CN105820311A - Desulphurization gypsum-polyurethane compounded fireproof and heat-preservation board and preparing method thereof - Google Patents

Abstract

The invention discloses a desulfurized gypsum-polyurethane composite fireproof insulation board, which contains two groups of components A and B, and the component A is composed of the following raw materials: polyether polyol, polyester polyol, polypropylene glycol, structural type Flame retardant polyol, modified desulfurized gypsum powder, foam stabilizer, gel catalyst, trimerization catalyst, liquid flame retardant, foaming agent; B component is polymethylene polyphenyl polyisocyanate, A group Stir separately and add the foaming agent evenly, then add component B, after high-speed stirring, pour into the desulfurized gypsum-polyurethane composite fireproof insulation board obtained by foaming, curing, and demoulding in a constant temperature mold. The invention makes full use of desulfurized gypsum, an industrial by-product of coal power plants, and successfully organically modifies desulfurized gypsum powder to enhance compatibility with polyurethane raw materials; the product of the invention has high fire resistance and good mechanical properties at the same time, and the combustion performance meets National standard A level requirements.

Description

A desulfurized gypsum-polyurethane composite fireproof insulation board and its preparation method

technical field

The invention relates to thermal insulation building materials, in particular to a desulfurized gypsum polyurethane composite board capable of achieving fire prevention and thermal insulation effects.

Background technique

With the advancement of science and technology and the improvement of the national economy, building energy conservation has increasingly become a hot spot and focus of national and social attention, and thermal insulation and fire prevention are the key direction of building energy conservation. In terms of thermal insulation effect, polyurethane rigid foam stands out among many polymer materials. It has the advantages of low thermal conductivity, good compressive strength and dimensional stability, relatively light weight, waterproof, and aging resistance. However, pure polyurethane rigid foam is extremely flammable, and it will immediately generate flames when it comes into contact with a fire source, and its flame retardancy is poor, which greatly limits its application. At present, as the country has higher and higher requirements for the performance of flame-retardant products in public places, the challenge of polyurethane rigid foam in terms of fire resistance is also increasing.

In general, the method used to improve the flame retardancy of polyurethane rigid foam materials is to add flame retardants to polyurethane raw materials. Flame retardants are divided into two types: additive and reactive. A chemical reaction occurs, and it is only filled and dispersed into the polyurethane matrix in a physical form, such as aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, silicon dioxide, expandable graphite and other inorganic flame retardants, melamine, ammonium polyphosphate , organic flame retardants such as dimethyl methylphosphonate, additive flame retardants have poor compatibility with the polyurethane matrix, and when the filling amount is large, the matrix will easily fall off and the mechanical properties are poor; reactive flame retardants are used in the synthesis of polyurethane Participate in the polymerization reaction and combine flame retardant elements on the main chain or side chain, such as polyether polyols of phosphate esters, polyether polyols of nitrogen-containing heterocyclic rings, etc. Reactive flame retardants have good compatibility with the polyurethane matrix and high flame retardant efficiency due to their participation in the polymerization reaction, but the synthesis process is complicated and the cost is high.

Some inorganic materials with zero calorific value or low calorific value are favored by manufacturers and related scientific research institutions due to their small combustion calorific value, non-toxicity, cheapness and easy availability. However, there is no uniform standard and method for applying inorganic materials to the field of building insulation. For example, the Chinese patent with the publication number CN103397735A is an autoclaved fly ash straw foamed polyurethane insulation board. First, lime and fly ash are ball-milled to a particle size of ≤0.5mm, and then blanks are prepared, autoclaved and molded at room temperature. Curing for 28 days, so that the moisture content is ≤ 2%, that is, forming a calcium silicate board (1) at one time; then crushing the straw to a particle size ≤ 5mm, then adding foamed polyurethane and stirring at a high speed, and foaming when the room temperature reaches > 15°C , then casting and forming, and finally cutting and forming the foamed polyurethane insulation layer (2), and the foamed polyurethane insulation layer is pasted with aluminum foil on both sides; finally, the foamed polyurethane insulation layer (2) is tightly packed into the calcium silicate board (1) The gaps serve as thermal insulation wall panels. The insulation board of the invention has a long preparation period, and the calcium silicate board and the polyurethane board have disadvantages such as falling off of the board when encountering a fire source due to poor adhesion. The Chinese patent with the publication number CN104672415A discloses a polyurethane-rock wool thermal insulation and fireproof material and its preparation method. The rock wool is ground into powder with a grinder, and the polyether mixture and the rock wool powder are premixed at low pressure for more than 30 minutes. The material is fully Mix evenly, and pressurize to 3.0-1.0MPa high pressure state through a booster pump, and then further add foaming agent, foam stabilizer, etc. Due to the existence of rock wool, the prepared thermal insulation board will have disadvantages such as high bulk density, poor waterproof performance, and high construction technology requirements.

Desulfurization gypsum powder is solid waste produced in the desulfurization process section of coal power plants. Its chemical composition is similar to natural gypsum. Using desulfurization gypsum as a filler for building insulation wallboards can not only solve the outlet for desulfurization gypsum, but also reduce the production cost of composite materials. Moreover, in the event of a fire, desulfurized gypsum can release crystal water to play a role in fire prevention. Desulfurized gypsum itself is also a material with an extremely low calorific value and is non-combustible.

Contents of the invention

Aiming at the problems of low fireproof performance, high production cost and poor heat preservation effect in the existing heat preservation materials, the main purpose of the present invention is to provide a desulfurized gypsum-polyurethane composite fireproof heat preservation board and its preparation method, while maintaining the original heat preservation effect, The fire performance is improved, the mechanical strength is enhanced, and the production cost is reduced at the same time. Since desulfurized gypsum powder itself does not participate in the polymerization process of rigid polyurethane foam, it does not affect the overall pore-forming and thermal insulation performance of rigid polyurethane foam, and desulfurized gypsum powder itself can replace part of the flame retardant to improve the fire resistance of composite materials performance. The present invention also adopts a novel structural flame retardant aliphatic boron-based polyol as one of the raw materials for polyurethane rigid foam.

The technical scheme adopted in the present invention is:

A desulfurized gypsum-polyurethane composite fireproof insulation board, which contains two components, A and B, and the component A is composed of the following raw materials in parts by mass: polyether polyol: 40-60 parts, polyester polyol: 10-20 parts, polypropylene glycol: 5-10 parts, structural flame-retardant polyol: 15-25 parts, modified desulfurized gypsum powder: 25-40 parts, foam stabilizer: 2-3.5 parts, gel catalyst: 0.5-2 parts, trimerization catalyst: 1-3 parts, liquid flame retardant: 10-20 parts, foaming agent: 25-40 parts; the mass parts of component B are: polymethylene polyphenyl polyisocyanate : 100-180 parts, stir component A evenly and add foaming agent, then add component B, after high-speed stirring, pour into the desulfurized gypsum-polyurethane composite fireproof insulation board obtained by foaming, curing and demoulding in a constant temperature mold.

In the above-mentioned fireproof insulation board, the structural flame-retardant polyol is an aliphatic boron-based flame-retardant polyol.

The above-mentioned fire-proof insulation board, the polyether polyol in the A component is one or more of polytetrahydrofuran polyol or polyoxypropylene polyol, the hydroxyl value is 420-480mgKOH/g, and the viscosity is 2000-3500mPa.s (25°C), preferably one or more of polyether polyol 403, polyether polyol 380, polyether polyol 4110, and polyether polyol 635C. The polyester polyol is one or more of aliphatic polyester polyol or aromatic polyester polyol, the hydroxyl value is 400-440mgKOH/g, the viscosity is 4000-6000mPa.s (25°C), preferably poly One or more of ester polyol P-455N, polyester polyol SKR-400E, polyester polyol 3152. The polypropylene glycol is polypropylene glycol 1000, the hydroxyl value is 100-130 mgKOH/g, and the viscosity is 1000-1300 mPa.s (25° C.).

The above-mentioned fireproof insulation board, the catalyst in the A component includes a gel catalyst and a trimerization catalyst, wherein the gel catalyst is preferably one or both of dibutyltin dilaurate, stannous octoate or triethylenediamine, The trimerization catalyst is preferably N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, pentamethyldiethylene triazine One or any combination of several amines.

For the above-mentioned fireproof insulation board, the liquid flame retardant in the A component is preferably tricresyl phosphate (TCP), dimethyl methyl phosphonate (DMMP), triethyl phosphate, tetraphenylresorcinol bis One or any combination of polyphosphate (RDP).

For the above-mentioned fireproof insulation board, the foam stabilizer in component A is one or more of polysiloxane, polyether siloxane or polyether modified siloxane. Preferably, it is one or more of foam stabilizers AK-8801, AK-8805, AK8812 (Jiangsu Mesid Chemical Co., Ltd.), polyether modified silicone oil HK-102 (Jining Huakai Resin Co., Ltd.).

In the fire-proof insulation board mentioned above, the foaming agent in component A is one or more of fluorodichloroethane or cyclopentane.

A kind of method for making above-mentioned fireproof insulation board, it comprises the following steps:

Step 1. Weigh the raw materials according to the mass parts of the above-mentioned component A, mix polyether polyol, polyester polyol, polypropylene glycol, structural flame-retardant polyol, and modified desulfurized gypsum powder evenly, and then add foam stabilization agent, gel-type catalyst, trimerization catalyst, liquid flame retardant, stir well and add foaming agent;

Step 2. Weigh the polymethylene polyphenyl polyisocyanate according to the mass fraction of the above-mentioned component B, mix the components with the B component, stir at high speed, and quickly inject the liquid foam into a constant temperature mold to foam after the liquid foam is milky white. Ripening and demoulding to obtain desulfurized gypsum-polyurethane composite fireproof insulation board.

The method for making the above-mentioned fireproof insulation board, the preparation method of the modified desulfurized gypsum powder in the described A component is:

The amount of the coupling agent is 5%-10% of the mass of the desulfurized gypsum powder, and it is configured as an ethanol solution containing 2%-4% of the coupling agent, and the desulfurized gypsum powder is placed in the ethanol solution containing the coupling agent, and stirred evenly After filtration, the filter cake is dried at 100°C-120°C for 2 hours to obtain modified desulfurized gypsum powder, wherein the coupling agent is silane coupling agent KH550 or tetrabutyl titanate.

In the method for making the above-mentioned fire-proof insulation board, the structural flame-retardant polyol in the A component is an aliphatic boron-based flame-retardant polyol, and its preparation method is:

Boric acid, 1,3-propanediol and xylene were reacted under the protection of nitrogen according to the mass ratio of 5:24:15. The reaction temperature was 130-145°C. During the process, the generated water was continuously separated through the water separator, and the reaction time was 2.5 -4h, then cooled and separated, purified to obtain aliphatic boron-based flame-retardant polyols, the detected hydroxyl value (OH) was 400-450mgKOH/g, the acid value was 2.5-5.0mgKOH/g, and the viscosity was 800-1600mPa.s (25°C) .

The present invention comprehensively utilizes the excellent thermal insulation effect of polyurethane, the small thermal conductivity and the incombustibility of low calorific value inorganic materials. The compatibility of the material matrix, and the modified desulfurized gypsum powder can form a stable thixotropic dispersion system in polyols. After polyurethane foam molding, the modified desulfurized gypsum powder will be distributed on the cell wall and cell material In the skeleton, the rigidity of the cell wall and the foam is enhanced, and the modified desulfurized gypsum powder also has the advantages of non-toxicity, non-volatility, good thermal stability, and no precipitation; on the other hand, the reactive flame retardant aliphatic boron-based Polyols react with isocyanates to reduce the amount of polyether polyols used as raw materials, and the molecules contain boron flame-retardant elements, which improve the flame-retardant properties of foams.

The beneficial effect of the present invention relative to prior art:

(1) Use solid waste - desulfurized gypsum to reduce production costs, reduce waste of resources, achieve energy saving and emission reduction, and develop circular economy;

(2) In the present invention, the desulfurized gypsum powder is organically modified, so that the modified desulfurized gypsum powder has good compatibility with the polyurethane matrix, and the modification method is simple and easy to operate, and is also suitable for scale-up to industrial production;

(3) The present invention prepares a reactive flame-retardant boron-containing polyol, which can partially replace the raw material polyether polyol, and at the same time, the flame-retardant element boron is connected to the polyurethane rigid foam molecular chain, and also increases the flame-retardant properties of polyurethane foam. performance;

(4) The desulfurized gypsum-polyurethane composite fire-proof insulation board made by the present invention has good thermal insulation and flame-retardant performance, and the limiting oxygen index of the material obtained through testing can reach 36%, and the combustion performance reaches A in GB8624-2012 Grade non-combustible, thermal conductivity around 0.025W/m.k, high compressive strength, good dimensional stability.

detailed description

A kind of desulfurization gypsum-polyurethane composite fireproof insulation board and its preparation method of the present invention will be described in detail by using the following examples. Examples are to further describe the present invention in detail, but they do not limit the present invention.

The desulfurization gypsum-polyurethane composite fireproof and heat preservation board of the present invention is prepared according to the following method:

Weigh polyether polyol, polyester polyol, polypropylene glycol, structural flame retardant polyol (made by the method above), and mix evenly with modified desulfurized gypsum powder according to the following formula, then add foam stabilizer and gel catalyst , trimerization catalyst, liquid flame retardant, stir evenly and add foaming agent; then weigh polymethylene polyphenyl polyisocyanate according to the formula, continue to mix and stir with the above mixture, and inject it into the constant temperature mold quickly after the liquid foam is milky Medium foaming, curing, and demoulding to obtain desulfurized gypsum-polyurethane composite fireproof insulation board.

Example 1:

The raw material formula for preparing desulfurized gypsum-polyurethane composite fireproof insulation board is as follows: polyether polyol 403 (a company in Shandong): 30 parts, polyether polyol 4110 (a company in Shandong): 20 parts, polyester polyol 3152 (a company in Beijing) company): 10 parts, polypropylene glycol 1000 (a company in Shandong): 8 parts, structural flame-retardant polyol (self-made): 15 parts, modified desulfurized gypsum powder: 30 parts, foam stabilizer AK-8801 (a company in Jiangsu ) 1 part, foam stabilizer AK-8805 (a company in Jiangsu): 1 part, dibutyltin dilaurate (a company in Jiangsu): 0.5 parts, N, N-dimethylcyclohexylamine (a company in Zhejiang): 2 parts , tricresyl phosphate (TCP) (a company in Tianjin): 15 parts, HCFC-141B (a company in Shandong): 25 parts; polymethylene polyphenyl polyisocyanate: 150 parts.

Example 2:

The raw material formula for preparing desulfurized gypsum-polyurethane composite fireproof insulation board is as follows: polyether polyol 635C (a company in Shandong): 10 parts, polyether polyol 380 (a company in Shandong): 20 parts, polyether polyol 403 (a company in Shandong) Company): 10 parts, polyester polyol P-455N (a company in Beijing): 10 parts, polyester polyol SKR-400E (a company in Beijing): 10 parts, polypropylene glycol 1000 (a company in Shandong): 6 parts, Structural flame retardant polyol (self-made): 22 parts, modified desulfurized gypsum powder: 40 parts, foam stabilizer AK-8812 (a company in Jiangsu) 1.5 parts, foam stabilizer AK-8805 (a company in Jiangsu) 0.5 parts, Foam stabilizer HK-102 (a company in Shandong): 0.5 part, stannous octoate (a company in Jiangsu): 1 part, 1,3,5-tris(dimethylaminopropyl) hexahydrotriazine (a company in Jiangsu): 3 parts, dimethyl methylphosphonate (DMMP) (a company in Shenzhen): 20 parts, cyclopentane (a company in Shandong): 35 parts; polymethylene polyphenyl polyisocyanate: 180 parts.

Example 3:

The raw material formula for preparing desulfurized gypsum-polyurethane composite fireproof insulation board is as follows: polyether polyol 4110 (a company in Shandong): 20 parts, polyether polyol 380 (a company in Shandong): 5 parts, polyether polyol 403 (a company in Shandong) Company): 5 parts, polyether polyol 635C (a company in Shandong): 20 parts, polyester polyol 3152 (a company in Beijing): 15 parts, polypropylene glycol 1000 (a company in Shandong): 5 parts, structural flame retardant Polyol (self-made): 25 parts, modified desulfurized gypsum powder: 35 parts, foam stabilizer polyether modified silicone oil HK-102 (a company in Shandong) 3.5 parts, stannous octoate (a company in Jiangsu): 0.5 parts, two Dibutyltin laurate (a company in Jiangsu): 1.5 parts, pentamethyldiethylenetriamine (a company in Jiangsu): 1 part, tetraphenylresorcinol bispolyphosphate (RDP) (a company in Guangdong): 10 parts Parts, fluorodichloroethane HCFC-141B (a company in Shandong): 40 parts; polymethylene polyphenyl polyisocyanate: 100 parts.

Example 4:

The raw material formula for preparing desulfurized gypsum-polyurethane composite fireproof insulation board is as follows: polyether polyol 4110 (a company in Shandong): 60 parts, polyester polyol 3152 (a company in Beijing): 8 parts, polyester polyol P-455N ( A company in Beijing): 10 parts, polypropylene glycol 1000 (a company in Shandong): 10 parts, structural flame-retardant polyol (self-made): 20 parts, modified desulfurized gypsum powder: 25 parts, foam stabilizer AK-8812 (Jiangsu A company) 2.5 parts, foam stabilizer polyether modified silicone oil HK-102 (a company in Shandong): 0.5 parts, dibutyltin dilaurate (a company in Jiangsu): 1.5 parts, N, N-dimethylcyclohexylamine ( A company in Zhejiang): 1 part, 1,3,5-tris(dimethylaminopropyl) hexahydrotriazine (a company in Jiangsu): 1.5 parts, tetraphenylresorcinol bispolyphosphate (RDP) ( A company in Guangdong): 18 parts, HCFC-141B (a company in Shandong): 30 parts; polymethylene polyphenyl polyisocyanate: 120 parts.

The relevant performance test results of the composite fireproof and thermal insulation boards of the above examples are shown in Table 1.

Table 1

According to the test results in Table 1, the desulfurized gypsum-polyurethane composite thermal insulation and fireproof board prepared in the above embodiments of the present invention has excellent flame retardancy, and the combustion performance has reached Class A non-combustibility, while maintaining a low thermal conductivity and good thermal insulation performance , the mechanical properties have high compressive strength, so it can be widely used in the field of building exterior wall insulation construction.

Claims (10)

1. desulfurated plaster-polyurethane composite fireproof heat preservation board, is characterized in that: it includes A, B two groups Composition, described A group composition is made up of the raw material of following masses number: polyether polyol: 40-60 part, polyester Polyhydric alcohol: 10-20 part, polypropylene glycol: 5-10 part, structural type flame-proof polyol: 15-25 part, modified de- Sulfur Gypsum Fibrosum powder: 25-40 part, foam stabilizer: 2-3.5 part, gel-type catalyst: 0.5-2 part, catalyst for trimerization: 1-3 part, liquid flame retardant: 10-20 part, foaming agent: 25-40 part；The mass parts of B component is: many methylenes Quito polyphenyl polyisocyanate: 100-180 part, is stirring evenly and then adding into foaming agent by component A, is subsequently added B component, pour into after high-speed stirred the foaming of constant temperature mould, ripening, the demoulding prepare desulfurated plaster-polyurethane multiple Close fireproof heated board.

Fireproof heated board the most according to claim 1, is characterized in that: described polyether polyol is poly-four One or more of hydrogen furan polyols or polyoxypropylene polyol, hydroxyl value is 420-480mgKOH/g, viscous Degree is 2000-3500mPa.s (25 DEG C).Described PEPA is aliphatic polyester polyols or fragrance adoption One or more of ester polyol, hydroxyl value is 400-440mgKOH/g, and viscosity is 4000-6000mPa.s (25℃).Described polypropylene glycol is polypropylene glycol 1000, and hydroxyl value is 100-130mgKOH/g, and viscosity is 1000-1300mPa.s(25℃)。

Fireproof heated board the most according to claim 1, is characterized in that: described structural type is fire-retardant polynary Alcohol is aliphatic boryl flame-proof polyol.

Fireproof heated board the most according to claim 1, is characterized in that: catalyst bag in described component A Including gel-type catalyst and catalyst for trimerization, wherein gel-type catalyst is dibutyl tin laurate, octanoic acid Asia One or both of stannum or triethylene diamine, catalyst for trimerization is N, N-dimethyl cyclohexyl amine, N, N-diformazan Base benzylamine, 1,3,5-tri-(dimethylamino-propyl) Hexahydrotriazine, the one of pentamethyl-diethylenetriamine or several Kind.

Fireproof heated board the most according to claim 1, in described component A, liquid flame retardant is tricresyl phosphate Toluene ester (TCP), dimethyl methyl phosphonate (DMMP), triethyl phosphate, tetraphenyl resorcinol are double The combination in any of one or more in poly phosphate (RDP).

Fireproof heated board the most according to claim 1, in described component A foam stabilizer be polysiloxanes, One or more of polyether silicone or polyether modified siloxane.

Fireproof heated board the most according to claim 1, in described component A, foaming agent is fluorine two chloroethene One or more of alkane or Pentamethylene..

8. a preparation method for the fireproof heated board described in claim 1, is characterized in that comprising the following steps:

Mass fraction in step 1, component A as described in claim 1 weighs raw material, by polyether polyol, PEPA, polypropylene glycol, structural type flame-proof polyol, modified desulfurization gypsum powder mix homogeneously, add Foam stabiliser, gel-type catalyst, catalyst for trimerization, liquid flame retardant, it is stirring evenly and then adding into foaming agent；

Mass fraction in step 2, B component as described in claim 1 weighs the many isocyanides of polymethylene polyphenyl Acid esters, high-speed stirred after component A and B component are mixed, after liquid foam is milky white, it is rapidly injected constant temperature mould Tool foams, ripening, the demoulding, obtain described desulfurated plaster-polyurethane composite fireproof heat preservation board.

The preparation method of fireproof heated board the most according to claim 6, is characterized in that in described component A modified The preparation method of desulfurization gypsum powder is:

Take the 5%-10% that amount is desulfurization gypsum powder quality of coupling agent, be configured to the ethanol containing coupling agent 2%-4% Solution, is placed in desulfurization gypsum powder in the ethanol solution containing coupling agent, filters after stirring, and filter cake exists Being dried 2h at 100 DEG C-120 DEG C, prepare modified desulfurization gypsum powder, wherein coupling agent is Silane coupling agent KH550 Or butyl titanate.

The preparation method of fireproof heated board the most according to claim 6, is characterized in that tying in described component A Configuration flame-proof polyol is aliphatic boryl flame-proof polyol, and its preparation method is:

Boric acid, 1,3-PD and dimethylbenzene are reacted under nitrogen protection according to the mass ratio of 5:24:15, instead Answer temperature to be 130-145 DEG C, during constantly distribute the water of generation by water knockout drum, response time 2.5-4h, Then cool down layering, purification obtains aliphatic boryl flame-proof polyol, detection hydroxyl value (OH) 400-450mgKOH/g, acid number 2.5-5.0mgKOH/g, viscosity 800-1600mPa.s (25 DEG C).