CN114854213B

CN114854213B - Plate flame-retardant additive and application thereof

Info

Publication number: CN114854213B
Application number: CN202210681354.1A
Authority: CN
Inventors: 魏任重; 周明吉; 王洪松; 毕海明
Original assignee: Treezo New Meterial Science and Technology Group Co Ltd
Current assignee: Treezo New Meterial Science and Technology Group Co Ltd
Priority date: 2022-06-15
Filing date: 2022-06-15
Publication date: 2023-03-21
Anticipated expiration: 2042-06-15
Also published as: CN114854213A

Abstract

The invention discloses a plate flame-retardant additive which comprises the following components in parts by weight: 100-200 parts of polymeric phosphorus-nitrogen flame retardant, 100-200 parts of magnesium hydroxide, 50-80 parts of melamine, 10-30 parts of zinc borate, 10-30 parts of sodium stannate and 10-15 parts of filler. The board flame retardant provided by the invention can realize non-halogenation of the flame retardant, and the interaction of the polymeric phosphorus-nitrogen flame retardant, the magnesium hydroxide, the melamine, the zinc borate and the sodium stannate can improve the compatibility of the board flame retardant and materials and further improve the mechanical property and the physical and chemical properties of the bamboo shaving board.

Description

Plate flame-retardant additive and application thereof

Technical Field

The invention belongs to the technical field of flame-retardant materials, and particularly relates to a flame-retardant additive for a plate and application thereof.

Background

The bamboo shaving board is one of shaving board varieties, and the board is made of moso bamboo as a raw material and simulates the technological process of a wood shaving board. The bamboo shaving board has the characteristics of difficult deformation, smooth surface, stable physical properties and the like which are not possessed by natural wood, has small production energy consumption, low cost, low requirement on the quality of production raw materials and excellent mechanical properties, and is widely applied to industries of furniture, decoration, building materials and the like. However, since the bamboo shaving board is made of bamboo cellulose material, which is flammable, when the temperature of the ignition point is reached, the bamboo shaving board will burn up quickly and spread quickly, and once a fire breaks out, the bamboo shaving board will cause disastrous losses. Therefore, it is required to manufacture a bamboo particle board having flame retardant properties.

Particle boards now mainly have two flame retardant technologies: firstly, impregnating a fire retardant on the wood shavings, and drying to obtain wood shavings raw materials with fire retardant property; secondly, a large amount of filling type flame retardant is added into the wood shavings to improve the flame retardance of the shaving board. Commonly used flame retardants can be classified into halogen-based, phosphorus-based and nitrogen-based. Halogen flame retardants with chlorine and bromine are common in the current market, and have the advantages of low production cost, large production capacity, rich raw materials and the like as flame retardants with early development and good flame retardant effect, but the halogen flame retardants can be decomposed to generate toxic gas hydrogen halide when heated and even can generate carcinogenic substance dioxin. The common phosphorus flame retardant can realize non-halogenation of the flame retardant, has a plasticizing function, can improve the flow processability of plastic during molding, and can inhibit residues after combustion. However, most phosphate flame retardants also have disadvantages such as high volatility, poor heat resistance, poor compatibility, and the generation of dripping during combustion. The nitrogen flame retardant has the defects of low flame retardant efficiency when used alone and poor compatibility with partial materials.

Disclosure of Invention

In order to solve the problems that the flame retardant is poor in flame retardant property in the prior art and the mechanical property of the flakeboard is poor due to the fact that a large amount of flame retardant with common flame retardant property is filled in the flakeboard, the invention aims to provide the flame retardant additive for improving the flame retardant capability of the bamboo flakeboard.

In order to achieve the purpose, the invention adopts the following technical means:

the invention provides a flame retardant additive for a plate, which comprises the following components in parts by weight: 100-200 parts of polymeric phosphorus-nitrogen flame retardant, 100-200 parts of magnesium hydroxide, 50-80 parts of melamine, 10-30 parts of zinc borate, 10-30 parts of sodium stannate and 10-15 parts of filler.

Preferably, the filler consists of the following components in percentage by mass: 40-60% of montmorillonite, 10-30% of fly ash and 20-40% of talcum powder.

Preferably, the polymeric phosphorus nitrogen flame retardant has the structural formula shown in formula I below:

wherein n is an integer between 50 and 100.

Further preferably, the preparation method of the polymeric phosphorus-nitrogen flame retardant is shown as the reaction (1),

reaction (1);

the method comprises the following specific steps: dissolving 2-hydroxy-5-aminopyridine in chloroform in a reactor to obtain a monomer reaction solution, and simultaneously heating and opening an electric stirrer to stir at 280 r/min; then dissolving phenyl phosphoryl dichloride in trichloromethane, slowly dripping the solution into the reaction solution, uniformly stirring, heating to the reflux temperature, continuing to perform polymerization reaction for 2 hours, and cooling the obtained solution to room temperature; dissolving an acid-binding agent in chloroform, slowly dripping the solution into a compound solution of 2-hydroxy-5-aminopyridine and phenyl phosphoryl dichloride, heating to a reflux temperature, condensing steam by using a condensing tube, flowing back into a three-mouth bottle for continuous polymerization reaction for 5 hours, and cooling to room temperature; and finally dissolving terephthalaldehyde in trichloromethane, slowly dropwise adding the trichloromethane into the reaction solution, stirring uniformly, heating to a reflux temperature, condensing steam by using a condensing tube, flowing back into a three-neck flask for continuous polymerization for 5 hours, cooling the solution to room temperature, taking out the solution, extracting the obtained solution, collecting residues with high boiling point when the extracted solid is distilled, washing the extracted polymer by using deionized water, removing impurities in the system, carrying out suction filtration on the obtained solid, drying the obtained solid in a 60 ℃ blast drying box for 12 hours, and grinding the dried solid into powder to obtain the polymeric phosphorus-nitrogen flame retardant.

A second aspect of the invention is to provide the use of said board fire retardant additive in bamboo particle board.

The third aspect of the present invention provides a method for preparing a bamboo shaving board, comprising the steps of:

sequentially adding 200-300 parts by weight of deionized water, 100-200 parts by weight of polymeric phosphorus-nitrogen flame retardant, 100-200 parts by weight of magnesium hydroxide, 50-80 parts by weight of melamine, 10-30 parts by weight of zinc borate and 10-30 parts by weight of sodium stannate into a treatment tank, and uniformly stirring to obtain a first mixed slurry;

s2, screening and cleaning the bamboo shavings, drying the bamboo shavings, adding the bamboo shavings into the mixed slurry, stirring for 1-2 hours at a stirring speed of 100-120r/min, adding 10-15 parts by weight of filler, and continuously stirring for 0.5-1 hour to obtain second mixed slurry;

and S3, respectively placing a layer of low-alkali glass fiber grey cloth on two surfaces of the die, adding the second mixed slurry obtained in the step S2 in the middle, performing roll forming, curing for 7-12 hours at 30-50 ℃ and 80-90% humidity, demolding, curing for 72 hours at 30-40 ℃ and 65-70% humidity, and curing for 7 days at normal temperature.

Preferably, the weight ratio of the bamboo shavings to the board flame retardant additive is 5:8-10.

The invention has the advantages of

Compared with the prior art, the invention has the following beneficial effects:

the board flame retardant provided by the invention can realize non-halogenation of the flame retardant, and the interaction of the polymeric phosphorus-nitrogen flame retardant, the magnesium hydroxide, the melamine, the zinc borate and the sodium stannate can improve the compatibility of the board flame retardant and materials and further improve the mechanical property of the bamboo shaving board.

Detailed Description

Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.

The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from the lower value to the upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a compositional, physical or other property (e.g., molecular weight, melt index, etc.) is stated to be from 100 to 1000, it is intended that all individual values, e.g., 100, 101, 102, etc., and sub ranges, e.g., 100 to 166, 155 to 170, 198 to 200, etc., are expressly enumerated. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1,1.5, etc.), then 1 unit is considered to be 0.0001,0.001,0.01, or 0.1, as appropriate. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. These are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application.

When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms thereof.

The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the exclusion of any doubt, all compositions herein using the terms "comprising", "including", or "having" may include any additional additive, adjuvant, or compound, unless explicitly stated otherwise. Rather, the term "consisting essentially of 8230 \8230; \8230composition" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, insofar as they are necessary for performance. The term "consisting of 823070 \8230composition" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.

In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments.

Examples

The following examples are used herein to demonstrate preferred embodiments of the invention. It will be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function in the invention, and thus can be considered to constitute preferred modes for its practice. Those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit or scope of the invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the disclosures and references cited herein and the materials to which they refer are incorporated by reference.

Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims.

Experiment-preparation of polymeric phosphorus-nitrogen flame retardant:

firstly, dissolving 2-hydroxy-5-aminopyridine in chloroform to obtain a monomer reaction solution, introducing nitrogen into a three-neck flask, then draining the monomer solution into the three-neck flask, and simultaneously heating and opening an electric stirrer to stir at 280 r/min; then dissolving phenyl phosphoryl dichloride in trichloromethane, slowly dripping the solution into the reaction solution, uniformly stirring, heating to the reflux temperature, continuing to perform polymerization reaction for 2 hours, and cooling the obtained solution to room temperature; dissolving triethylamine as an acid-binding agent in chloroform, slowly dropwise adding triethylamine monomer solution into the compound solution of 2-hydroxy-5-aminopyridine and phenyl phosphoryl dichloride, heating to reflux temperature, condensing steam by using a condensing tube, flowing back to a three-mouth bottle, continuing polymerization for 5 hours, and cooling to room temperature; and finally dissolving terephthalaldehyde in trichloromethane, slowly dripping a monomer solution into the reaction solution, uniformly stirring, heating to a reflux temperature, condensing steam by using a condensing tube, flowing back into a three-neck flask for continuous polymerization for 5 hours, cooling the solution to room temperature, taking out the solution, extracting the obtained solution, collecting residues with high boiling point when the extracted solid is distilled, washing the extracted polymer by using deionized water, removing triethylamine and impurities in the system, carrying out suction filtration on the obtained solid, drying the obtained solid in a 60-DEG C forced air drying oven for 12 hours, and grinding the dried solid into powder to obtain the polymeric phosphorus-nitrogen flame retardant.

Example 1

The embodiment provides a plate flame retardant additive which comprises the following components in parts by weight: 100 parts of polymeric phosphorus-nitrogen flame retardant, 100 parts of magnesium hydroxide, 50 parts of melamine, 10 parts of zinc borate, 10 parts of sodium stannate and 10 parts of filler.

The filler comprises the following components in percentage by mass: 50% of montmorillonite, 20% of fly ash and 30% of talcum powder;

this example also provides a method for preparing a bamboo particle board using the flame retardant additive for boards, comprising the following steps: s1, sequentially adding 200 parts by weight of deionized water, 100 parts by weight of polymeric phosphorus-nitrogen flame retardant, 100 parts by weight of magnesium hydroxide, 50 parts by weight of melamine, 10 parts by weight of zinc borate and 10 parts by weight of sodium stannate into a treatment tank, and uniformly stirring to obtain mixed slurry;

s2, screening and cleaning the bamboo shavings, drying the bamboo shavings, adding the bamboo shavings into the mixed slurry, stirring for 1.5 hours at a stirring speed of 110r/min, adding 10 parts by weight of filler according to the proportion, and continuously stirring for 0.5 hour to obtain colloidal mixed slurry;

and S3, respectively placing a layer of low-alkali glass fiber grey cloth on two surfaces of the die, adding the colloidal mixed slurry obtained in the step S2 in the middle, performing roll forming, curing at 40 ℃ and 85% humidity for 10 hours, demolding, curing at 35 ℃ and 68% humidity for 72 hours, and curing at normal temperature for 7 days.

Example 2

The embodiment provides a plate flame retardant additive which comprises the following components in parts by weight: 200 parts of polymeric phosphorus-nitrogen flame retardant, 200 parts of magnesium hydroxide, 80 parts of melamine, 30 parts of zinc borate, 30 parts of sodium stannate, 15 parts of filler and 300 parts of deionized water.

this example also provides a method for preparing a bamboo particle board using the flame retardant additive for boards, comprising the following steps: s1, sequentially adding 200 parts by weight of deionized water, 200 parts by weight of polymeric phosphorus-nitrogen flame retardant, 200 parts by weight of magnesium hydroxide, 80 parts by weight of melamine, 30 parts by weight of zinc borate and 30 parts by weight of sodium stannate into a treatment tank, and uniformly stirring to obtain mixed slurry;

s2, screening and cleaning the bamboo shavings, drying the bamboo shavings, adding the bamboo shavings into the mixed slurry, stirring for 1.5 hours at a stirring speed of 110r/min, adding 15 parts by weight of filler according to the proportion, and continuously stirring for 1 hour to obtain colloidal mixed slurry;

and S3, respectively placing a layer of low-alkali glass fiber grey cloth on two surfaces, adding the colloidal mixed slurry obtained in the step S2 in the middle, rolling and forming, curing at 40 ℃ and 85% humidity for 10 hours, demolding, curing at 35 ℃ and 68% humidity for 72 hours, and curing at normal temperature for 7 days.

Comparative example 1

Comparative example 1 is compared to example 1 except that comparative example 1 does not contain a polymeric phosphorus nitrogen flame retardant.

Comparative example 2

Compared with the example 1, the difference of the comparative example 2 is that the flame retardant additive in the comparative example 2 comprises the following components in parts by weight: 50 parts of polymeric phosphorus-nitrogen flame retardant, 30 parts of magnesium hydroxide, 30 parts of melamine, 10 parts of zinc borate, 10 parts of sodium stannate, 10 parts of filler and 200 parts of deionized water.

the preparation method of the bamboo shaving board is the same as that of example 1.

Comparative example 3

Comparative example 3 is compared with example 1 except that in comparative example 3 calcium hydroxide is used instead of magnesium hydroxide and sodium silicate is used instead of sodium stannate.

Comparative example 4

Comparative example 4 is compared to example 1 except that in comparative example 4 the polymeric phosphorus nitrogen flame retardant is replaced with an amine polyphosphate.

Performance testing

The bamboo particle boards prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to a combustion performance test according to GB 8624 to 2012, the test criteria being given in table 1.

The bamboo particle boards prepared in examples 1-3 and comparative examples 1-3 were subjected to mechanical property tests according to GB/T34717-2017.

TABLE 1 flammability rating and grading criterion for flat building materials and products

The results of the performance tests performed on examples 1-3 and comparative examples 1-3 are shown in tables 2 and 3.

TABLE 2 grade of Combustion Performance

As can be seen from Table 2, the burning performance ratings of examples 1-2 were in accordance with the A rating, the burning performance rating of comparative example 1 was in accordance with the B2 rating, and the burning performance ratings of comparative examples 2-4 were in accordance with the B1 rating.

TABLE 3 results of Performance testing

Inspection item	Technical index	Example 1	Example 2	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Results
									Bulk density (t/m) ² )	-	1.08	1.07	1.10	1.08	1.09	1.08	Qualified
Shrinkage (%)	≯0.3	0.18	0.16	0.19	0.20	0.18	0.19	Qualified
									Wet swelling Rate (%)	≯0.6	0.21	0.18	0.43	0.29	0.27	0.29	Qualified
Factory moisture content (%)	≯8	3.2	3.3	4.1	3.8	3.9	3.7	Qualified
									Formaldehyde emission (mg/mL)	-	0.04	0.03	0.10	0.06	0.08	0.07	Lower than the European standard
Flexural strength (MPa)	≥12	48	49	39	40	43	44	Qualified
									Impact strength (kJ/m 2)	≥2.5	6.7	7.0	3.2	4.1	4.9	5.0	Qualified
Breaking strength in water (MPa)	-	37.2	38.3	28.9	32.1	34.5	34.8	Qualified
									Screw holding power (N/m)	≥25	75	81	56	63	68	69	Qualified

As can be seen from table 3, the bamboo particle boards prepared in examples 1-2 have excellent mechanical properties.

All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.

Claims

1. The flame-retardant additive for the plates is characterized by comprising the following components in parts by weight: 100-200 parts of polymeric phosphorus-nitrogen flame retardant, 100-200 parts of magnesium hydroxide, 50-80 parts of melamine, 10-30 parts of zinc borate, 10-30 parts of sodium stannate and 10-15 parts of filler,

the filler comprises the following components in percentage by mass: 40-60% of montmorillonite, 10-30% of fly ash, 20-40% of talcum powder,

the polymeric phosphorus-nitrogen flame retardant has a structural formula shown in formula I:

formula I

Wherein n is an integer between 50 and 100.

2. The flame retardant additive for sheet material as claimed in claim 1, wherein the polymeric phosphorus-nitrogen flame retardant is prepared by reacting 2-hydroxy-5-aminopyridine, phenyl phosphoryl dichloride and terephthalaldehyde with chloroform as a solvent under the condition of chloroform reflux.

3. A method of making a bamboo particle board comprising the step of using the flame retardant additive of claim 1.

4. A method of manufacturing a bamboo particle board as claimed in claim 3, comprising the steps of:

s1, sequentially adding 200-300 parts by weight of deionized water, 100-200 parts by weight of polymeric phosphorus-nitrogen flame retardant, 100-200 parts by weight of magnesium hydroxide, 50-80 parts by weight of melamine, 10-30 parts by weight of zinc borate and 10-30 parts by weight of sodium stannate into a treatment tank, and uniformly stirring to obtain first mixed slurry;

and S3, respectively placing a layer of low-alkali glass fiber grey cloth on two surfaces of the mold, adding the second mixed slurry obtained in the step S2 into the mold, performing roll forming, curing at the temperature of 30-50 ℃ and the humidity of 80-90% for 7-12 hours, demolding, curing at the temperature of 30-40 ℃ and the humidity of 65-70% for 72 hours, and curing at normal temperature for 7 days.

5. The method for preparing the bamboo shaving board as claimed in claim 4, wherein the weight ratio of the bamboo shavings to the board flame retardant additive in the step S2 is 5:8-10.