phosphorus nitrogen flame retardant dispersion liquid of the present invention in the preparation of flame retardant viscose fiber:

Weigh each raw material according to the following weight (unit: part):

70 parts of deionized water, 1 part of ethylene glycol, 4 parts of polycarboxylate sodium salt dispersant, 1 part of high molecular weight alkanolamide, 0.5 part of defoamer, N, ^N' -bis(5,5-dimethyl - 23.5 parts of 2-phospha-2-thio-1,3-dioxan-2-yl) ethylenediamine flame retardant.

Production Process:

1. Add 70 parts of deionized water and 2 parts of ethylene glycol into the tank and mix evenly at a speed of 100 r/min;

2. Put 4 parts of polycarboxylate sodium salt dispersant and 1 part of high-molecular-weight alkoxyaminoamide dispersant into the cylinder, and perform high-speed dispersion at a speed of 370 r/min for 18 min;

3. Add 0.5 parts of organopolysiloxane defoamer into the tank until the bubbles disappear;

4. Add 23.5 parts of N, ^N' -bis(5,5-dimethyl-2-phospha-2-thioxo-1,3-dioxan-2-yl)ethylenediamine flame retardant into the pulley Stir and disperse in the tank for 25 min at a speed of 320 r/min;

5. Grind the obtained solution with a bead mill for 2 hours until the particle size is 300 nm.

The flame retardant dispersion produced by this process has a particle size of 300 nm, good dispersion, and no flocculation and stratification. The dispersion is added to the viscose at 22% of the α-cellulose content, and the flame retardant viscose is filtered. The value is 162.5 ml and the viscosity is 36 s. It is a viscose spinning solution with good spinnability. The indicators of the viscose fiber spun are: dry breaking strength: 2.10 cN/dtex; wet breaking strength: 1.10 cN /dtex; dry elongation at break: 20.5%; linear density deviation: -1.1%; whiteness: 78%; oil content: 2.2%; moisture regain: 12%; residual sulfur: 7 mg/100 g; limiting oxygen index (LOI) 31.5.

Claims (7)

1. a phosphorus-nitrogen containing flame retardant dispersion liquid is characterized in that, comprises the following component of meter by weight:

Phosphorus-nitrogen containing flame retardant 25-30 part, wetting agent 1-2 part, macromolecule dispersing agent 3-5 part, separate flocculant dispersant 1-2 part, antifoaming agent 0.5-1 part, deionized water 60-70 part;

Described phosphorus-nitrogen containing flame retardant is N, N ^'-two (5,5-dimethyl-2-phospha-2-sulfo--1,3-diox-2-yl) ethylenediamine;

Described macromolecule dispersing agent is pH value 7-8, and active component is at polycarboxylate sodium's dispersant or the ammonium polyacrylate of 43-47%;

The said flocculation dispersant of separating is that molecular weight is the alkane hydroxyl amino amidolysis flocculation dispersant B YK-109 of 4000-6000.

2. a kind of phosphorus-nitrogen containing flame retardant dispersion liquid according to claim 1 is characterized in that: described wetting agent is ethanol, propyl alcohol, ethylene glycol, propylene glycol or isopropyl alcohol.

3. a kind of phosphorus-nitrogen containing flame retardant dispersion liquid according to claim 1 is characterized in that: said antifoaming agent is dimethicone, SXP antifoaming agent, SG antifoaming agent, GXP antifoaming agent, OS antifoaming agent, WH_1 antifoaming agent or PGA antifoaming agent.

4. the preparation method of a kind of phosphorus-nitrogen containing flame retardant dispersion liquid according to claim 1 is characterized in that: comprise following processing step:

A, with 60-70 part deionized water, 1-2 part wetting agent adds in the scuffing of cylinder bore and stirs, and mixes;

B, with 3-5 part macromolecule dispersing agent, 1-2 part is separated flocculant and is put into scuffing of cylinder bore, is to carry out high speed dispersion 10-20 min under the 300-400 r/min at rotating speed;

C, speed of agitator is reduced to 150-200 r/min, the antifoaming agent with 0.5-1 part adds in the scuffing of cylinder bore while stirring;

D, treating the bubble cancellation, is under the stirring of 250-350 r/min at rotating speed, and the phosphorus-nitrogen containing flame retardant with 25-30 part slowly adds in the scuffing of cylinder bore dispersed with stirring 20-30 min simultaneously;

E, be 100-500nm, promptly obtain a kind of phosphorus-nitrogen containing flame retardant dispersion liquid that is applicable to viscose according to the invention gained soln using ball mill grinding to particle diameter.

5. the preparation method of a kind of phosphorus-nitrogen containing flame retardant dispersion liquid according to claim 4 is characterized in that: the rotating speed in the stirring described in the steps A is 100-150 r/min.

6. the preparation method of a kind of phosphorus-nitrogen containing flame retardant dispersion liquid according to claim 4 is characterized in that: the milling time with gained soln using ball mill grinding described in the step e is 2-3h.

7. according to the application of the described a kind of phosphorus-nitrogen containing flame retardant dispersion liquid of one of claim 1-3 in the preparation FRC.