CN107868169A - A kind of ingrain fireproofing Wood plastic composite and preparation method thereof - Google Patents

Abstract

A kind of ingrain fireproofing Wood plastic composite and preparation method thereof, the composite includes ingrain fireproofing fabric and core, and the ingrain fireproofing fabric is mainly made up by vinyl phosphoric acid, along 3 bromoacrylic acid ethyl esters, hexacholorocyclopentadiene, acrylic acid, melamine, pentabromophenol of primary raw material.The ingrain fireproofing core mainly can be made up of brominated epoxy resin, thermoplastic phenolic resin, wood powder, lubricant, aluminium hydroxide, compatilizer of raw material.The Wood plastic composite of the present invention has lasting anti-flammability.

Description

A kind of bulk flame-retardant plastic-wood composite material and preparation method thereof

technical field

The invention belongs to the technical field of flame-retardant materials, and in particular relates to a body flame-retardant plastic-wood composite material and a preparation method thereof.

Background technique

The weather resistance of acrylic resin is very good, it is the first choice of outdoor weather resistance resin, it is often used in the top coat of the car body, and the co-extruded plastic-wood composite material, the fabric should be exposed to the outdoors for a long time, and as a co-extruded plastic-wood material The flame retardant performance of the surface layer directly affects the flame retardant performance of the plastic wood material. If the flame retardant performance is excellent, then the external heat source cannot touch the core material at all, so the flame retardant performance of the co-extruded plastic wood composite material must be very outstanding. .

Currently commonly used fabric materials such as polyurethane, PE, PP, etc., have average weather resistance and poor flame retardancy. In traditional flame-retardant wood-plastic composite materials, the method of adding flame retardants is basically used, such as ammonium polyphosphate, as disclosed in CN 1837278A, or additional flame retardants tris (dibromophenyl) phosphate, decabromo Diphenyl ether, etc., as disclosed in CN 102321376A, even if the plastic-wood composite material adopts co-extrusion flame retardant, it basically adopts an external flame retardant to blend to form a flame retardant fabric or core material, as disclosed in CN104149427A, CN 105566755A . Due to the problems that the added flame retardants are easily decomposed and lost with rainwater in the process of outdoor use, the flame retardancy of plastic-wood composite materials used outdoors decreases rapidly until they disappear, and with the loss of the added flame retardants , causing the surface of plastic wood to be uneven and the flame retardancy to drop sharply.

Therefore, it is necessary to develop flame-retardant plastic-wood composites with stable flame-retardant properties.

Contents of the invention

Therefore, one of the objectives of the present invention is to provide a bulk flame-retardant wood-plastic composite material. The wood-plastic composite material of the invention has durable flame retardancy.

For reaching above-mentioned object, the present invention adopts following technical scheme:

A bulk flame-retardant wood-plastic composite material, comprising a bulk flame-retardant fabric and a core material. The bulk flame-retardant fabric is mainly composed of vinylphosphonic acid, cis-3-bromoethyl acrylate, hexachlorocyclopentadiene, acrylic acid , melamine, and pentabromophenol are made of raw materials, and the raw materials of the body flame-retardant fabric are composed as follows by mass fraction:

The body flame-retardant plastic-wood composite material of the present invention can be prepared by co-extruding the body flame-retardant fabric and the core material.

Preferably, the initiator is azobisisobutyronitrile and/or dibenzoyl peroxide.

Preferably, the catalyst is tetra-tert-butyl titanate and/or tributyl tin chloride.

The main body flame retardant fabric can be prepared using the existing preparation method. As a preference, the preparation process of the main body flame retardant fabric is as follows:

(1) By vinyl phosphoric acid, cis-3-ethyl bromoacrylate, hexachlorocyclopentadiene, acrylic acid in xylene solvent, copolymerization reaction occurs under the action of initiator;

(2) adding melamine and pentabromophenol and the carboxyl group in the copolymer to the step (1) reaction system to carry out amidation and esterification modification reaction under catalyst action;

(3) After the reaction in step (2), the xylene solvent is removed and dried to obtain the specially synthesized body flame-retardant fabric. The acid value of the fabric is less than 1mgKOH/g, and the obtained bulk flame-retardant fabric can be pelletized, for example, by a twin-screw extruder.

Preferably, the temperature of the copolymerization reaction in step (1) is above 90°C, preferably 110-130°C, and the time is above 0.5h, preferably 1-3h.

Preferably, the molecular weight of the polymer obtained in step (1) is 50,000-80,000, and the body flame-retardant fabric product within this molecular weight range has better binding force to the core material.

Preferably, the temperature of the amidation and esterification modification reaction in step (2) is 120-180° C., preferably 140-150° C., and the time is more than 1 h, preferably 2-4 h.

Preferably, the core material is mainly composed of brominated epoxy resin, thermoplastic phenolic resin, wood powder, lubricant, aluminum hydroxide, compatibilizer, and the raw materials of the core material are composed as follows by mass fraction:

Aiming at the problems existing in the prior art, this scheme is based on the thermoplastic acrylic resin with strong weather resistance, and uses flame-retardant alkenyl monomers for copolymerization to obtain bulk flame-retardant thermoplastic acrylic copolymer resins, and then synthesized The flame-retardant modification of the copolymerized resin is used to obtain a body flame-retardant fabric with excellent flame-retardant properties. The core material is made of its own flame-retardant resin, such as thermoplastic brominated epoxy resin, thermoplastic phenolic resin, and flame-retardant inorganic filler aluminum hydroxide, and then the synthesized body flame-retardant fabric and flame-retardant core material are co-extruded A flame-retardant co-extruded wood-plastic composite material is obtained.

The body flame-retardant fabric of the present invention does not burn itself, and its oxygen index reaches more than 65%. The core material wood-plastic particles are obtained by using self-flame-retardant brominated epoxy resin and thermoplastic phenolic resin instead of traditional PE, PP, etc. as plastic components, combined with flame-retardant filler aluminum hydroxide and other additives, and have excellent flame-retardant properties. , the oxygen index reaches more than 45%, which is a flame retardant material. The wood-plastic composite material finally obtained in the present invention has super flame-retardant and fire-retardant properties, and is flame-retardant in itself, and will not be lost with rainwater after long-term use outdoors, which greatly prolongs the service life of the wood-plastic composite material outdoors.

Preferably, the brominated epoxy resin is a plastic grade brominated epoxy resin, preferably a thermoplastic brominated epoxy resin, such as EP-15K and/or EP-20K produced by Jiangsu Xingsheng Chemical Co., Ltd.

Preferably, the thermoplastic phenolic resin is 2123 phenolic resin and/or 2402 phenolic resin.

Preferably, the lubricant is polyethylene wax and/or stearic acid.

Preferably, the compatibilizer is a polypropylene compatibilizer, such as polypropylene compatibilizer SZ23 and/or SZ27 produced by Huangshan Beinuo Technology Co., Ltd.

The core material of the present invention can be prepared by the methods in the prior art, and can also be prepared by the following method: fully mix the raw materials at 130-150°C, discharge them into cold mixing, cool down and discharge them. The temperature can be lowered to 50-90°C, preferably 70°C.

One of the purposes of the present invention is also to provide a method for preparing the flame-retardant plastic-wood composite material of the present invention, comprising the following steps:

A. Extrude and granulate the prepared body flame-retardant fabric and core material respectively to obtain flame-retardant fabric particles and core material particles;

B. Melt the core material particles obtained in step A and enter the core material cavity of the co-extrusion mold; melt the flame-retardant fabric particles and enter the flame-retardant fabric cavity of the co-extrusion mold, and obtain the flame-retardant fabric after shaping and cooling. Wood-burning composite material. After forming, it can be cut to length to make finished products.

Preferably, the granulation in step A is carried out in a parallel twin-screw extruder.

Preferably, during granulation, the cylinder temperature is 150-190° C., and the screw speed is 200-300 rpm.

Preferably, the melting process in step B is carried out by an extruder.

Shaping can be carried out by shaping moulds.

The invention adopts a specially synthesized body flame-retardant fabric, and its structure is a body flame-retardant polymer material. When exposed to the outdoors, the flame-retardant components will not be lost and have lasting flame resistance. At the same time, the flame retardancy of the core material is not only achieved by adding a flame retardant, but by using its own flame retardant resin such as thermoplastic brominated epoxy resin, thermoplastic phenolic resin and flame retardant inorganic filler aluminum hydroxide to achieve flame retardancy. The present invention essentially changes the flame retardant way of adding flame retardant to the current flame retardant plastic wood composite material, and realizes body flame retardant and durable flame retardant in a real sense.

Detailed ways

In order to facilitate understanding of the present invention, the present invention enumerates the following examples. Those skilled in the art should understand that the examples are only used to help understand the present invention, and should not be regarded as specific limitations on the present invention.

Example 1

A body flame-retardant plastic-wood composite material, the body flame-retardant fabric is composed of raw materials in terms of mass fraction:

Vinyl Phosphate 8%;

cis-3-ethyl bromoacrylate 30%;

Hexachlorocyclopentadiene 10%;

Acrylic acid 14.49%;

Melamine 15%;

Pentabromophenol 17%;

Xylene 5%;

Initiator 0.01%;

Catalyst 0.5%.

The raw material composition of the core material is as follows according to the mass fraction:

The preparation method comprises the following steps:

A. Fully mix the raw materials of the flame retardant core material according to the formula at 130-150°C, and discharge them into the cold mix, cool down to 70°C and discharge to make a special premix;

B. Add the core material special premix and body flame retardant fabric materials into the parallel twin-screw extruder to extrude and granulate separately to obtain core material particles and fabric particles respectively; the process conditions are: the temperature of the barrel is 150 -190°C, the screw speed is 200-300rpm;

C, the core material pellet that step B is made enters the core material cavity of the co-extrusion mold after melting through the extruder; After the flame-retardant fabric particle enters the flame-retardant fabric cavity of the co-extrusion mold after being melted by the extruder, The co-extruded flame-retardant plastic-wood composite material can be obtained after being shaped by a shaping mold, cooled and formed, and cut to length to obtain a finished product.

Example 2

A body flame-retardant plastic-wood composite material, the body flame-retardant fabric is composed of raw materials in terms of mass fraction:

Vinyl Phosphate 20%;

Cis-3-Ethyl Bromoacrylate 10%;

Hexachlorocyclopentadiene 29.85%;

Acrylic 12%;

Melamine 5%;

Pentabromophenol 8%;

Xylene 15%;

Initiator 0.1%;

Catalyst 0.05%.

The raw material composition of the core material is as follows according to the mass fraction:

The preparation method is the same as in Example 1.

Example 3

A body flame-retardant plastic-wood composite material, the body flame-retardant fabric is composed of raw materials in terms of mass fraction:

Vinyl Phosphate 20%;

cis-3-ethyl bromoacrylate 15%;

Hexachlorocyclopentadiene 17%;

Acrylic 11%;

Melamine 11%;

Pentabromophenol 15.7%;

Xylene 10%;

Initiator 0.05%;

Catalyst 0.25%.

The raw material composition of the core material is as follows according to the mass fraction:

The preparation method is the same as in Example 1.

Example 4

A body flame-retardant plastic-wood composite material, the body flame-retardant fabric is composed of raw materials in terms of mass fraction:

Vinyl Phosphate 15%;

cis-3-ethyl bromoacrylate 20%;

Hexachlorocyclopentadiene 21.57%;

Acrylic 10%;

Melamine 10%;

Pentabromophenol 15%;

Xylene 8%;

Initiator 0.03%;

Catalyst 0.4%.

The raw material composition of the core material is as follows according to the mass fraction:

The preparation method is the same as in Example 1.

Comparative example 1

A body flame-retardant plastic-wood composite material, the body flame-retardant fabric is composed of raw materials in terms of mass fraction:

cis-3-ethyl bromoacrylate 38%;

Hexachlorocyclopentadiene 22%;

Acrylic 10%;

Melamine 10%;

Pentabromophenol 14.49%;

Xylene 5%;

Initiator 0.01%;

Catalyst 0.5%.

Vinyl phosphoric acid is not contained, and other conditions are the same as in Example 1.

Comparative example 2

A body flame-retardant plastic-wood composite material, the body flame-retardant fabric is composed of raw materials in terms of mass fraction:

Vinyl Phosphate 38%;

Hexachlorocyclopentadiene 22%;

Acrylic 10%;

Melamine 10%;

Pentabromophenol 14.49%;

Xylene 5%;

Initiator 0.01%;

Catalyst 0.5%.

Does not contain cis-3-ethyl bromoacrylate, and other conditions are the same as in Example 1.

Comparative example 3

A body flame-retardant plastic-wood composite material, the body flame-retardant fabric is composed of raw materials in terms of mass fraction:

Vinyl Phosphate 15%;

cis-3-ethyl bromoacrylate 35%;

Acrylic 20%;

Melamine 10%;

Pentabromophenol 14.49%;

Xylene 5%;

Initiator 0.01%;

Catalyst 0.5%.

Hexachlorocyclopentadiene is not contained, and other conditions are the same as in Example 1.

Comparative example 4

A body flame-retardant plastic-wood composite material, the body flame-retardant fabric is composed of raw materials in terms of mass fraction:

Vinyl Phosphate 20%;

cis-3-ethyl bromoacrylate 35%;

Hexachlorocyclopentadiene 10%;

Acrylic 15%;

Pentabromophenol 14.49%;

Xylene 5%;

Initiator 0.01%;

Catalyst 0.5%.

Melamine is not contained, and other conditions are the same as in Example 1.

Comparative example 5

A body flame-retardant plastic-wood composite material, the flame-retardant fabric is made by adding a flame retardant, and the raw material composition is as follows in terms of mass fraction:

Polyethylene 30%;

Ammonium polyphosphate 28%;

Hexabromocyclododecane 12%;

Melamine 15%;

Pentabromophenol 15%;

Other conditions are with embodiment 1.

Comparative example 6

A body flame-retardant plastic-wood composite material, the flame-retardant fabric is made by adding a flame retardant, and the raw material composition is as follows in terms of mass fraction:

Polypropylene 30%;

Ammonium polyphosphate 18%;

Hexabromocyclododecane 22%;

Melamine 10%;

Pentabromophenol 20%;

Other conditions are with embodiment 1.

Comparative example 7

A body flame-retardant plastic-wood composite material, the core material is composed of the following raw materials in terms of mass fraction:

Do not contain brominated epoxy resin, other conditions are with embodiment 1.

Comparative example 8

A body flame-retardant plastic-wood composite material, the core material is composed of the following raw materials in terms of mass fraction:

No thermoplastic phenolic resin is contained, and other conditions are the same as in Example 1.

Comparative example 9

A kind of body flame retardant plastic wood composite material, the core material does not use body flame retardant thermoplastic resin, such as thermoplastic phenolic resin, brominated epoxy resin, but uses polyethylene plus flame retardant for flame retardant, according to mass fraction The raw material composition is as follows:

Other conditions are with embodiment 1.

Comparative example 10

A flame-retardant wood-plastic composite material. The core material does not use flame-retardant thermoplastic resins, such as thermoplastic phenolic resins and brominated epoxy resins, but uses polypropylene plus flame retardants for flame retardancy, calculated by mass fraction The composition of raw materials is as follows:

Other conditions are with embodiment 1.

Performance Testing

The composite materials prepared in the above examples and comparative examples were tested for 24h water absorption, boiling water resistance and static bending strength according to the standard of GB17657-2013.

The oxygen index test is based on GBT 2406.2-2009 Determination of combustion behavior of plastics by oxygen index method. The test results are shown in Table 1 below.

Table 1

Table 1 continued

It can be seen from the table that the flame-retardant plastic-wood composite material of the present invention achieves a very good long-lasting flame-retardant effect through the synergistic cooperation of the main body flame-retardant fabric and the specific components in the core material, and has excellent mechanical properties at the same time.

Apparently, the above-mentioned embodiments are only examples for clear description, rather than limiting the implementation. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. It is not necessary and impossible to exhaustively list all the implementation manners here. And the obvious changes or changes derived therefrom are still within the scope of protection of the present invention.

Claims (9)

1. a kind of ingrain fireproofing Wood plastic composite, including ingrain fireproofing fabric and core, the ingrain fireproofing fabric mainly by Vinyl phosphonate, cis- 3- bromoacrylic acids ethyl ester, hexacholorocyclopentadiene, acrylic acid, melamine, pentabromophenol are raw material system Into, the ingrain fireproofing fabric raw material form as mass fraction it is as follows：

2. ingrain fireproofing Wood plastic composite according to claim 1, it is characterised in that the initiator is that azo two is different Butyronitrile and/or dibenzoyl peroxide；

Preferably, catalyst is tetra-tert titanate esters and/or tributyltin chloride.

3. ingrain fireproofing Wood plastic composite according to claim 1 or 2, it is characterised in that the ingrain fireproofing fabric Preparation process is as follows：

(1) by vinyl phosphoric acid, cis- 3- bromoacrylic acids ethyl ester, hexacholorocyclopentadiene, acrylic acid in xylene solvent, It is copolymerized under initiator effect；

(2) melamine and pentabromophenol are added into step (1) reaction system with the carboxyl in copolymer in catalyst action Lower progress amidatioon and esterification modification reaction；

(3) step (2) reaction removes dimethylbenzene after terminating, and the ingrain fireproofing fabric is obtained after drying.

4. ingrain fireproofing Wood plastic composite according to claim 3, it is characterised in that copolyreaction in step (1) Temperature is more than 90 DEG C, and preferably 110-130 DEG C, the time is more than 0.5h, preferably 1-3h；

Preferably, the molecular weight of step (1) resulting polymers is 5-8 ten thousand.

5. the ingrain fireproofing Wood plastic composite according to claim 3 or 4, it is characterised in that in step (2) amidatioon and The temperature of esterification modification reaction is 120-180 DEG C, and preferably 140-150 DEG C, the time is more than 1h, preferably 2-4h.

6. according to the ingrain fireproofing Wood plastic composite described in claim any one of 1-5, it is characterised in that the ingrain fireproofing Core is mainly made up of brominated epoxy resin, thermoplastic phenolic resin, wood powder, lubricant, aluminium hydroxide, compatilizer, the core The raw material of material forms as follows as mass fraction：

7. ingrain fireproofing Wood plastic composite according to claim 6, it is characterised in that the brominated epoxy resin is modeling Expect level brominated epoxy resin, preferably thermoplasticity brominated epoxy resin；

Preferably, the thermoplastic phenolic resin is 2123 phenolic resin and/or 2402 phenolic resin；

Preferably, lubricant is Tissuemat E and/or stearic acid；

Preferably, the compatilizer is polypropylene compatilizer；

Preferably, the core is prepared via a method which：Raw material is mixed at 130-150 DEG C, and discharged into cold mix, drop Temperature, which discharges, to be produced.

8. a kind of preparation method of any one of claim 1-7 ingrain fireproofing Wood plastic composites, comprises the following steps：

A, obtained ingrain fireproofing fabric and core are distinguished into extruding pelletization, respectively obtains inflaming retarding fabric particle and core material particles；

B, the core cavity of co-extruding mould will be entered after inflaming retarding core material particle fusion made from step A；Inflaming retarding fabric particle is melted Enter the inflaming retarding fabric cavity of co-extruding mould after melting, through sizing, cooling and shaping obtain the flame-resistant plastic-wood composite materials.

9. preparation method according to claim 8, it is characterised in that be granulated in step A in parallel double-screw extruder Carry out；

Preferably, barrel zone temperature is 150-190 DEG C during granulation, screw speed 200-300rpm；

Preferably, the melting process in step B is carried out by extruder.