CN102352099B - Expansion type flexible fire retardant decorative material, and preparation method and application thereof - Google Patents

Abstract

The invention belongs to the technical field of polymer matrix composite materials and relates to a decorative material applicable to exterior wall foamed plastic insulation works for buildings, i.e., an expansion type flexible fire retardant decorative material and a preparation method thereof. A technical scheme for the invention is as follows: a blended polymer emulsion is prepared by adding silicone-acrylate copolymer emulsion into an aqueous polyurethane emulsion and compounding and blending the two emulsions. The expansion type flexible fire retardant decorative material is a novel functional material; components in the material swell when burned by a fire, and a stable structural carbon layer is formed; the swollen structural carbon layer can isolate heat transfer and has a fire resistant effect. The material can be used for preparing products with a certain degree of flexibility, is convenient to construct and apply and can be used to substitute ceramic tiles and used for fire retardant decorative layers of buildings.

Description

An intumescent flexible fireproof facing material and its preparation method and application

technical field

The invention belongs to the technical field of polymer-based composite materials, and relates to a facing material suitable for building exterior wall foam plastic insulation engineering, that is, an intumescent flexible fireproof facing material and a preparation method thereof.

Background technique

In buildings, the heat loss of the external wall enclosure structure is relatively large, and the wall is the main component of the external enclosure structure. According to the principle of value engineering, the development of external wall insulation technology has become an important link to realize building energy saving. It saves a lot of energy, and can also provide residents with a comfortable environment and bring many benefits. With the rapid development of building energy-saving technology, the requirements for thermal insulation of buildings are constantly increasing. At present, the external thermal insulation of external walls mainly adopts the technical measures of covering the wall with foamed plastic materials. Since the foamed plastics are made of polystyrene foam and polyurethane Foam plastics are the main materials, which are combustible materials. Due to their low fire resistance, they cannot meet the fire prevention requirements, and there are great safety hazards in use. In addition, inorganic ceramic tiles are used for covering protection and finishing, which are non-combustible materials, which avoid fire and combustion. , but the use of ceramic tile veneer, due to its heavy quality, will bring safety hazards if it falls off, and it is inconvenient to use ceramic tile veneer in some more complicated details.

Contents of the invention

The object of the present invention is to overcome the deficiencies of the prior art and provide an intumescent flexible fireproof facing material, which is a light, flexible, polymer-based composite material with fire retardant effect, which can replace ceramic tiles The surface can reduce the building load and improve the safety of the project. At the same time, the invention also provides a preparation method of the intumescent flexible fireproof facing material.

In order to solve the above-mentioned technical problems, the technical solution of the present invention is: a polymer blend emulsion, which is prepared by the following method: adding silicon-acrylic copolymer emulsion to the water-based polyurethane emulsion, and preparing the polymer blend emulsion through compound blending . Preparation of water-based polyurethane emulsion and silicone-acrylic copolymer emulsion to form a blended polymer emulsion. The blended polymer emulsion is used as an adhesive base material, which has high adhesion to inorganic components and has good flexibility, durability and resistance. Flammability. The polyurethane component used produces nitrogen gas when it burns, which can keep gas and expand.

The preparation of the aqueous polyurethane resin that the present invention uses:

1) Preparation of prepolymer, add 280~320 PHR polyether (2020:3050 is 2:1) into a temperature-adjustable reactor equipped with vacuum and stirring cooling device, and vacuum dehydrate to The water content is lower than 0.8~0.5%. When the temperature is lowered to 65~60°C, slowly add 75~ 85 PHR of IPDI (control the reaction temperature not to exceed 100°C), and keep it at 80°C for 1 hour to make a prepolymer containing free isocyanate groups.

2) Chain extension reaction: Slowly add diethylene glycol 60~80PHR dropwise to the prepolymer, continue to keep warm at 80°C for 2~3 hours, and cool down the prepolymer after chain extension to 60~50°C. Add 500-600PHR of 5% tartrate-acetone solution by mass, raise the temperature to 55-60°C, keep it under reflux for 1 hour, then add 800-850PHR of acetone to dilute to reduce the viscosity.

3) For emulsification, cool the polymer to room temperature, slowly add 100~110PHR of 15% triethylamine acetone solution by mass, and stir evenly. After that, slowly add distilled water under high-speed stirring (about 400-500 rpm) at room temperature to form an emulsion.

4) Separation, put the liquid into a distillation device, stir, and when the temperature rises to 50-60°C, start vacuuming (vacuum degree is 410-460×133.322 Pa), and distill acetone to obtain a milky white water-based polyurethane emulsion .

The blended polymer emulsion is prepared by the following method: 200-400 PHR of water-based polyurethane emulsion, 100-200 PHR of silicone-acrylic copolymer emulsion, stirring and mixing at room temperature for 10-15 minutes to obtain the blended polymer emulsion.

A polymer flame retardant slurry, prepared by a method comprising the steps of:

(1) Add dispersant and dissolve in a certain amount of water, add emulsifier and flame retardant plasticizer, stir to make premixed liquid;

(2) Add pigments, flame retardants, expansion agents, and charring agents to the premixed liquid prepared in step (1), stir and grind to obtain a mixed slurry;

(3) Add the polymer blend emulsion and stabilizer to the mixed slurry prepared in step (2), and prepare the flame-retardant polymer blend slurry through blending and stirring.

Further, a polymer flame retardant slurry is prepared by a method comprising the following steps:

(1) In 150-200 PHR water, stir and add dispersant 3-5PHR to make an aqueous solution, add emulsifier 4-6PHR and flame retardant plasticizer 15-22PHR in 50-100PHR water, stir to make a premixed liquid;

(2) Add 30-46PHR of pigments, 200-240PHR of flame retardants, 20-60PHR of expansion agents, and 60-100PHR of char-forming agents to the premixed liquid prepared in step (1), stir and grind to obtain a mixed slurry;

(3) Add 400PHR of the blended polymer emulsion to the mixed slurry prepared in step (2), and prepare the blended polymer flame-retardant slurry through blending and stirring.

The emulsifier of the present invention is OP-10, the dispersant is hydroxyethyl cellulose and/or sodium hexametaphosphate, the stabilizer is hydroxyethyl cellulose, the pigment is titanium dioxide and/or calcium carbonate, and the flame retardant is Ammonium polyphosphate, expansion agent is melamine, carbon forming agent is pentaerythritol, flame retardant plasticizer is chlorinated paraffin.

A preparation method for polymer flame retardant slurry, comprising the steps of:

(1) In 150-200 PHR water, stir and add dispersant 3-5PHR to make an aqueous solution, add emulsifier 4-6PHR and flame retardant plasticizer 15-22PHR in 50-100PHR water, stir at 500-800 rpm After 30 minutes, it is sent to the grinding equipment for grinding, and the fineness is ≤60 microns, and it is made into a premixed liquid;

(2) Add 30-46PHR of pigments, 200-240PHR of flame retardants, 20-60PHR of expansion agents, and 60-100PHR of char-forming agents to the premixed liquid prepared in step (1), stir and grind to obtain a mixed slurry;

(3) Add 400 PHR of the blended polymer emulsion to the mixed slurry prepared in step (2), and stir for 10 minutes at a stirring speed of 100-200 rpm to prepare a blended polymer flame-retardant slurry.

The emulsifier of the present invention is OP-10, the dispersant is hydroxyethyl cellulose and/or sodium hexametaphosphate, the stabilizer is hydroxyethyl cellulose, the pigment is titanium dioxide and/or calcium carbonate, and the flame retardant is Ammonium polyphosphate, expansion agent is melamine, carbon forming agent is pentaerythritol, flame retardant plasticizer is chlorinated paraffin.

An intumescent flexible fireproof facing material is prepared by the following method: adding 20-120 mesh colored sand 400-800PHR and thickener 4-8PHR to the polymer flame-retardant slurry prepared above, The rotational speed of the stirrer is 100-150 rpm, and the stirring is performed for 10-15 minutes to obtain a polymer-based expansion type flexible fireproof facing material.

A method for preparing an intumescent flexible fireproof facing material. Add 20-120 mesh colored sand 400-800PHR and thickener 4-8PHR to the polymer flame-retardant slurry prepared above, and the agitator rotates at 100-150 rev/min, stirring for 10-15 minutes to obtain a polymer-based intumescent flexible fireproof facing material.

An application of an intumescent flexible fireproof facing material, the mortar can be directly coated and used, or can be made into flexible facing bricks for pasting.

Inject the fireproof facing material into the mold cavity, and scrape the surface to obtain the polymer-based intumescent flexible fireproof-faced flexible brick parison. The parison is cured in hot air, dried, and cut into pieces to obtain the polymer-based intumescent flexible brick parison. Fireproof facing flexible brick.

The properties of the prepared intumescent flexible fireproof facing flexible brick: flexibility, 150mm diameter cylindrical bending, no cracks; temperature denaturation resistance, no cracks, peeling, bulging after 10 low temperature cycles; artificial aging, 1000 hours, no cracking, no cracking Drum, peeling; combustion performance, evaluation of combustion level, A2 level, combustion oxygen index 40. The invention can make the thermal insulation wall achieve the external decoration with the effect of ceramic tiles, and enrich the means of expression for the external wall decoration projects that cannot be decorated with ceramic tiles. Weight, the benefits of replacing ceramic tiles are obvious. Compared with ordinary polymer-based composite materials, the invention has high flame-retardant performance, meets the requirement of non-combustibility, and plays an important role in the safety of external wall insulation projects using foam plastics. The composition used in the invention can be flame-retardant, ablated into carbon, and the carbon layer expands to prevent heat transfer. Compared with polymer-based flame-retardant materials using flame retardants alone, the material technology system has smaller mass and more reliable fire-retardant effect.

The beneficial effects of the present invention are: the intumescent flexible fireproof facing material is a new type of functional material, and the material components will self-expand when exposed to fire and form a stable structural carbon layer. effect. The material can be prepared into products with a certain degree of flexibility, which is convenient for construction and application, and can replace ceramic tiles for fireproof building exterior layers. It is a kind of lightweight, flexible, and fire-retardant polymer-based composite material. The combustion performance of the material meets the requirements of flame-resistant grade A2. It can be used for wall decoration of building exterior foam plastic insulation projects. It can be applied to other wall finishes, and it can play a certain role in fire resistance when it burns in a fire. The material can be directly coated, or made into flexible tiles for pasting. The material is light, flexible and easy to construct. Due to the use of flame retardant components and carbon-forming thermal insulation components, the fire retardant performance is reliable.

Detailed ways

Example 1

1. Preparation of waterborne polyurethane emulsion:

1) Prepolymer preparation, put 280 grams of polyether (2020:3050 mass ratio is 2:1) into a temperature-adjusted reactor, and vacuum dehydrate when the temperature rises to 110~120°C until the water content is lower than 0.8%. Slowly add 75 parts of IPDI when the temperature drops to 65~60°C (control the reaction temperature not to exceed 100°C). Incubate at 80°C for 1 hour to prepare a prepolymer containing free isocyanate groups.

2) Chain extension reaction: Slowly add 60 grams of diethylene glycol dropwise to the prepolymer, continue to keep warm at 80°C for 2-3 hours, and cool down the extended prepolymer to 60-50°C. Add 500 grams of 5% tartrate in acetone, raise the temperature to 55-60 ° C, keep it under reflux for 1 hour, then add 800 grams of acetone to dilute to reduce the viscosity.

3) For emulsification, cool the polymer to room temperature, slowly add 100 grams of 15% triethylamine acetone solution, and stir evenly. After that, slowly add distilled water under high-speed stirring (400-500 rpm) at room temperature to form an emulsion.

4) Separation, put the liquid into a distillation device, stir, and when the temperature rises to 50-60°C, start vacuuming (vacuum degree is 410-460×133.322 Pa), and distill acetone to obtain a milky white water-based polyurethane emulsion .

2. Preparation of premixed liquids

Add 180 grams of water to 1 gram of sodium hexametaphosphate and 3 grams of hydroxyethyl cellulose, stir to form an aqueous solution for later use. Add 4 grams of OP-10 emulsifier and 18 grams of chlorinated paraffin into 80 grams of water, and stir to form a uniform emulsion. Combine the above solution with the emulsion to obtain a premixed liquid.

3. Preparation of polymer flame retardant slurry

Add 30 grams of titanium dioxide, 200 grams of ammonium polyphosphate, 20 grams of melamine, and 60 grams of pentaerythritol into the premixed liquid, stir at high speed for 30 minutes, and then send it to the grinding equipment for grinding to a fineness of ≤60 microns. Add 200 grams of water-based polyurethane emulsion, 100 grams of silicone-acrylic copolymer emulsion, and the above-mentioned premixed liquid, and stir at a speed of 100-200 rpm to obtain a polymer slurry of the material.

4. Preparation of intumescent flexible fireproof facing material and flexible brick

Add the above-mentioned polymer flame retardant slurry into the mixer, start stirring and slowly add 500 grams of colored sand and 5 grams of thickener, the mixer speed is 100-150 rpm, and stir for 15 minutes to obtain an intumescent flexible fireproof finish Material. Inject the expandable flexible fireproof facing material into the mold cavity. The mold cavity size is: depth 3-5mm, width 200-400mm, length 400-600mm, and scrape the surface to obtain the parison of the flexible facing brick. Carry out hot air curing and drying on the parison, the process temperature of hot air is 60-80 ^OC , the hot air curing time is 4~6 hours, then dry at room temperature for 24~36 hours, and cut into pieces to obtain flame retardant flexible facing brick products .

The combustion grade of the product reaches B2 level, and the oxygen index reaches 35.

Example 2

1. Preparation of water-based polyurethane emulsion

1) Prepolymer preparation, put 320 grams of polyether (2020:3050 is 2:1) into a temperature-adjusted reactor, and vacuum dehydrate when the temperature is raised to 110~120°C until the water content is lower than 0.5%. Slowly add 85 grams of IPDI when the temperature drops to 65~60°C (control the reaction temperature not to exceed 100°C). Incubate at 80°C for 1 hour to prepare a prepolymer containing free isocyanate groups.

2) Chain extension reaction: Slowly add 80 grams of diethylene glycol dropwise to the prepolymer, continue to keep warm at 80°C for 2-3 hours, and cool down the extended prepolymer to 60-50°C. Add 600 parts of 5% tartrate in acetone solution, raise the temperature to 55-60°C, keep it under reflux for 1 hour, then add 850 grams of acetone to dilute to reduce the viscosity.

3) For emulsification, cool the polymer to room temperature, slowly add 110 grams of 15% triethylamine acetone solution, and stir evenly. After that, slowly add distilled water under high-speed stirring (400-500 rpm) at room temperature to form an emulsion.

4) Separation, put this liquid into a distillation device, stir, when the temperature rises to 60°C, start vacuuming (vacuum degree is 410-460×133.322 Pa), distill acetone, and obtain a milky white water-based polyurethane emulsion.

2. Preparation of premixed liquids

Put 200 grams of water into the mixing tank, start stirring, add 2 grams of sodium hexametaphosphate and 5 grams of hydroxyethyl cellulose, and prepare an aqueous solution for later use. Add 100 grams of water, add 6 grams of OP-10 emulsifier and 22 grams of chlorinated paraffin, and stir to form a uniform emulsion. Combine the solution with the emulsion to obtain a premixed liquid,

3. Preparation of polymer flame retardant slurry

In the above premixed liquid, gradually add 46 grams of titanium dioxide, 240 grams of ammonium polyphosphate, 60 grams of melamine, and 100 grams of pentaerythritol, with intervals of 5 minutes and high-speed stirring for 30 minutes. Send it to the grinding equipment for grinding, and the fineness can reach ≤60 microns. Add 300 grams of water-based polyurethane emulsion and 100 grams of silicone-acrylic copolymer emulsion, stir for 10 minutes at a stirring speed of 100-200 rpm, and obtain the polymer slurry of the material.

4. Preparation of intumescent flexible fireproof facing material and flexible brick

Add the above-mentioned polymer flame retardant slurry into the mixer, start stirring and slowly add 600 grams of colored sand and 6 grams of thickener, the mixer speed is 100-150 rpm, and stir for 15 minutes to obtain an intumescent flexible fireproof decoration surface material. Inject the expandable flexible fireproof facing material into the mold cavity. The mold cavity size is: depth 3-5mm, width 200-400mm, length 400-600mm, and scrape the surface to obtain the parison of the flexible facing brick. The parison is cured and dried, the curing temperature is 60-80 ^OC , the curing time is 4-6 hours, and then dried at room temperature for 24-36 hours, and cut into pieces to obtain flame-retardant flexible facing brick products.

The combustion grade of the product reaches A2 grade, and the oxygen index reaches 35.

Example 3

Implementation steps are the same as example 2, consumption: 200 grams of water-based polyurethane emulsion, 200 grams of silicone acrylic copolymer emulsion; 800 grams of colored sand; other dispersant, emulsifier, thickener, film former consumption and use are equal to example 2.

The combustion grade of the product reaches A2 grade, and the oxygen index reaches 35.

Example 4

Implementation steps are the same as example 2, consumption: 300 grams of water-based polyurethane emulsion, 100 grams of silicone acrylic copolymer emulsion, 400 grams of colored sand; other dispersant, emulsifier, thickener, film former consumption and use are equal to example 2.

The combustion grade of the product reaches A2 grade, and the oxygen index reaches 35.

Claims (7)

1. A polymer flame retardant slurry, characterized in that: the polymer flame retardant slurry is prepared by a method comprising the following steps: (1) Add dispersant and dissolve in a certain amount of water, add emulsifier and flame retardant plasticizer, stir to make premixed liquid; (2) Add pigments, flame retardants, expansion agents, and charring agents to the premixed liquid prepared in step (1), stir and grind to obtain a mixed slurry; (3) Adding the polymer blend emulsion to the mixed slurry prepared in step (2), and blending and stirring to prepare the polymer blend flame retardant slurry; The blended polymer emulsion is prepared by the following method: adding silicone-acrylic copolymer emulsion to the water-based polyurethane emulsion, and the blended polymer emulsion is obtained by compound blending, specifically by the following method: water-based polyurethane emulsion 200 -400PHR, add 100-200PHR of silicone-acrylic copolymer emulsion, stir and mix at room temperature for 10-15 minutes to obtain a blended polymer emulsion; The polymer flame retardant slurry is prepared by a method comprising the following specific steps: (1) In 150-200 PHR water, stir and add dispersant 3-5PHR to make an aqueous solution, add emulsifier 4-6PHR and flame retardant plasticizer 15-22PHR in 50-100PHR water, stir to make a premixed liquid; (2) Add 30-46PHR of pigments, 200-240PHR of flame retardants, 20-60PHR of expansion agents, and 60-100PHR of char-forming agents to the premixed liquid prepared in step (1), stir and grind to obtain a mixed slurry; (3) Add 400PHR of the blended polymer emulsion to the mixed slurry prepared in step (2), and prepare the blended polymer flame-retardant slurry through blending and stirring. 2. A kind of polymer flame-retardant slurry according to claim 1, characterized in that: the emulsifier is OP-10, the dispersant is hydroxyethyl cellulose and/or sodium hexametaphosphate, and the pigment is Titanium dioxide and/or calcium carbonate, the flame retardant is ammonium polyphosphate, the expansion agent is melamine, the carbon forming agent is pentaerythritol, and the flame retardant plasticizer is chlorinated paraffin. 3. A preparation method for polymer flame retardant slurry, characterized in that: comprising the steps of: (1) In 150-200 PHR water, stir and add dispersant 3-5PHR to make an aqueous solution, add emulsifier 4-6PHR and flame retardant plasticizer 15-22PHR in 50-100PHR water, and stir to make a premixed liquid; (2) Add 30-46PHR of pigments, 200-240PHR of flame retardants, 20-60PHR of expansion agents, and 60-100PHR of char-forming agents to the premixed liquid prepared in step (1), stir and grind to obtain a mixed slurry; (3) Add 400PHR of blended polymer emulsion to the mixed slurry prepared in step (2), and prepare blended polymer flame-retardant slurry through blending and stirring. The blended polymer emulsion is prepared by the following method: adding silicone-acrylic copolymer emulsion to the water-based polyurethane emulsion, and the blended polymer emulsion is obtained by compound blending, specifically by the following method: water-based polyurethane emulsion 200 -400PHR, add 100-200PHR of silicone-acrylic copolymer emulsion, stir and mix at room temperature for 10-15 minutes to obtain blended polymer emulsion. 4. the preparation method of a kind of polymer flame retardant slurry according to claim 3 is characterized in that: described emulsifier is OP-10, and dispersant is hydroxyethyl cellulose and/or sodium hexametaphosphate , the pigment is titanium dioxide and/or calcium carbonate, the flame retardant is ammonium polyphosphate, the expansion agent is melamine, the char forming agent is pentaerythritol, and the flame retardant plasticizer is chlorinated paraffin. 5. An intumescent flexible fireproof facing material, characterized in that: it comprises the polymer flame retardant slurry according to claim 1, and the intumescent flexible fireproof material is prepared by a method comprising: making in claim 1 400-800PHR of 20-120-mesh colored sand and 4-8PHR of thickener are added to the obtained polymer flame-retardant slurry, and stirred to obtain a polymer-based expandable flexible fireproof facing material. 6. A method for preparing an intumescent flexible fireproof facing material, characterized in that: 20-120 mesh colored sand 400-800PHR and thickener 4- 8PHR, stirring to obtain a polymer-based intumescent flexible fireproof facing material. 7. The application of an intumescent flexible fireproof facing material according to claim 5, characterized in that: the intumescent flexible fireproof facing material can be directly coated and used, or can be made into flexible tiles for pasting.