CN114524985A

CN114524985A - Biomass flame-retardant floor

Info

Publication number: CN114524985A
Application number: CN202210285407.8A
Authority: CN
Inventors: 唐道远
Original assignee: Anhui Sentai Wpc Group Share Co ltd
Current assignee: Anhui Sentai Wpc Group Share Co ltd
Priority date: 2022-03-23
Filing date: 2022-03-23
Publication date: 2022-05-24
Anticipated expiration: 2042-03-23
Also published as: CN114524985B

Abstract

The invention relates to the technical field of wood-plastic composite boards, in particular to a biomass flame-retardant floor. The composite material is a microsphere taking polytrifluorochloroethylene resin as a shell and a mixture of a flame retardant, wood flour and aluminum sulfate as a core, and a gap is formed between the core and the shell. The biomass flame-retardant floor has the advantages of ultrahigh nail-holding power, extremely low water absorption, higher bending strength, better flame-retardant property and the like, and can be widely applied to the field of buildings.

Description

Biomass flame-retardant floor

Technical Field

The invention relates to the technical field of wood-plastic composite boards, in particular to a biomass flame-retardant floor.

Background

Floor, i.e. the surface layer of the floor or floor of a house. Made of wood or other materials, the floor is classified into a plurality of categories, including according to the structure: solid wood floors, laminate wood floors, three-layer solid wood laminate floors, bamboo and wood floors, anti-corrosion floors, cork floors, and the most popular multilayer solid wood laminate floors at present; classified by use are: household, commercial, antistatic floor, outdoor floor, special floor for stage dance, special floor for sports stadium, special floor for track and field, etc. The existing wood floor has poor flame retardant effect, when a fire disaster happens, the fire rapidly spreads along the floor, great threat is generated to the life and property of users, and the requirement on the flame retardant effect of the floor is higher especially in places with intensive personnel such as markets, KTVs and the like.

At present, the flame retardant effect of wood boards is usually improved by adding flame retardant into the wood boards, such as a plastic wood floor disclosed in patent document with publication number CN106065192A, which is made of the following raw materials in parts by weight: 20-40 parts of high-density polyethylene, 10-20 parts of glass fiber, 40-50 parts of wood powder, 5-10 parts of inorganic micro powder, 0.5-2 parts of compatilizer, 1-2 parts of flame retardant, 2-5 parts of plasticizer, 0.5-1.5 parts of colorant and 0.5-2 parts of antibacterial agent. Wherein, the fire retardant adopts layered aluminum silicate with the fineness of 300-400 meshes. The inorganic filler adopts modified attapulgite powder. The plastic wood floor has the advantages that the tensile strength reaches 25.4MPa and the bending strength reaches 36.9MPa except the flame retardant effect.

However, the wood board is still deficient in the nail-holding power because: the wood powder and the superfine aluminum silicate have certain water absorption capacity, and the whole material is compact without gaps, so that the wood board is easy to expand and deform after absorbing water; the nail holding power means whether the nail is easy to fix a nail hole and loosen and fall off after the nail enters the plate; when the wood board expands and deforms, the nail holes are inevitably enlarged, and the problem of insufficient nail holding force is caused.

Disclosure of Invention

The invention aims to solve the problems and provides a biomass flame-retardant floor with excellent nail-holding power.

The technical scheme for solving the problems is to provide a biomass flame-retardant floor which comprises polyethylene resin, an auxiliary agent, glass fiber, a compatilizer, calcium hydroxide and a composite material, wherein the composite material is a microsphere taking polychlorotrifluoroethylene resin as a shell and a mixture of a flame retardant, wood powder and aluminum sulfate as a core, and a gap is formed between the core and the shell.

WhereinThe polyethylene resin is preferably high-density polyethylene with the density of 0.940-0.976 g/cm³Within the range. The auxiliary may be any one or more of components that provide some necessary function to the floor, and preferably, the auxiliary includes an antioxidant and a light stabilizer to improve the weather resistance of the floor. The antioxidant can be selected from various antioxidant materials, such as antioxidant 1010 and antioxidant 168; the choice of light stabilizer can be varied, for example UV2628, UV 944.

In the present application, the improvement of the nail-holding power is embodied in two cases based on the use of the composite material:

in the first case: when the nail is driven into the wood board, the shell of the composite material is not damaged. In this application, combined material's polychlorotrifluoroethylene resin shell has high tensile, compressive strength and hardness, and polychlorotrifluoroethylene resin surface is fairly smooth, cooperates the use of compatilizer, and the combined material is whole and each component homodisperse, and compact nothing space between the component, through the glass fiber and the polychlorotrifluoroethylene resin shell of high strength, effectively improves the nail-holding power.

Wherein the compatilizer influences the uniform mixing property among the components, as the optimization of the invention, the compatilizer comprises maleic anhydride grafted compatilizer, and the melt index of the maleic anhydride grafted compatilizer is not less than 5.0g/10 min.

The glass fiber and the composite material microsphere are main improving components of the nail-holding power, and the diameter of the glass fiber is 3-5mm as the optimization of the invention. Preferably, the diameter of the composite material is 1-3 mm.

Meanwhile, the flame retardant with water absorption and the wood powder are coated in the polychlorotrifluoroethylene resin, and the polychlorotrifluoroethylene resin also has good non-hygroscopicity and flame retardance, so that the problem of water absorption expansion of the flame retardant and the wood powder is avoided. And, different from the direct coating in the prior art, the application is provided with the gap between the shell of the polychlorotrifluoroethylene resin and the core of the flame retardant and the wood powder, even if the coating of the core by the polychlorotrifluoroethylene resin is incomplete, the flame retardant and the wood powder absorb water to cause the expansion of the part of the wood board, the expansion is only in the range inside the shell of the polychlorotrifluoroethylene resin, and the deformation of the whole composite material can not be generated. Therefore, even if the composite material and other components are compact and have no clearance, the deformation is not continuously transmitted like a compact structure in the prior art, so that the whole body is expanded, and the problem of the nail-holding power is further caused.

Although the polychlorotrifluoroethylene resin case has high strength and is not easily broken, the second case is considered: when the nail is driven into the wood board, the shell of the composite material at the driven part is damaged. At this time, the gap between the composite core-shells may have an influence on the nail-holding power. But in fact, on one hand, the flame retardant and the wood powder in the composite material are exposed and are easy to absorb water and expand, but the flame retardant and the wood powder can fill the gap between the wood board and the nail to ensure the nail-holding power; on the other hand, in the application, calcium hydroxide is added into the floor components, aluminum sulfate is added into the composite material, and after the composite material is broken, the aluminum sulfate is exposed to contact with the calcium hydroxide and can also generate a certain expansion effect so as to extrude the nail to improve the nail-holding power.

The preparation method of the composite material can refer to the preparation method of the hollow microspheres, and as the optimization of the invention, the preparation method of the composite material comprises the following steps: coating the mixture with a template agent to form a template; initiating chlorotrifluoroethylene polymerization on the template; the templating agent is then removed.

It can be seen that the removal of the flame retardant and aluminium sulphate needs to be avoided when the templating agent is removed, and therefore, the corresponding templating agent and flame retardant need to be specifically selected.

Preferably, in one embodiment of the present invention, the template agent is melamine-formaldehyde resin, and the flame retardant comprises ammonium polyphosphate. The melamine-formaldehyde resin is removed with hydrochloric acid solution.

Preferably, the flame retardant further comprises chlorinated polyethylene. The chlorinated polyethylene particles are hydrophobic high polymer materials, have rough surfaces but compact interiors, and are beneficial to improving the nail-holding power.

Preferably, in another embodiment of the present invention, the template agent is polystyrene, and the flame retardant comprises magnesium hydroxide. The polystyrene was removed with acetone.

In addition, the proportion of each component in the wood board also has influence on the nail-holding power. The composite material comprises, by mass, 50-60 parts of polyethylene resin, 0.5-1 part of an auxiliary agent, 20-30 parts of glass fiber, 10-20 parts of a compatilizer, 3-8 parts of calcium hydroxide and 30-50 parts of a composite material.

The invention has the beneficial effects that:

1. in this application, through adding the fire retardant, improved the fire behaviour on living beings floor, solved current timber apron flame retardant efficiency not good, when the conflagration takes place, the problem that the intensity of a fire stretchs rapidly along the floor.

2. In the application, the polychlorotrifluoroethylene resin which has good non-hygroscopicity, flame retardance, high strength and good compatibility with other components is taken as a shell, the flame retardant and the wood powder are coated, and meanwhile, a gap is arranged between the polychlorotrifluoroethylene resin shell and the flame retardant wood powder core, so that the floor water absorption problem caused by water absorption of the flame retardant and the wood powder and the nail holding force problem caused by water absorption expansion are avoided.

3. In this application, add glass fiber and further improved the mechanical strength of living beings floor, especially nail-holding power.

Detailed Description

The following are specific embodiments of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.

Composite material a 1:

according to the mass parts, 18 parts of ammonium polyphosphate, 10 parts of wood flour and 2 parts of aluminum sulfate are mixed, added into a grinding machine and ground for 1 hour by taking zirconium beads as grinding media, and a mixture is obtained. And adding the mixture into a beaker, adding styrene maleic anhydride resin as an emulsifier, and shearing for 10min at the speed of 10000r/min by using a shearing machine to obtain a mixed system for later use.

Mixing a mixture of 1: and 3, adding the melamine and formaldehyde solution into a three-neck flask, and reacting for 30min at 65 ℃ to obtain the transparent melamine-formaldehyde prepolymer. Adding the mixed system under stirring, raising the temperature to 65 ℃ again, and magnetically stirring for 3 hours at the speed of 600r/min to obtain the product.

And carrying out suction filtration on the product for 4-5 times, washing the product for 2-3 times by using distilled water, and drying the product for 12 hours at 55 ℃ to obtain a mixture coated by the melamine-formaldehyde resin.

The mixture coated by the melamine-formaldehyde resin is sequentially dipped in 1g/L sodium polystyrene sulfonate and 1g/L poly diallyl dimethyl ammonium chloride for 20min, then added into a 2L high-pressure reaction kettle together with sodium carbonate, sodium bisulfite and ammonium persulfate, vacuumized, added with chlorotrifluoroethylene from a gas phase port, and reacted for 12h at the stirring speed of 25 ℃ and 500r/min to obtain a polymerization product.

And (3) soaking the polymerization product in 0.1mol/L hydrochloric acid solution, stirring, centrifuging and precipitating, washing the precipitate until the pH value is neutral to obtain the composite material, and detecting that the diameter of the composite material is 3mm and recording the diameter as A1.

Composite material a 2:

the preparation method is basically consistent with that of the composite material A1, and only differs from the following steps: according to the mass parts, 10 parts of ammonium polyphosphate, 8 parts of chlorinated polyethylene, 10 parts of wood flour and 2 parts of aluminum sulfate are mixed and then added into a grinding machine. A2 has a diameter of 3 mm.

Composite material a 3:

according to the mass parts, 18 parts of magnesium hydroxide, 10 parts of wood powder and 2 parts of aluminum sulfate are mixed and then added into a grinding machine to be ground for 1 hour by taking zirconium beads as grinding media, and a mixture is obtained.

The mixture was added to a three-necked flask containing absolute ethanol and deionized water, and stirred at a rate of 400r/min at 55 ℃ for 30min to obtain a mixed system.

Adding benzoyl peroxide into styrene, and stirring uniformly. And then dropwise adding the mixed system at the rate of 1 drop/s, after dropwise adding, slowly raising the temperature of the oil bath to 75 ℃ at the temperature rise speed of 2 ℃/min, stirring at constant temperature for 1-2h, carrying out polymerization reaction on styrene through an initiator, raising the temperature to 80 ℃, and stopping the reaction after 6h to obtain the polystyrene-coated mixture.

The polystyrene-coated mixture, sodium carbonate, sodium bisulfite and ammonium persulfate are added into a 2L high-pressure reaction kettle, vacuum pumping is carried out, then chlorotrifluoroethylene is added from a gas phase port, and the reaction is carried out for 12h at the temperature of 25 ℃ and the stirring speed of 500r/min, thus obtaining the polymerization product.

The polymerization product was immersed in acetone, stirred, centrifugally precipitated, and washed to obtain a composite material, which was found to have a diameter of 1mm and was designated as A3.

Example 1

A biomass flame retardant floor is prepared by the following steps:

(1) according to the mass parts, 55 parts of high-density polyethylene resin, 0.2 part of antioxidant 1010, 0.2 part of antioxidant 168, 0.2 part of UV2628, 0.2 part of UV944, 25 parts of glass fiber with the diameter of 3mm, 15 parts of maleic anhydride graft compatilizer with the melt index of 5.0g/10min, 5 parts of calcium hydroxide and 40 parts of composite material A1 are prepared.

(2) Putting the components into a high-speed stirrer for mixing and processing to obtain a mixed material; the mixed materials are prepared into granules by a parallel double-screw extruder, the granulation processing temperature is 200 ℃, the rotating speed is 160 r/min, and the granules with the diameter of 3mm are prepared. Adding the particles into a conical double-screw extruder, extruding and polishing at the main machine rotation speed of 7 revolutions per minute and the temperature of 145 ℃ and the die temperature of 150 ℃ to obtain the wood floor with the thickness of 2 cm and the thickness of 1 square meter.

Example 2

This embodiment is substantially the same as embodiment 1, except that:

40 parts of composite A2 were used.

Example 3

This embodiment is substantially the same as embodiment 1, except that:

40 parts of composite A3 were used.

Example 4

A biomass flame retardant floor is prepared by the following steps:

(1) according to the mass parts, 50 parts of high-density polyethylene resin, 0.2 part of antioxidant 1010, 0.1 part of antioxidant 168, 0.1 part of UV2628, 0.1 part of UV944, 20 parts of glass fiber with the diameter of 1mm, 10 parts of maleic anhydride graft compatilizer with the melt index of 6.0g/10min, 3 parts of calcium hydroxide and 30 parts of composite material A1 are prepared.

(2) Putting the components into a high-speed stirrer for mixing and processing to obtain a mixed material; the mixed materials are prepared into granules by a parallel double-screw extruder, the granulation processing temperature is 250 ℃, the rotating speed is 200 r/min, and the granules with the diameter of 3mm are prepared. And (3) adding the particles into a conical double-screw extruder, extruding and polishing at the main machine rotation speed of 10 revolutions per minute and the die temperature of 185 ℃ to obtain the wood floor with the thickness of 2 cm and the square meter.

Example 5

A biomass flame retardant floor is prepared by the following steps:

(1) according to the mass parts, 60 parts of high-density polyethylene resin, 0.3 part of antioxidant 1010, 0.3 part of antioxidant 168, 0.2 part of UV2628, 0.2 part of UV944, 30 parts of glass fiber with the diameter of 2mm, 20 parts of maleic anhydride grafted compatilizer with the melt index of 5.5g/10min, 8 parts of calcium hydroxide and 50 parts of composite material A1 are prepared.

(2) Putting the components into a high-speed stirrer for mixing and blending to obtain a mixed material; the mixed materials are prepared into granules by a parallel double-screw extruder, the granulation processing temperature is 220 ℃, the rotating speed is 180 r/min, and the granules with the diameter of 3mm are prepared. Adding the particles into a conical double-screw extruder, extruding and polishing at the main machine rotation speed of 8 revolutions per minute and the temperature of 165 ℃ and the die temperature of 160 ℃ to obtain the wood floor with the thickness of 2 cm and the thickness of 1 square meter.

Comparative example 1

This comparative example is essentially the same as example 1 except that:

40 parts of composite material A1 was replaced with 18 parts of ammonium polyphosphate, 10 parts of wood flour, 2 parts of aluminum sulfate and 10 parts of polychlorotrifluoroethylene resin.

Comparative example 2

This comparative example is essentially the same as example 1 except that:

40 parts of composite A1 were replaced with 30 parts of melamine-formaldehyde resin-coated mixture (intermediate product in the preparation of composite A1), 10 parts of polychlorotrifluoroethylene resin.

Comparative example 3

Conventional wood flooring of the same size is commercially available.

[ Water absorption detection ]

The method is detected according to the specification of 4.6 in GB/T17657-2013 artificial board and veneer artificial board physical and chemical property test method, and the soaking time is (72 +/-0.5) h.

[ detection of nail-holding Power ]

And (3) detecting according to the specification of 4.21 in GB/T17657 and 2013 artificial board and veneer artificial board physical and chemical property test method.

[ MEASUREMENT OF BENDING STRENGTH ]

And (4) detecting according to the specification of 4.7 in GB/T17657 and 2013 artificial board and veneer artificial board physical and chemical property test method.

[ flame retardancy grade detection ]

Flame retardant testing and classification was performed according to EN 13501.

The results are shown in Table 1 below:

table 1.

As can be seen from Table 1, the biomass flame-retardant floor prepared by the invention has the advantages of ultrahigh nail-holding power, extremely low water absorption, higher bending strength, better flame retardant property and the like, and can be widely applied to the field of buildings.

As can be seen from comparison of example 1 with comparative examples 1 and 2, in the present application, the flame retardant and wood powder are coated, and at the same time, a gap is formed between the core of the flame retardant wood powder and the shell of polychlorotrifluoroethylene, which can lower the water absorption rate of the flooring and improve the nail-holding power.

The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims

1. A biomass flame-retardant floor is characterized in that: the composite material is a microsphere which takes polychlorotrifluoroethylene resin as a shell and a mixture of a flame retardant, wood flour and aluminum sulfate as a core, and a gap is arranged between the core and the shell.

2. The biomass fire retardant floor as recited in claim 1, wherein: the preparation method of the composite material comprises the following steps: coating the mixture with a template agent to form a template; initiating chlorotrifluoroethylene polymerization on the template; the templating agent is then removed.

3. The biomass fire retardant floor as recited in claim 2, wherein: the template agent is melamine-formaldehyde resin, and the flame retardant comprises ammonium polyphosphate.

4. The biomass fire retardant floor as recited in claim 3, wherein: the flame retardant also includes chlorinated polyethylene.

5. The biomass fire retardant floor as recited in claim 2, wherein: the template agent is polystyrene, and the flame retardant comprises magnesium hydroxide.

6. The biomass fire retardant floor as recited in claim 1, wherein: according to the mass parts, the composite material comprises 50-60 parts of polyethylene resin, 0.5-1 part of auxiliary agent, 20-30 parts of glass fiber, 10-20 parts of compatilizer, 3-8 parts of calcium hydroxide and 30-50 parts of composite material.

7. The biomass fire retardant floor as recited in claim 1, wherein: the compatilizer comprises maleic anhydride grafted compatilizer, and the melt index of the maleic anhydride grafted compatilizer is not less than 5.0g/10 min.

8. The biomass fire retardant floor as recited in claim 1, wherein: the auxiliaries include antioxidants and light stabilizers.

9. The biomass fire retardant floor as recited in claim 1, wherein: the diameter of the glass fiber is 3-5 mm.

10. The biomass fire retardant floor as recited in claim 1, wherein: the diameter of the composite material is 1-3 mm.