CN104130685A - Reaction type halogen-free flame-retardant spray polyurea elastomer coating and preparation method thereof - Google Patents

Abstract

The invention discloses a reactive halogen-free flame-retardant spray polyurea elastomer coating, which consists of component A and component B. The raw materials of component A are: polyisocyanate, polyether polyol, halogen-free Phosphorus polyol; the raw material composition of the B component: amino-terminated polyether, amine chain extender, composite flame retardant, catalyst. The preparation method of the coating is also disclosed: including steps: preparation of component A: dehydrating polyether polyol, adding polyisocyanate for reaction, adding halogen-free phosphorus-containing polyol for reaction, cooling, filtering and packaging; component B Preparation: Fully disperse amino-terminated polyether and amine chain extender, then add composite flame retardant, fully disperse, filter and pack. The raw materials of the invention are easy to obtain, the production process is simple and feasible, and the two components of the paint can be quickly formed into films by spraying with high-temperature and high-pressure special spraying equipment, and the construction efficiency is high. The coating film formed by spraying has good flame retardant effect, environmental protection, good mechanical properties and good aging resistance.

Description

A reactive halogen-free flame-retardant spray polyurea elastomer coating and its preparation method

technical field

The invention relates to a reactive halogen-free flame-retardant spray polyurea elastomer coating and a preparation method thereof.

Background technique

Polyurea Elastomer (PUA for short) is a new type of environmentally friendly coating that has emerged after high-solid coatings, water-based coatings, light-curing coatings, powder coatings and other low (no) pollution coatings in foreign countries in the past 20 years. It is developed on the basis of reaction injection molding (RIM) technology. The Polyurea Development Association (PDA) defines polyurea as a polymer formed by the reaction of an isocyanate-terminated prepolymer (A component) and an amino compound component (R component). A component and R component are sprayed by high temperature and high pressure equipment. The process is a rapid response spraying system, the raw material system does not contain solvents, the curing speed is fast, the process is simple, and it can be easily sprayed on the facade and curved surface with a thickness of more than ten millimeters without sagging. The coating has excellent strength and elasticity, and has excellent water resistance, chemical corrosion resistance and aging resistance, and has developed rapidly in recent years.

As the application of polyurea continues to expand, its defects are increasingly exposed. For example, the rapid film formation of polyurea is not conducive to bonding because it cannot guarantee a sufficient wetting angle, and it is prone to the problem of overall shedding; also due to the characteristics of rapid response, it is easy to peel off between polyurea layers. Therefore, in recent years, in addition to improving the physical and chemical properties of polyurea coatings, researchers have focused on the research and development of polyurea supporting primers, supporting interlayer adhesives and supporting aliphatic topcoats. in application. Polyurea elastomer itself is a flammable high polymer. As polyurea is more and more widely used in high-grade building insulation and waterproofing, in the inner wall of ship cabins, in stage props, and in petrochemical anticorrosion and other fields, customers are interested in The demand for flame retardant polyurea is also becoming more and more urgent.

Chinese patent CN 201110215861.8 authorizes a flame-retardant spray polyurea elastomer coating and its preparation method. The coating is composed of A and B components. The A component is synthesized from polyether polyol and polyisocyanate, and the B component is composed of amino-terminated polyether, amino-terminated chain extender, composite flame retardant and catalyst. The composite flame retardant is composed of tetrabromophthalic anhydride diol, TCPP, chlorinated paraffin and antimony trioxide. After A and B components are mixed according to a certain ratio, they are sprayed to form a film. The coating utilizes the synergistic mechanism of halogen and antimony trioxide to achieve flame retardant effect. Although it can achieve a better flame retardant effect, the smoke contains greater toxicity due to the halogen content.

Chinese patent CN 201010606500.1 discloses an intumescent fireproof material with polyurea resin as a film former and its application. The paint contains two components A and B. A component contains: isocyanate prepolymer, B component contains: amino-terminated polyether, polyamine chain extender, diluent, carbon forming catalyst, char forming agent, blowing agent, flame retardant, smoke inhibitor, pigment Fillers, additives, mixed solvents. The coating uses the mechanism of burning the paint film into charcoal, forming a carbonized layer, and hindering the combustion for flame retardancy. However, due to the addition of more carbon-forming substances and fillers, the viscosity of component B is not easy to control, and it is more difficult to use spraying.

Chinese patent CN 200710130184.3 authorizes spraying flame retardant flexible polyurea composition and its application. The coating is composed of A and R components. A component is a semi-prepolymer synthesized from polyisocyanate and flame-retardant polyol, and the free isocyanate content of the semi-prepolymer is between 13 and 18%; R component is composed of chain extender, flame retardant and amino-terminated polyol. Ether combination. Among them, the flame retardant polyol is tetrabromophthalate diol, and the flame retardant is melamine composite flame retardant, pentabromodiphenyl ether, and decabromodiphenyl ether. The invention adopts the flame retardant mechanism of halogens to form incombustible hydrogen halides to insulate the air, and to inhibit the chain reaction of burning polymer materials to scavenge free radicals.

Contents of the invention

The object of the present invention is to provide a reactive halogen-free flame-retardant spray polyurea elastomer coating and a preparation method thereof.

The technical scheme that the present invention takes is:

A reactive halogen-free flame-retardant spray polyurea elastomer coating, which consists of component A and component B. The raw materials of component A are proportioned as follows in terms of mass percentage: 50-60% polyisocyanate, 30- 40% polyether polyol, 5-15% halogen-free phosphorus-containing polyol;

The ratio of the raw materials of the B component is as follows in terms of mass percentage: 20-40% amino-terminated polyether, 10-30% amine chain extender, 30-50% composite flame retardant, 0.1-1 % catalyst;

The raw materials of the composite flame retardant are as follows according to mass percentage: 30-50% phosphate flame retardant, 40-60% halogen-free phosphorus-containing polyol, 5-15% nano-aluminum hydroxide, 1~3% coupling agent.

The polyisocyanate is at least one of aliphatic polyisocyanate, alicyclic polyisocyanate and aromatic polyisocyanate.

The polyisocyanate is at least one of 4,4'-MDI, 2,4'-MDI, 2.2'-MDI, MDI-100LL, PAPI, TDI, HDI, IPDI, HMDI, XDI, NDI, PPDI, CHDI kind.

The polyether polyol is at least one of the following substances with a number average molecular weight of 500-5000: polyoxypropylene polyol, polycaprolactone polyol, polyacrylate polyol, polybutadiene polyol, poly carbonate diol.

The halogen-free phosphorus-containing polyols are tris(dipropylene glycol) phosphite, N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid diethyl ester, N,N-bis(2- Hydroxyethyl) at least one of dimethyl aminomethylphosphonate.

The amino-terminated polyether is at least one of the following substances with a number average molecular weight of 400-5000: polyether diamine and polyether triamine.

The amine chain extender is at least one of diethyltoluenediamine and 4,4'-bis-sec-butylaminodiphenylmethane.

The catalyst is at least one of an organic tin catalyst and an organic bismuth catalyst.

The preparation method of reactive halogen-free flame-retardant polyurea elastomer coating includes the preparation of A component and B component, and is characterized in that:

The preparation method of component A is as follows: add accurately measured polyether polyols into the reaction kettle and fully dehydrate; control the temperature below 60°C, add accurately measured polyisocyanate, and heat up to 80°C to 85°C for reaction; finally Add accurately measured halogen-free phosphorus-containing polyols for reaction; cool down to below 60°C, filter and pack; obtain component A;

The preparation method of the composite flame retardant is as follows: add the measured phosphate flame retardant into the closed dispersion kettle, start the dispersion; add the measured coupling agent into the phosphate flame retardant, heat to 80- At 100°C, add nano-aluminum hydroxide and disperse fully to obtain a homogeneous solution; finally add a measured amount of halogen-free phosphorus-containing polyol to disperse fully; cool down to below 60°C; filter and seal the package to obtain a composite flame retardant.

The preparation method of component B is as follows: pour the measured amino-terminated polyether and amine chain extender into the dispersion tank, fully disperse, add the measured catalyst, fully disperse; then add the compound flame retardant, fully disperse, Filter and pack to obtain component B.

In the preparation method of component A, polyisocyanate is added, and the temperature is raised to 80° C. to 85° C. for 2.5 hours of reaction; halogen-free phosphorus-containing polyol is added for 1.5 hours of reaction.

The beneficial effects of the invention are: the raw materials of the invention are easy to obtain, the production process is simple and feasible, the two components of the paint can be quickly formed into films by spraying with high-temperature and high-pressure special spraying equipment, and the construction efficiency is high. The coating film formed by spraying has good flame retardant effect, environmental protection, good mechanical properties and good aging resistance.

Detailed ways

A reactive halogen-free flame-retardant spray polyurea elastomer coating, which consists of component A and component B. The raw materials of component A are proportioned as follows in terms of mass percentage: 50-60% polyisocyanate, 30- 40% polyether polyol, 5-15% halogen-free phosphorus-containing polyol;

The ratio of the raw materials of the B component is as follows in terms of mass percentage: 20-40% amino-terminated polyether, 10-30% amine chain extender, 30-50% composite flame retardant, 0.1-1 % catalyst;

The raw materials of the composite flame retardant are as follows according to mass percentage: 30-50% phosphate flame retardant, 40-60% halogen-free phosphorus-containing polyol, 5-15% nano-aluminum hydroxide, 1~3% coupling agent.

The polyisocyanate is at least one of aliphatic polyisocyanate, alicyclic polyisocyanate and aromatic polyisocyanate; preferably, the polyisocyanate is 4,4'-MDI, 2,4'-MDI, 2. At least one of 2'-MDI, MDI-100LL, PAPI, TDI, HDI, IPDI, HMDI, XDI, NDI, PPDI, CHDI.

The polyether polyol is at least one of the following substances with a number average molecular weight of 500-5000: polyoxypropylene polyol, polycaprolactone polyol, polyacrylate polyol, polybutadiene polyol, poly carbonate diol.

The halogen-free phosphorus-containing polyols are tris(dipropylene glycol) phosphite, N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid diethyl ester, N,N-bis(2- Hydroxyethyl) at least one of dimethyl aminomethylphosphonate.

The amino-terminated polyether is at least one of the following substances with a number average molecular weight of 400-5000: polyether diamine and polyether triamine.

The amine chain extender is at least one of diethyltoluenediamine and 4,4'-bis-sec-butylaminodiphenylmethane.

The catalyst is at least one of an organic tin catalyst and an organic bismuth catalyst.

The coupling agent is at least one of silane coupling agent, titanate coupling agent, zirconate coupling agent, aluminate coupling agent, preferably, titanate coupling agent, silane At least one of the coupling agents, more preferably, at least one of titanate coupling agents, KH550, KH560, KH570, KH580, KH602, and KH792.

The preparation method of reactive halogen-free flame-retardant polyurea elastomer coating includes the preparation of A component and B component, and is characterized in that:

The preparation method of component A is as follows: Add accurately measured polyether polyols into the reaction kettle, stir at a constant speed, heat to 100-110°C, keep the temperature at 100°C-110°C for 1.5h under reduced pressure; cool down to 60°C Next, add accurately measured polyisocyanate, heat up to 80°C to 85°C, and react for 2.5 hours; finally add accurately measured flame-retardant polyether polyol, react for 1.5h; cool down to below 60°C, filter and pack; that is, Group A point;

The preparation method of the composite flame retardant is as follows: add the measured phosphate flame retardant into the closed dispersion tank, and start the dispersion; add the measured coupling agent into the phosphate flame retardant, continue to disperse and simultaneously Heating; heating to 80°C, adding nano-aluminum hydroxide, and fully dispersing until a homogeneous solution is obtained; finally adding a measured amount of flame-retardant polyether polyol, dispersing for 0.5-1h; cooling to below 60°C; filtering, sealing and packaging, and the compound is obtained flame retardant.

The preparation method of component B is as follows: pour the measured amino-terminated polyether and amine chain extender into the dispersion tank, disperse for 0.5-1h, then add the measured catalyst, disperse for 0.5-1h; continue to add compound flame retardant The agent is dispersed for 0.5-1h, filtered and packaged to obtain component B.

During spraying construction, components A and B shall be carried out according to the volume ratio of 1:1.

Compared with the traditional spray polyurea elastomer, the present invention has the following prominent features:

1. Through the use of halogen-free phosphorus-containing polyols, flame retardant elements are directly introduced into the polymer molecules to achieve the effect of intrinsic flame retardancy, which not only avoids the volatilization loss of liquid flame retardants during spraying, but also improves the flame retardancy through intrinsic flame retardancy. While improving the combustion effect, it reduces the impact on the mechanical properties of the material. At the same time, the introduction of flame retardant elements through the reaction can combine the flame retardant elements with the film-forming substances, avoiding the disadvantages of liquid flame retardants that decrease in flame retardant effect over time, and achieve permanent flame retardant effects;

2. All raw materials of the coating, including flame retardants, are halogen-free and environmentally friendly. During the combustion process, a large amount of halogen-containing toxic and harmful gases will not be produced, thereby reducing the harm of burning smoke to the human body;

3. Inorganic flame retardants have a high decomposition temperature. In addition to the flame retardant effect, they also have the effect of inhibiting smoke and hydrogen chloride formation. However, inorganic flame retardants generally need to be added in a considerable amount to have a good flame retardant effect. Spraying polyurea elastomers requires the viscosity of the system to be as low as possible. Adding inorganic flame retardants will lead to increased viscosity, and improper handling will lead to uneven mixing. The present invention uses coupling agent and phosphate flame retardant to modify the nano-inorganic hydroxide flame retardant through a special production process, supplemented with halogen-free phosphorus-containing polyols to prepare a composite flame retardant, which not only solves the problem of solid-state flame retardant The disadvantage of poor compatibility between the flame retardant and polyether, and the high-efficiency nano-inorganic hydroxide flame retardant can be uniformly dispersed in the system, and through the synergy with the low-volatility phosphoric acid ester liquid flame retardant, the flame retardant is improved. Combustion effect, and improve the storage stability of the system;

4. Since the addition of flame retardants will affect the strength of the material, by using highly active amino-terminated polyethers and suitable amine chain extenders to increase the cross-linking density of the system, the prepared polyurea elastomer flame-retardant coatings are both It has good flame retardant effect, and has excellent strength and toughness, and can adapt to waterproof, anti-corrosion and other application fields that require flame retardant performance.

5. The present invention achieves the flame retardant effect through the joint action of reactive halogen-free phosphorus-containing polyols, liquid phosphate flame retardants, and nano-aluminum hydroxide. Since a large amount of flame retardant powder is not added alone, Group A The partial viscosity can be controlled below 1000 centipoise (25°C), the viscosity of component B can be controlled below 1300 centipoise (25°C), and the viscosities of the two components are close. When spraying polyurea (type XP3 equipment), the paint can be mixed uniformly at a volume ratio of 1:1, and the mechanical properties of the cured paint film are good.

Below in conjunction with specific embodiment, formula of the present invention is described further:

Example 1:

A reactive halogen-free flame-retardant spray polyurea elastomer coating, which is composed of A component and B component, and its formula composition is as follows:

Table 1:

The performance test results are shown in Table 2:

Table 2:

 

Comparative example 1:

A spraying polyurea elastomer coating is composed of component A and component B, and its formulation is as follows:

table 3:

The performance test results of Comparative Example 1 are as follows:

Table 4:

 

Both components A and B in Example 1 have reactive flame retardant tris(dipropylene glycol) phosphite, supplemented by liquid additive type flame retardant dimethyl methylphosphonate and inorganic flame retardant Fuel powder nano aluminum hydroxide. Comparative Example 1 only has the liquid-added flame retardant 3-dichloropropyl phosphate. The overall flame retardant effect includes environmental flame retardant indicators such as smog toxicity, and Example 1 is better than Comparative Example 1. From the above experimental data, it can be concluded that the mechanical properties of Comparative Example 1 are slightly lower than those of Example 1, which means that the intrinsic flame retardancy of Example 1 has little influence on the mechanical properties of the material; After 3150MJ/m ² (1512h), the flame retardant performance of Example 1 did not decrease significantly, while the flame retardant performance of Comparative Example 1 decreased significantly. It can be said that Example 1 maintains the flame retardant effect for a longer period of time because it is essentially flame retardant.

Example 2:

A reactive halogen-free flame-retardant spray polyurea elastomer coating, which is composed of A component and B component, and its formula composition is as follows:

table 5:

The performance test results are shown in Table 6:

Table 6:

 

Example 3:

A reactive halogen-free flame-retardant spray polyurea elastomer coating, which is composed of A component and B component, and its formula composition is as follows:

Table 7:

 

The performance test results are shown in Table 8:

Table 8:

 

Example 4:

A reactive halogen-free flame-retardant spray polyurea elastomer coating, which is composed of A component and B component, and its formula composition is as follows:

Table 9:

 

The performance results are tested in Table 10 as follows:

Table 10:

Claims (10)

1. a response type halogen-free flameproof spray polyurea elastomer coating, formed by A component and B component, it is characterized in that: proportioning is as follows by mass percentage for the raw material of described A component: 50～60% polyisocyanates, 30～40% polyether glycol, 5～15% halogen-free phosphorus-containing polyvalent alcohol;

Proportioning is as follows by mass percentage for the raw material of described B component: 20～40% ending amino polyether, 10～30% amine chain extender, 30～50% composite flame-retardant agent, 0.1～1% catalyzer;

The raw material of described composite flame-retardant agent by mass percentage proportioning is as follows: 30～50% phosphoric acid ester fire retardant, 40～60% halogen-free phosphorus-containing polyvalent alcohol, 5～15% nano-aluminum hydroxide, 1～3% coupling agent.

2. a kind of response type halogen-free flameproof spray polyurea elastomer coating according to claim 1, is characterized in that: described polyisocyanates is at least one in aliphatic polyisocyante, alicyclic polyisocyanates, aromatic polyisocyanate.

3. a kind of response type halogen-free flameproof spray polyurea elastomer coating according to claim 2, it is characterized in that: described polyisocyanates is 4,4 '-MDI, 2, at least one in 4 '-MDI, 2.2'-MDI, MDI-100LL, PAPI, TDI, HDI, IPDI, HMDI, XDI, NDI, PPDI, CHDI.

4. a kind of response type halogen-free flameproof spray polyurea elastomer coating according to claim 1, is characterized in that: described polyether glycol is that number-average molecular weight is at least one in the following material of 500-5000: polyoxypropylene polyol, polycaprolactone polyol, polyacrylate polyol, polybutadiene polyol, polycarbonate diol.

5. a kind of response type halogen-free flameproof spray polyurea elastomer coating according to claim 1, it is characterized in that: described halogen-free phosphorus-containing polyvalent alcohol is three (dipropylene glycol) phosphorous acid ester, N, N-bis-(2-hydroxyethyl) AminomethylphosphoniAcid Acid diethyl ester, N, at least one in N-bis-(2-hydroxyethyl) AminomethylphosphoniAcid Acid dimethyl ester.

6. a kind of response type halogen-free flameproof spray polyurea elastomer coating according to claim 1, is characterized in that: described Amino Terminated polyether(ATPE) is that number-average molecular weight is at least one in 400～5000 following material: polyethers diamine, polyethers tertiary amine.

7. a kind of response type halogen-free flameproof spray polyurea elastomer coating according to claim 1, is characterized in that: described amine chain extender is diethyl toluene diamine, 4, at least one in 4 '-bis-Zhong Ding ADP methylmethanes.

8. a kind of response type halogen-free flameproof spray polyurea elastomer coating according to claim 1, is characterized in that: described catalyzer is at least one in organotin catalysts, organic bismuth catalyst.

9. the preparation method of response type halogen-free flameproof polyurea elastomer coating claimed in claim 1, comprises the preparation of A component and the preparation of B component, it is characterized in that:

The preparation method of A component is as follows: the polyether glycol of accurate measurement is joined in reactor, fully dehydration; Control temperature below 60 DEG C, add the polyisocyanates of accurate measurement, be warming up to 80 DEG C～85 DEG C and react; Finally add the halogen-free phosphorus-containing polyvalent alcohol of accurate measurement to react; Be cooled to below 60 DEG C, filter and package; Obtain A component;

The preparation method of composite flame-retardant agent is as follows: the phosphoric acid ester fire retardant measuring is added in airtight Scattered Kettle, starts and disperse; The coupling agent measuring is added in phosphoric acid ester fire retardant, is heated to 80-100 DEG C, add nano-aluminum hydroxide, fully disperse, obtain homogeneous solution; Finally add the halogen-free phosphorus-containing polyvalent alcohol of metering, fully disperse; Be cooled to below 60 DEG C; Filtration packs, and obtains composite flame-retardant agent;

The preparation method of B component is as follows: the Amino Terminated polyether(ATPE) measuring and amine chain extender are poured in dispersion cylinder, fully disperseed, add the catalyzer measuring, fully disperse; Add again composite flame-retardant agent, fully disperse, filter and package, obtain B component.

10. the preparation method of response type halogen-free flameproof polyurea elastomer coating according to claim 9, is characterized in that: in the preparation method of A component, add polyisocyanates, be warming up to 80 DEG C～85 DEG C and react 2.5h; Add halogen-free phosphorus-containing polyvalent alcohol to react 1.5h.