CN106700920A - Reaction type polysiloxane flame-retardant coating and preparation method thereof - Google Patents

Abstract

The invention discloses a reactive polysiloxane flame retardant coating and a preparation method thereof, belonging to the technical field of flame retardant coatings. The coating composition is composed of silane coupling agent, ammonium polyphosphate, film forming agent, polysiloxane flame retardant, wetting agent and ethanol. The film-forming agent of the present invention and the silane coupling agent play a film-forming effect simultaneously, and the silane coupling agent can interact with the synthesized polysiloxane flame retardant again, and both the silane coupling agent and the flame retardant can Ammonium polyphosphate can be microencapsulated and then reacted to obtain a reactive polysiloxane flame-retardant coating with a spatially cross-linked network structure. The coating uses ethanol as a solvent, and the raw materials in the entire system are environmentally friendly reagents. No harm to the environment and operators; the coating is a reactive coating with high flame retardant efficiency, which can make the limiting oxygen index LOI of polypropylene reach 31.3% and pass the UL‑94 V0 test without affecting the mechanics of the substrate at all Performance, can be deformed together with the matrix without falling off.

Description

A kind of reactive polysiloxane flame retardant coating and preparation method thereof

technical field

The invention relates to a reactive polysiloxane flame retardant coating and a preparation method thereof, belonging to the technical field of flame retardant coatings.

Background technique

In modern life, fires caused by improper fire control occur frequently, which lead to huge loss of life and property. However, a large number of commonly used materials are flammable, so it is imperative to endow these materials with flame retardancy to reduce the probability of fire occurrence.

Usually, in terms of flame retardant treatment methods, there are flame retardants blended with the matrix, preparation of intrinsic flame retardant polymers, and application of high polymer flame retardant coatings. Intrinsic polymers are difficult to prepare, their types are small, and their applications are limited. The additive type requires a large amount of addition to have a flame retardant effect, and this will bring the following problems: first, the flame retardant migrates to the surface after a period of time to make the composition uneven; second, the combination of the additive type and the matrix is relatively weak. Fragility, which creates weak points in the matrix and reduces the mechanical properties of the matrix.

It is a better method to achieve the purpose of flame retardant by using flame retardant coating, and it is also a hot research topic at present. Compared with the other two methods, since the flame retardant coating is attached to the surface of the polymer matrix without destroying the internal structure of the matrix, it will not have adverse effects on the mechanical properties of the matrix and maintain the original properties of the matrix material . In addition, the flame retardant coating can be dissolved in some solvents to achieve the purpose of recycling the substrate. However, there are few reports on the application of flame retardant coatings to the surface of polymer engineering plastics. The main reasons are as follows: First, due to the low polarity and high hydrophobicity of the surface of polymer engineering plastics, the bonding force between the coating and the substrate is reduced, it is easy to fall off, and the good flame retardant effect cannot be achieved. Second, the flexibility of the coating is not enough, it is difficult to adapt to some polymer engineering plastics, such as the coating is easy to break and fall off when the polypropylene is bent. Therefore, in order to solve the flammability problem of polymer engineering plastics by coating, it is necessary to consider the flame retardancy of the coating, the bonding force between the coating and the substrate, and the flexibility of the coating/substrate after the coating is applied.

Chinese Patent Publication No. CN104862970A discloses a "high flame retardant and non-toxic fabric coating material and its preparation method". Resin, and finally paint. This method has low production cost and wide application fields, but its preparation steps are cumbersome and its flame-retardant performance is limited, and it does not explain the influence of the coating on the properties of the substrate.

Chinese Patent Publication No. CN105419607A discloses "a light-cured composite coating for construction and its preparation method", the steps of which include the following steps: (1) mixing o-cresol novolac epoxy acrylate, water-soluble anionic polyurethane, formazan 2-hydroxyethyl acrylate, diphenylacetone, and polydimethylsilane are evenly mixed, and then added with deionized water and stirred to make an emulsion; (2) adding pH regulators butylethanolamine, tolyldiphenyl Stir and disperse the phosphate ester at 30°C for 30 minutes, and then place it in an oven at 50°C for half an hour to obtain a composite coating; (3) The composite coating is cured under ultraviolet light for 30-40s. The patent does not mention the flame-retardant properties of the flame-retardant coating, and if the coating needs to be applied to substrates such as buildings and wood, it needs to be modified. The curing of the coating needs to be completed under ultraviolet light. Cumbersome and limited in application.

The document "Jimenez, M.; Duquesne, S.; Bourbigot, S., Fire protection of polypropylene and polycarbonate by intumescent coatings. Polymers for Advanced Technologies 2012, 23 (1), 130-135." discloses the use of intumescent flame retardant coatings Flame retardant finishing of polypropylene and polycarbonate. After finishing the coating, the flame retardancy of the two polymers has been greatly improved. The flame retardant coating is an intumescent varnish. There is no mention in the literature whether the coating has good mechanical properties and whether the coating has good mechanical properties. influence on the mechanical properties of the matrix.

Chinese Patent Publication No. CN101925660A discloses "Organosilane Coating Composition and Its Application". The preparation steps of the composition include: (1) in the presence of a catalyst, organosilane is hydrolyzed; (2) organometallic precursor performing chelation; (3) mixing the hydrolyzed silane with the chelated organometallic precursor; (4) hydrolyzing the organosilane-organometallic precursor mixture. The patent introduces the preparation method and application of the composition in detail, and the coating design is reasonable and the effect is remarkable. However, if it is used in the field of flame retardancy, its binding force with the polymer matrix is weak, it is easy to peel off, and it cannot play a good protective role.

The Chinese Patent Publication No. CN103059727A discloses "a metal surface silane treatment agent containing hexamethylphosphoric triamide and its preparation method". The treatment agent of the invention can improve the corrosion resistance of the metal after treating the metal. There are many patents similar to this patent, and many of them introduce silane coupling agents or substances containing -Si-O-CH ₂ CH ₃ and silanol into the coating, and connect other components with the metal surface through it to implement metal protection. protection to achieve corrosion resistance. However, it is rare to introduce silane coupling agent into the flame retardant finishing of high polymer coating, which may be due to the large difference in polarity, wettability and roughness between the metal surface and the polymer surface. Many coatings applied to metal anti-corrosion cannot be directly applied to high polymers for flame retardancy, because factors such as the bonding force between the coating and the polymer matrix, the composition of the coating, and the like must be considered.

The Chinese Patent Publication No. CN102218883A discloses "a wood-plastic board coated with a silicon flame-retardant coating". Advantages such as flammability, but its thickness is much larger than the thickness in this patent. In addition, the patent does not mention the effect of flame retardant coating on the mechanical properties of wood and the adhesion between coating and wood.

Contents of the invention

The present invention aims to provide a reactive polysiloxane flame retardant coating and its preparation method. The coating components can react with each other during the preparation process and when heated. The coating preparation method is simple and has good resistance to fire. Flammability and flexibility.

The invention provides a reactive polysiloxane flame retardant coating, which is characterized in that its spatial structure is:

The structural formula of polysiloxane flame retardant is:

Among them, m>0, n>0, x≥0; m and n are positive integers, and x is a non-negative integer;

R ₁ and R ₂ are respectively one of H, CH ₃ or OH;

R ₃ is CH ₂ CH(CH ₂ OH)-P(=O)-OC ₁₂ H ₈ , CH ₂ CH(OH)-CH ₂ -P(=O)-OC ₁₂ H ₈ , CH ₂ -CH(OH )-CH ₂ -P(=O)-(C ₆ H ₅ ) ₂ , CH ₂ -CH(CH ₂ OH)-P(=O)-(C ₆ H ₅ ) ₂ , CH(OH)-CH ₂ One of -P(=O)(OH) ₂ , CH(OH)-CH ₂ -P(=O) ₂ or CH(OH)-CH ₂ -P(=O)(OH)H;

R ₄ is (CH ₂ ) ₃ -Si-(O-CH ₂ CH ₃ ) ₃ , (CH ₂ ) ₃ -Si-(O-CH ₃ ) ₃ , ((CH ₃ ) ₂ )Si-NCO,

((CH ₃ ) ₂ )Si-NHC(=O)-(CH ₃ )Si(-OL)-R ₁ or ((CH ₃ ) ₂ )Si-NHC(=O)-(CH ₃ )Si(- OL)-R ₂ in one; wherein R ₁ and R ₂ are the same as above, and L represents the -Si-O-Si- main chain in the molecule.

The reactive polysiloxane flame-retardant coating is made of the following raw materials in parts by weight:

5-7 parts of film-forming agent;

3-5 parts of ammonium polyphosphate;

2-6 parts of polysiloxane flame retardant;

10-30 parts of silane coupling agent;

Wetting agent 1-2 parts;

50-150 parts of ethanol;

The resulting flame-retardant coating has strong adhesion and is firmly combined with the substrate;

Wherein said polysiloxane flame retardant is made from the raw material of following parts by weight:

5-10 parts of hydrogen-containing silicone oil;

30-50 parts of allyl glycidyl ether;

5-20 parts of isocyanatosilane;

30-50 parts of phosphorus-containing active substances;

During the reaction process, the amount of catalyst used is: 1.8004*10 ^-1 -4.501*10 ^-1 parts; the amount of solvent used is: 160-280 parts; the amount of washing solvent used is: 80-150 parts.

Further, the film-forming agent is one or more of polyvinyl formal, polyvinyl alcohol, polyenyl acetal, polyvinyl butyral or polyvinyl formal; when two or, the mass ratio of the two is 1:1.

Further, the wetting agent is sodium lauryl sulfate, xylitol anhydride fatty acid ester, polyoxyethylene (20) sorbitan monooleate, polyoxyethylene fatty acid ester or polyoxyethylene One or two kinds of alkyl phenyl ethers; when two kinds are selected, the mass ratio is 1:1.

Further, the silane coupling agent is γ-glycidyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, Isocyanatopropyltriethoxysilane, ureapropyltriethoxysilane, N-aminoethyl-γ-aminopropyltrimethoxysilane, divinyltriaminopropyltrimethoxysilane or dimethyl One or two kinds of diisocyanatosilanes; when two kinds are selected, the molar ratio is 1:1.

Further, the catalyst is two of Speier catalyst, Karstdet catalyst, triphenylphosphine or triethanolamine;

The hydrogen-containing silicone oil is polymethylhydrogensiloxane, poly(methylhydrogensiloxane-dimethylsiloxane copolymer), 1,3,5,7-tetramethylcyclotetrasiloxane or One of the hydrogen-terminated polydimethylsiloxanes;

The isocyanatosilane is one of 3-isocyanatopropyl trimethoxysilane, isocyanatopropyl triethoxysilane or dimethyl diisocyanatosilane;

The phosphorus-containing active substance is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphoric acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid, dialkyl phosphite or diphenyl One of the base phosphorus oxides;

Described solvent is one or both in Virahol, dehydrated alcohol, toluene, benzene, acetone, methylene chloride, chloroform, N, N-dimethylformamide; When using two kinds, The volume ratio of the two solvents is 1:1;

The washing solvent is one or two of acetone, absolute ethanol, deionized water, and N,N-dimethylformamide; when two are used, the volume ratio of the two is 1:1.

The applicable substrate of the reactive polysiloxane flame-retardant coating can be polypropylene, polyethylene, polystyrene or polyester plastic, and it is also suitable for the protection of paper, wood or metal materials.

The invention provides a preparation method of the above-mentioned reactive polysiloxane flame retardant coating, comprising the following steps:

(1) Add ethanol to the beaker, control the stirring speed to 800-1000r/min, then add the film-forming agent, and continue stirring for 20-40min after adding;

(2) Add ammonium polyphosphate at the same speed, and keep stirring for 10-30min;

(3) Add silane coupling agent to the above solution at room temperature to 70°C, and stir at constant temperature for 10-30 minutes;

(4) Add polysiloxane flame retardant to the mixed liquid obtained in step (3), and stir thoroughly for 20-40 minutes;

(5) Add a wetting agent to step (4), and evaporate the ethanol at a stirring speed of 400-600r/min and a temperature of 80-100°C until it becomes viscous and stop heating.

In the above-mentioned method, the preparation method of described polysiloxane flame retardant comprises the following steps:

(1) Add hydrogen-containing silicone oil, catalyst and 50-70 parts of solvent into a four-necked flask equipped with a reflux condenser, a thermometer, magnetic stirring, and an inert atmosphere, heat up to 60-80°C, and stir at a constant temperature for 10-30 minutes;

(2) After heating up to 90-110°C, add the isocyanatosiloxane and 10-30 parts of solvent in the constant pressure funnel dropwise into the four-necked flask within 2-4 hours, and react at constant temperature for 6-12 hours;

(3) Add allyl glycidyl ether and 20-40 parts of solvent in the constant pressure funnel to the four-necked flask dropwise within 1-3 hours, and react at constant temperature for 4-10 hours;

(4) Remove the solvent and unreacted substances by distillation under reduced pressure to obtain the flame retardant intermediate API;

(5) Add the flame retardant intermediate API, phosphorus-containing active substance, catalyst and 80-140 parts of solvent obtained in step (4) into a four-necked flask, configure a reflux condenser, a thermometer and magnetic stirring, and pass in nitrogen, Heat up to 90-110°C and then react at constant temperature for 10-24h;

(6) The above solution is distilled under reduced pressure to obtain the product, washed several times with a washing solvent, and then dried at 80-100°C for 12-24 hours to obtain a polysiloxane flame retardant containing nitrogen, phosphorus and silicon.

Further, the catalyst is added to the reaction system twice, the catalyst used in step (1) is one of Speier catalyst and Karstdet catalyst, the catalyst used in step (5) is triphenylphosphine and triethanolamine One of them; during the reaction process, the dosages of the two catalysts are 4*10 ^-5 -10 ^-4 parts and 0.18-0.45 parts respectively.

The coating in the invention obtains a reactive coating with strong adhesion and excellent flame retardancy through rational selection of components and rational design of the preparation process. The reaction principle is: the film-forming agent and the silane coupling agent play a film-forming role at the same time, and the silane coupling agent can interact with the synthesized polysiloxane flame retardant. The silane coupling agent and the flame retardant can both The microencapsulation of ammonium polyphosphate can react at a certain temperature and under the action of ethanol to obtain a space cross-linked network structure with higher thermal stability; thus better bonding force and adhesion between the coating and the substrate can be achieved. The force test can reach 5B (5B is the level of adhesion, according to the parameters tested by ASTM D3359-09 using the 3M tape adhesion test method), and the flame retardant performance is good. This coating is a reactive coating, and the reaction can be carried out during the preparation process of the coating and during the heating process, especially when it is heated, the reaction is more complete, so that it has a good flame retardant effect; at the same time, the flame retardant coating The silane coupling agent can be replaced with other substances containing -Si-O-CH ₂ CH ₃ or -Si-OH, and the ammonium polyphosphate can be replaced with other excellent substances, so as to obtain a multifunctional reactive coating with ideal properties.

Beneficial effects of the present invention:

(1) The flame retardant coating in the present invention is a reactive coating, and the silane coupling agent in the flame retardant coating can be replaced by any other substance containing -Si-O-CH ₂ CH ₃ groups and -Si-OH , and ammonium polyphosphate can also be replaced by other substances with excellent properties, so as to obtain a multifunctional reactive coating with ideal properties;

(2) The coating has a good flame retardant effect. The microencapsulated structure and space cross-linked network structure in the coating make the coating still obtain a good flame retardant effect when the amount of addition is small;

(3) The coating has good adhesion and can firmly adhere to the surface of plastics such as polypropylene, polyethylene, polystyrene, polyester, etc. and paper, metal, etc., and has good aging resistance properties such as Water resistance, UV resistance;

(4) The coating has no adverse effect on the mechanical properties of the substrate, and the flame-retardant coating has high flexibility and adhesion, and can deform together with the substrate when the substrate is deformed, and will not fall off due to fracture ;

(5) When polypropylene with low surface energy is selected as the base material, the coating obtained is still smooth and has a certain aesthetic feeling;

(6) Ethanol is used as a solvent in the preparation process of the coating, and the flame retardant coating can be dissolved in ethanol, so that the substrate and the flame retardant can be recycled and reused separately, without any harm to the environment;

(7) The preparation process of the coating is simple and easy. When it is applied to the surface of the substrate, it only needs to be dried in an oven without ultraviolet curing. The preparation method is simple and it is easy to realize industrial production.

Description of drawings

Fig. 1 is the infrared spectrogram of the polysiloxane flame retardant obtained in Example 1.

Figure 2 is the thermal gravimetric spectrum of the polysiloxane flame retardant obtained in Example 1.

3 is a schematic diagram of the contact angle of the polysiloxane flame retardant obtained in Example 1.

Fig. 4 is the test of the surface adhesion between the polysiloxane flame retardant coating obtained in Example 1 and polypropylene.

Fig. 5 is the PP/polysiloxane flame retardant coating obtained in Example 1, the variation curve of the oxygen index of different samples under different coating thicknesses.

Fig. 6 is the flame retardant rating diagram of vertical burning of different samples of the PP/polysiloxane flame retardant coating obtained in Example 1 under different coating thicknesses.

Fig. 7 is the variation curve of the tensile strength of the PP/polysiloxane flame retardant coating obtained in Example 1 under the same coating thickness.

detailed description

The present invention is further illustrated by the following examples, but the examples described below are only part of the examples of the present invention, and the present invention is not limited to the following examples. Based on the embodiments of the present invention, the embodiments obtained by researchers in the field without performing creative experiments should all be within the protection scope of the present invention.

Example 1

Add 5 parts of poly(methylhydrogensiloxane-dimethylsiloxane copolymer), 6*10 ^-5 parts of Karstdet catalyst and 50 parts of isopropanol to an inert In a four-necked flask with an atmosphere, heat up to 70°C and stir at a constant temperature for 15 minutes; after warming up to 100°C, within 3 hours, mix 15 parts of propyltriethoxysilane isocyanate and 15 parts of isopropanol in a constant pressure funnel. Add it dropwise into the four-necked flask, and continue the constant temperature reaction for 6 hours; within 2 hours, add 35 parts of allyl glycidyl ether and 20 parts of isopropanol in the constant pressure funnel dropwise into the four-necked flask, and continue the constant temperature reaction for 6 hours; The solvent and unreacted substances were removed by distillation under reduced pressure to obtain the flame retardant intermediate API; all the flame retardant intermediate API obtained in the previous step, 40 parts of diphenylphosphine oxide, 0.29 part of triphenylphosphine and 100 parts of Add isopropanol to a four-necked flask, configure a reflux condenser, a thermometer and a magnetic stirrer, pass in nitrogen, raise the temperature to 100°C and react at a constant temperature for 12 hours; distill the above solution under reduced pressure to obtain the product, and use 80 parts of acetone and absolute ethanol (The volume ratio is 1:1) for washing, and then drying at 80° C. for 24 hours to obtain a polysiloxane flame retardant.

Add 50 parts of ethanol to the beaker, and add 7 parts of film-forming agent under the stirring condition of 900r/min, which are respectively polyvinyl formal and polyvinyl formal (the mass ratio of the two is 1:1). Then continue to stir for 30 minutes; add 5 parts of ammonium polyphosphate at the same speed, and continue to stir for 25 minutes; at 50 ° C, add 20 parts of silane coupling agent to the above solution: N-aminoethyl-γ-aminopropyltrimethyl Oxysilane and 3-aminopropyltriethoxysilane (the molar ratio of the two is 1:1), stir at constant temperature for 20 minutes; add 6 parts of the above polysiloxane flame retardant to the obtained mixed liquid, and stir thoroughly for 30 minutes; Add 1 part of wetting agent to the above solution under the stirring condition of 400r/min, and evaporate the ethanol at a temperature of 80°C until it becomes viscous and stop heating.

First dip the polypropylene sample strip into the viscous liquid, then pull it up, and finally dry it to prepare the polypropylene/polysiloxane coating composite material coated with polysiloxane coating. In the present invention The coating thickness involved is 40 μm-200 μm. The thickness of the coating is controlled by the number of pulls to obtain polypropylene/polysiloxane coating composites with different thicknesses. This method is also suitable for preparing coatings on metal and plastic surfaces such as polyethylene, polystyrene, and polyester.

Each serving in the examples of the present invention represents 1 g.

During the above experiment process, the infrared spectrum of the polysiloxane flame retardant is shown in Figure 1. Obviously, the stretching vibration peak of -PH located at 2384cm ^-1 in the phosphorus-containing active material completely disappeared in APID; the peak of the epoxy group located at 909cm ^-1 was due to the -PH and epoxy group The reaction basically disappears, and the characteristic peaks in phosphorus-containing active substances such as -P=O at 1288cm ^-1 and PO-Ph at 1118cm ^-1 can be found in APID, and carbon hydroxyl groups appear at 3430 cm ^-1 The characteristic peak of , which shows that the phosphorus-containing active substance has participated in the reaction, is grafted on the side chain of APID. In addition, new peaks appeared at 1639, 1540, and 3430cm ^-1 , which were the peaks of -C=O, -NH, and -NHCO respectively, while the -SiH peaks at 2168cm ^-1 and 906cm ^-1 disappeared completely, which is Description-SiH can react with isocyanatosilane under the action of Speier catalyst to obtain carbon-silane amide, and under the current conditions-SiH can react completely, which has the same structure as the target product. However, a very strong peak appeared at 3430 cm ^-1 , which was due to the overlapping of -NHCO and -PH contained in APID with the carbon hydroxyl formed by the reaction of epoxy group. The above evidence shows that the ideal flame retardant APID has been successfully prepared.

The thermogravimetric curves of the prepared polysiloxane flame retardant and the active phosphorus-containing substance of the raw material are shown in Figure 2. The initial decomposition temperature of the polysiloxane flame retardant is 237°C, which can meet the processing temperature of polymer materials. Moreover, when the temperature reaches 800°C, the residual weight of the synthesized polysiloxane flame retardant reaches 45.30%, indicating that the char-forming agent has good thermal stability and char-forming property.

The contact angle diagram of the prepared polysiloxane flame retardant is shown in Figure 3. The contact angle of the synthesized polysiloxane flame retardant reaches 118°, which is hydrophobic and can significantly improve the contact angle with the polymer matrix. compatibility.

The obtained PP/polysiloxane flame retardant coating of the present embodiment is tested for cohesion, and the reference standard ASTM D3359-09 adopts the 3M adhesive tape cohesion test method to test the cohesion between the coating and the substrate, and the results are shown in Figure 4 shows. (a) in Figure 4 is the photo before the flame retardant coating test, and (b) is the photo after the test. It can be seen from the figure that the edges of the cuts are very smooth, and none of the crystal lattices falls off, so the adhesion of the flame retardant coating can reach 5B level. The flame-retardant coating can be firmly attached to the surface of polypropylene, which can significantly improve the flame-retardant properties of polypropylene composites.

In the process of preparing the coating above, under the same preparation conditions, the addition ratio of the polysiloxane flame retardant was changed to obtain samples 1-4. Wherein sample 1 polysiloxane flame retardant content is 4%, polysiloxane flame retardant content is 6% in sample 2, polysiloxane flame retardant content is 8% in sample 3, test The polysiloxane flame retardant content in Sample 4 was 10%. Different performance tests were carried out for samples 1-4, as shown in Figures 5-7.

Fig. 5 is the obtained PP/polysiloxane flame retardant coating, the change curve of the oxygen index of the above four samples under different coating thicknesses. It can be seen from the figure that when the coating composition is the same, the oxygen index increases with the increase of thickness; when the coating thickness is the same, the oxygen index increases with the proportion of polysiloxane flame retardant . When the polysiloxane flame retardant content is 10%, the oxygen index has reached 31.3%, which shows that the polysiloxane coating in the present invention has good flame retardancy.

Fig. 6 is the obtained PP/polysiloxane flame retardant coating, and the variation curves of the vertical burning data of the above four samples under different coating thicknesses.

Fig. 7 is a graph showing the tensile strength data of the obtained PP/polysiloxane flame retardant coating under the same coating thickness. It can be seen from the figure that the tensile strength of the four samples is close to that of pure polypropylene, all around 34.5MPa, which indicates that the flame retardant coating has no effect on the mechanical properties of the matrix.

Example 2

Add 10 parts of 1,3,5,7-tetramethylcyclotetrasiloxane, 4*10 ^-5 parts of Speier's catalyst and 60 parts of toluene solvent into a four-phase tank equipped with a reflux condenser, a thermometer and magnetic stirring, and an inert atmosphere. In the flask, heat up to 70°C and stir at constant temperature for 10 minutes; after warming up to 95°C, add 10 parts of isocyanatopropyltriethoxysilane and 15 parts of toluene dropwise in the constant pressure funnel to the four-hole flask within 3 hours In the flask, continue the constant temperature reaction for 8h; within 2h, 30 parts of allyl glycidyl ether and 35 parts of toluene in the constant pressure funnel were added dropwise in the four-necked flask, and the constant temperature reaction was continued for 7h; the solvent was removed by distillation under reduced pressure and Unreacted matter, obtain flame retardant intermediate API; All flame retardant intermediate API obtained in the previous step, 35 parts 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxidized Add 1.8*10 ^-1 parts of triethanolamine catalyst and 110 parts of toluene solvent into a four-necked flask, configure a reflux condenser, a thermometer and a magnetic stirrer, feed in nitrogen, raise the temperature to 105°C and react at a constant temperature for 15 hours; The product was obtained by pressure distillation, washed with 120 parts of acetone and absolute ethanol (1:1 volume ratio), and then dried at 90°C for 24 hours to obtain a polysiloxane flame retardant.

Add 100 parts of ethanol to the beaker, add 5 parts of polyvinyl formal under the stirring condition of 800r/min, and continue stirring for 40 minutes after adding; add 3 parts of ammonium polyphosphate at the same speed, and continue stirring for 10 minutes; At ℃, add 25 parts of silane coupling agent to the above solution: 3-aminopropyltriethoxysilane and ureapropyltriethoxysilane (the molar ratio of the two is 1:1), stir at constant temperature for 10min; Add 5 parts of polysiloxane flame retardant to the obtained mixed liquid, and stir thoroughly for 25 minutes; add 2 parts of wetting agent to the above solution under the stirring condition of 600r/min, and make ethanol Evaporate and stop heating when thickened.

First dip the polyester sample into the viscous liquid, then pull it up, and finally dry it to prepare the polyester/polysiloxane coated composite material coated with polysiloxane coating. The number of times controls the thickness of the coating to obtain polyester/polysiloxane coating composites with different thicknesses (30μm-400μm).

Example 3

Add 6 parts of polymethylhydrogensiloxane, 7*10 ^-5 parts of Speier catalyst and 70 parts of toluene solvent into a four-necked flask equipped with a reflux condenser, a thermometer and magnetic stirring, and an inert atmosphere. After heating to 70°C Stir at constant temperature for 10 minutes; after heating up to 100°C, add 10 parts of 3-isocyanatopropyltrimethoxysilane and 15 parts of toluene in the constant pressure funnel dropwise into the four-necked flask within 4 hours, and continue the constant temperature reaction for 7 hours; Within 3 hours, 50 parts of allyl glycidyl ether and 20 parts of toluene in the constant pressure funnel were added dropwise into the four-necked flask, and the constant temperature reaction was continued for 5 hours; the solvent and unreacted substances were removed by vacuum distillation to obtain the flame retardant intermediate API; all the flame retardant intermediate API obtained in the previous step, 30 parts of phosphoric acid, 4.0* ^10-1 part of triphenylphosphine catalyst and 105 parts of acetone were added to a four-necked flask to prepare a reflux condenser, thermometer and magnetic Stir, feed nitrogen, heat up to 105°C and react at constant temperature for 12 hours; distill the above solution under reduced pressure to obtain the product, wash with 90 parts of acetone, and then dry at 80°C for 12 hours to obtain a polysiloxane flame retardant.

Add 80 parts of ethanol to the beaker, add 6 parts of polyvinyl formal under the stirring condition of 900r/min, and continue stirring for 30 minutes after adding; add 5 parts of ammonium polyphosphate at the same speed, and continue stirring for 20 minutes; Under the above conditions, add 30 parts of silane coupling agent to the above solution: γ-glycidyl etheroxypropyltrimethoxysilane and ureapropyltriethoxysilane (the molar ratio of the two is 1:1), and stir at constant temperature 30min; add 2 parts of polysiloxane flame retardant to the obtained mixed liquid, and stir thoroughly for 40 minutes; add 1 part of wetting agent to the above solution under the stirring condition of 550r/min, at a temperature of 100°C , to evaporate the ethanol and stop heating until it becomes viscous.

The metal/polysiloxane coating composite material with a coating thickness of 5 μm-80 μm can be prepared by impregnating the metal into the viscous liquid first, then pulling and drying. The viscous liquid can also be evenly coated on the metal surface with a brush, and then dried to obtain a metal/polysiloxane coating composite material.

Example 4

Add 5 parts of polymethylhydrogensiloxane, 6*10 ^-5 parts of Speier catalyst and 50 parts of benzene solvent into a four-necked flask equipped with a reflux condenser, a thermometer and magnetic stirring, and an inert atmosphere. After heating to 70°C Stir at constant temperature for 10 minutes; after the temperature rises to 90°C, add 20 parts of propyltriethoxysilane isocyanate and 30 parts of benzene solvent in the constant pressure funnel dropwise into the four-necked flask within 3 hours, and continue the constant temperature reaction for 12 hours; Within 2 hours, 35 parts of allyl glycidyl ether and 40 parts of benzene solvent in the constant pressure funnel were added dropwise into the four-necked flask, and the constant temperature reaction was continued for 9 hours; the solvent and unreacted substances were removed by vacuum distillation to obtain a flame retardant agent intermediate API; all the flame retardant intermediate API obtained in the previous step, 30 parts of phosphorous acid, 3.0*10 ^-1 triethanolamine catalyst and 120 parts of benzene solvent are added to a four-necked flask, and a reflux condenser, a thermometer and Stir magnetically, feed nitrogen, heat up to 90°C and react at a constant temperature for 18 hours; distill the above solution under reduced pressure to obtain the product, wash with 100 parts of acetone and absolute ethanol (volume ratio 1:1), and then heat at 80°C Dry for 12 hours to obtain a polysiloxane flame retardant.

Add 100 parts of ethanol to the beaker, and add 5 parts of film forming agent: polyvinyl formal and polyvinyl butyral (the mass ratio of the two is 1:1) under the stirring condition of 1000r/min. Continue stirring for 30 minutes; add 3 parts of ammonium polyphosphate at the same speed, and continue stirring for 10 minutes; add 30 parts of silane coupling agent 3-aminopropyltriethoxysilane to the above solution at 60°C, and stir at constant temperature for 20 minutes ; Add 6 parts of polysiloxane flame retardant to the obtained mixed liquid, and stir for 30 minutes; add 2 parts of wetting agent to the above solution under the stirring condition of 400r/min, and at a temperature of 100°C, The ethanol was allowed to evaporate until it became viscous without heating.

After stirring the viscous liquid evenly, brush the viscous liquid evenly on the wood along the longitudinal direction of the wood with a brush, so that the coating thickness reaches 100 μm-0.3 mm to obtain a wood/polysiloxane coating composite material.

Example 5

Add 4 parts of poly(methylhydrogensiloxane-dimethylsiloxane copolymer), 8*10 ^-5 parts of Speier catalyst and 70 parts of toluene solvent into a In a four-necked flask, the temperature was raised to 75°C and then stirred at constant temperature for 15 minutes; after the temperature was raised to 110°C, 5 parts of dimethyldiisocyanatosilane and 10 parts of toluene in the constant pressure funnel were added dropwise to the four-necked flask within 3 hours. In the four-necked flask, continue the constant temperature reaction for 8 hours; within 2 hours, add 40 parts of allyl glycidyl ether and 20 parts of toluene in the constant pressure funnel dropwise into the four-necked flask, continue the constant temperature reaction for 8 hours; remove the solvent by distillation under reduced pressure And unreacted substance, obtain flame retardant intermediate API; All flame retardant intermediate API that last step obtains, 30 parts of diphenylphosphine oxygen, 4.4*10 ^-1 part of triphenylphosphine catalyst and 100 parts of toluene The solvent was added to a four-necked flask, a reflux condenser, a thermometer and a magnetic stirrer were prepared, nitrogen gas was introduced, and the temperature was raised to 100°C, and then reacted at a constant temperature for 12 hours; the above solution was distilled under reduced pressure to obtain the product, washed with 80 parts of absolute ethanol, and then Dry at 80° C. for 15 hours to obtain a polysiloxane flame retardant.

Add 150 parts of ethanol to the beaker, and add 6 parts of film-forming agent: polyvinyl formal and polyvinyl butyral (the mass ratio of the two is 1:1) under the stirring condition of 950r/min, and continue to stir after adding 20min; add 4 parts of ammonium polyphosphate at the same speed, and continue to stir for 30min; at 70°C, add 10 parts of silane coupling agent to the above solution: 3-aminopropyltriethoxysilane and propyl isocyanate Triethoxysilane (the molar ratio of the two is 1:1), stirred at constant temperature for 30 minutes; added 5 parts of polysiloxane flame retardant to the obtained mixed liquid, and stirred fully for 20 minutes; under the stirring condition of 600r/min to Add 1 part of wetting agent to the above solution, and evaporate the ethanol at a temperature of 80°C until it becomes viscous and stop heating.

The paper is soaked in the viscous liquid, and then the excess viscous liquid is removed by extrusion, and then dried to obtain a paper/polysiloxane flame retardant coating with a coating thickness of 1 μm-15 μm. Coating thickness can be tuned by adjusting extrusion parameters.

Claims (10)

1. A reactive polysiloxane flame retardant coating, characterized in that: its spatial structure is: The structural formula of polysiloxane flame retardant is: Among them, m>0, n>0, x≥0; m and n are positive integers, and x is a non-negative integer; R ₁ and R ₂ are respectively one of H, CH ₃ or OH; R ₃ is CH ₂ CH(CH ₂ OH)-P(=O)-OC ₁₂ H ₈ , CH ₂ CH(OH)-CH ₂ -P(=O)-OC ₁₂ H ₈ , CH ₂ -CH(OH )-CH ₂ -P(=O)-(C ₆ H ₅ ) ₂ , CH ₂ -CH(CH ₂ OH)-P(=O)-(C ₆ H ₅ ) ₂ , CH(OH)-CH ₂ One of -P(=O)(OH) ₂ , CH(OH)-CH ₂ -P(=O) ₂ or CH(OH)-CH ₂ -P(=O)(OH)H; R ₄ is (CH ₂ ) ₃ -Si-(O-CH ₂ CH ₃ ) ₃ , (CH ₂ ) ₃ -Si-(O-CH ₃ ) ₃ , ((CH ₃ ) ₂ )Si-NCO, ((CH ₃ ) ₂ )Si-NHC(=O)-(CH ₃ )Si(-OL)-R ₁ or ((CH ₃ ) ₂ )Si-NHC(=O)-(CH ₃ )Si(- OL)-R ₂ in one; wherein R ₁ and R ₂ are the same as above, and L represents the -Si-O-Si- main chain in the molecule. 2. A kind of reactive polysiloxane flame-retardant coating according to claim 1, is characterized in that, is made of the raw material of following weight part: 5-7 parts of film-forming agent; 3-5 parts of ammonium polyphosphate; 2-6 parts of polysiloxane flame retardant; 10-30 parts of silane coupling agent; Wetting agent 1-2 parts; 50-150 parts of ethanol; The resulting flame-retardant coating has strong adhesion and is firmly combined with the substrate; Wherein said polysiloxane flame retardant is made from the raw material of following parts by weight: 5-10 parts of hydrogen-containing silicone oil; 30-50 parts of allyl glycidyl ether; 5-20 parts of isocyanatosilane; 30-50 parts of phosphorus-containing active substances; During the reaction process, the amount of catalyst used is: 1.8004*10 ^-1 -4.501*10 ^-1 parts; the amount of solvent used is: 160-280 parts; the amount of washing solvent used is: 80-150 parts. 3. reactive polysiloxane flame retardant coating according to claim 1, is characterized in that, described film-forming agent is polyvinyl formal, polyvinyl alcohol, polyenyl acetal, polyvinyl acetal, polyvinyl acetal One or both of vinyl butyral or polyvinyl formal; when both are selected, the mass ratio of the two is 1:1. 4. reactive polysiloxane flame retardant coating according to claim 1, is characterized in that, described wetting agent is sodium lauryl sulfate, xylitol anhydrous fatty acid ester, polyoxyethylene ( 20) One or two of sorbitan monooleate, polyoxyethylene fatty acid ester or polyoxyethylene alkylphenyl ether; when two are selected, the mass ratio is 1:1. 5. The reactive polysiloxane flame retardant coating according to claim 1, wherein said silane coupling agent is γ-glycidyl ether oxypropyltrimethoxysilane, γ-methylpropylene Acyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, isocyanatopropyltriethoxysilane, ureapropyltriethoxysilane, N-aminoethyl-γ-ammonia One or two of propyltrimethoxysilane, divinyltriaminopropyltrimethoxysilane or dimethyldiisocyanatosilane; when two are selected, the molar ratio is 1:1. 6. reactive polysiloxane flame retardant coating according to claim 1, is characterized in that, described catalyst is two kinds in Speier catalyst, Karstdet catalyst, triphenylphosphine or triethanolamine; The hydrogen-containing silicone oil is polymethylhydrogensiloxane, poly(methylhydrogensiloxane-dimethylsiloxane copolymer), 1,3,5,7-tetramethylcyclotetrasiloxane or One of the hydrogen-terminated polydimethylsiloxanes; The isocyanatosilane is one of 3-isocyanatopropyl trimethoxysilane, isocyanatopropyl triethoxysilane or dimethyl diisocyanatosilane; The phosphorus-containing active substance is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphoric acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid, dialkyl phosphite or diphenyl One of the base phosphorus oxides; Described solvent is one or both in Virahol, dehydrated alcohol, toluene, benzene, acetone, methylene chloride, chloroform, N, N-dimethylformamide; When using two kinds, The volume ratio of the two solvents is 1:1; The washing solvent is one or two of acetone, absolute ethanol, deionized water, and N,N-dimethylformamide; when two are used, the volume ratio of the two is 1:1. 7. The reactive polysiloxane flame retardant coating according to claim 1, wherein the substrate is one of polypropylene, polyethylene, polystyrene, polyester plastics, or paper, One of wood and metal materials. 8. a preparation method of the reactive polysiloxane flame retardant coating described in any one of claims 1 to 7, is characterized in that, comprises the following steps: (1) Add ethanol to the beaker, control the stirring speed to 800-1000r/min, then add the film-forming agent, and continue stirring for 20-40min after adding; (2) Add ammonium polyphosphate at the same speed, and keep stirring for 10-30min; (3) Add silane coupling agent to the above solution at room temperature to 70°C, and stir at constant temperature for 10-30 minutes; (4) Add polysiloxane flame retardant to the mixed liquid obtained in step (3), and stir thoroughly for 20-40 minutes; (5) Add a wetting agent to step (4), and evaporate the ethanol at a stirring speed of 400-600r/min and a temperature of 80-100°C until it becomes viscous and stop heating. 9. the preparation method of reactive polysiloxane flame retardant coating according to claim 8, is characterized in that, the preparation method of described polysiloxane flame retardant comprises the following steps: (1) Add hydrogen-containing silicone oil, catalyst and 50-70 parts of solvent into a four-necked flask equipped with a reflux condenser, a thermometer, magnetic stirring, and an inert atmosphere, heat up to 60-80°C, and stir at a constant temperature for 10-30 minutes; (2) After heating up to 90-110°C, add the isocyanatosiloxane and 10-30 parts of solvent in the constant pressure funnel dropwise into the four-necked flask within 2-4 hours, and react at constant temperature for 6-12 hours; (3) Add allyl glycidyl ether and 20-40 parts of solvent in the constant pressure funnel to the four-necked flask dropwise within 1-3 hours, and react at constant temperature for 4-10 hours; (4) Remove the solvent and unreacted substances by distillation under reduced pressure to obtain the flame retardant intermediate API; (5) Add the flame retardant intermediate API, phosphorus-containing active substance, catalyst and 80-140 parts of solvent obtained in step (4) into a four-necked flask, configure a reflux condenser, a thermometer and magnetic stirring, and pass in nitrogen, Heat up to 90-110°C and then react at constant temperature for 10-24h; (6) The above solution is distilled under reduced pressure to obtain the product, washed several times with a washing solvent, and then dried at 80-100°C for 12-24 hours to obtain a polysiloxane flame retardant containing nitrogen, phosphorus and silicon. 10. The preparation method of reactive polysiloxane flame retardant coating according to claim 9, characterized in that: the catalyst is added to the reaction system twice, and the catalyst used in step (1) is Speier catalyst With one of the Karstdet catalysts, the catalyst used in step (5) is one of triphenylphosphine and triethanolamine; during the reaction, the amounts of the two catalysts before and after are respectively 4*10 ^-5 -10 ^-4 parts, 0.18-0.45 parts.