CN109627758A - A kind of halogen-free flame-retardant glass fiber enhancing nylon - Google Patents
A kind of halogen-free flame-retardant glass fiber enhancing nylon Download PDFInfo
- Publication number
- CN109627758A CN109627758A CN201811546453.9A CN201811546453A CN109627758A CN 109627758 A CN109627758 A CN 109627758A CN 201811546453 A CN201811546453 A CN 201811546453A CN 109627758 A CN109627758 A CN 109627758A
- Authority
- CN
- China
- Prior art keywords
- halogen
- boric acid
- glass fiber
- nylon
- melamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The invention discloses a kind of halogen-free flame-retardant glass fibers to enhance nylon, and by weight percentage, raw material composition includes: nylon 30~60%；Glass fibre 20~40%；Halogen-free flameproof compound system 10~30%；Wherein, halogen-free flameproof compound system, by weight percentage, raw material composition includes: organic hypophosphites 60~85%；Polyphosphoric acid boric acid melamine salt 13~35%；Carbon forming agent 2~8%；Shown in the structural formula such as following formula (I) of the polyphosphoric acid boric acid melamine salt, in formula, m is the molar ratio of polyphosphoric acid melamine and two structural unit of boric acid, m=3~6.Halogen-free flame-retardant glass fiber enhancing nylon disclosed by the invention uses novel halogen-free flameproof compound system, the halogen-free flameproof compound system solubility is low, charring rate is high, the halogen-free flame-retardant glass fiber enhancing nylon of preparation obtains splendid flame retardant effect, can reach the flame-retardant standard of UL94-V0 (1.6mm).
Description
Technical field
The present invention relates to the technical fields of glass fiber enhanced nylon, and in particular to a kind of halogen-free flame-retardant glass fiber enhancing nylon.
Background technique
Glass fiber enhanced nylon (refers mainly to nylon66 fiber, nylon 6), due to good rigidity and impact resistance, low warpage
The performance characteristics such as property, high dimensional stability, good appearance and be widely used in field of electronics.Common Buddhist nun
Dragon is combustible material, but after it is compound with glass, due to the wick effect of glass, glass fiber enhanced nylon is made to become easier to fire
It burns, thus the flame retardant treatment of glass fiber enhanced nylon becomes a kind of inevitable demand, and the presence of wick effect makes its fire-retardant
Difficulty is bigger.
Currently, including the basic flame-retardant system of two classes: halogen system flame-retardant system for the fire-retardant of glass fiber reinforced nylon material
With non-halogen fire-retardant system.Halogen system flame-retardant system is primarily referred to as bromide fire retardant, including decabromodiphenylethane, brominated Polystyrene
Deng.A large number of studies show that the glass fiber reinforced nylon material added with bromide fire retardant can produce thick smoke in burning and hydrogen bromide
Etc. harmful substances, human body can be caused to suffocate.Therefore, for glass fiber reinforced nylon material develop safe and environment-friendly, halogen-free flame-retardant system at
For the hot spot of research, occur the novel halogen-free flame retardants or flame-retardant system applied to glass fiber reinforced nylon material in recent years.
According to the literature, mainly include two major classes primary structure applied to the halogen-free flame retardants of glass fiber reinforced nylon material:
One kind is red phosphorus；Another kind of is Intumscent Flame Retardant System.For red phosphorus, although its good flame retardation effect, it faces two problems:
First is that the color of red phosphorus, limits its scope of application, it is generally only to apply in black products；Second is that being easy in process
The violents in toxicity such as hydrogen phosphide are generated, bring environmental protection and safety problem, therefore red phosphorus is not the best choosing of glass fiber reinforced nylon material
It selects.For Intumscent Flame Retardant System, this is a kind of efficient flame-retardant system, and under the condition of high temperature, Intumscent Flame Retardant System can be
Nylon surface forms fine and close layer of charcoal, and the layer of charcoal is heat-insulated, presses down cigarette, does not generate toxic and harmful gas, flame retardant effect is good.
Polyphosphoric acid melamine (Melamine Poly-phosphate, MPP) is a kind of phosphorus nitrogen expansion type combustion inhibitor, tool
Have good thermostabilization, excellent fireproof performance, with the features such as substrate compatibility is good, Halogen, low cigarette.Currently, glass fiber reinforced nylon material
Diethyl hypo-aluminum orthophosphate compounding polyphosphoric acid melamine (MPP) system is namely based on using most Intumscent Flame Retardant Systems.It should
The synergistic effect of Intumscent Flame Retardant System phosphorus content with higher and phosphorus nitrogen, may be implemented to glass fiber reinforced nylon material
Highly effective flame-retardant, while there is very high decomposition temperature, in the high temperature working processes of glass fiber reinforced nylon material, phosphorus will not be generated
Change the hypertoxic gas such as hydrogen.But since polyphosphoric acid melamine is easy the moisture absorption, cause using upper inconvenience；Simultaneously as polyphosphoric acid
Melamine char yield is lower, and flame retarding efficiency is low, causes polyphosphoric acid melamine additive amount larger, leads to manufactured goods mechanical property
A series of problems, such as capable of declining, these all limit polyphosphoric acid melamine answering in glass fiber reinforced nylon material on a large scale
With.
Summary of the invention
The invention discloses a kind of halogen-free flame-retardant glass fibers to enhance nylon, using by novel bittern-free phosphorous-nitrogen expansion type flame retardant
The halogen-free flameproof compound system that polyphosphoric acid boric acid melamine salt and organic hypophosphites and carbon forming agent form, the halogen-free flameproof are multiple
Low with system solubility, charring rate is high, and the halogen-free flame-retardant glass fiber enhancing nylon of preparation obtains splendid flame retardant effect, can reach
The flame-retardant standard of UL94-V0 (1.6mm).
Specific technical solution is as follows:
A kind of halogen-free flame-retardant glass fiber enhancing nylon, by weight percentage, raw material composition includes:
Nylon 30~60%；
Glass fibre 20~40%；
Halogen-free flameproof compound system 10~30%；
Wherein, the halogen-free flameproof compound system, by weight percentage, raw material composition includes:
Organic hypophosphites 60~85%；
Polyphosphoric acid boric acid melamine salt 13~35%；
Carbon forming agent 2~8%.
The polyphosphoric acid boric acid melamine salt, shown in structural formula such as following formula (I):
In formula, m is the molar ratio of polyphosphoric acid melamine and two structural unit of boric acid, m=3~6.
The present invention use novel fire-retardant compound system, including polyphosphoric acid boric acid melamine salt, organic hypophosphites with
And carbon forming agent, three are applied to glass fiber reinforced nylon material system after compounding under specific ratio, show excellent fire-retardant
Efficiency.In the compounding flame retardant, polyphosphoric acid boric acid melamine salt is New-type halide-free phosphorus nitrogen first public in the present invention
Expansion type flame retardant, by the way that boric acid is introduced into polyphosphoric acid melamine, significantly improve product under fire retardant high temperature at
Charcoal amount improves the flame retarding efficiency of fire retardant.After boric acid introduces, glassy mass covering can be formed in the combustion process of material
On the surface of the material, the diffusion for having obstructed fuel gas improves the flame retardant property of material.
Discovery is further tested, when two be made of polyphosphoric acid boric acid melamine salt, organic hypophosphites are only added
When component flame-retardant system, although the flame retardant property for the glass fiber enhanced nylon being prepared can achieve the standard of UL94V-0, but
Discoloration is easy to happen in process；And the degradation of polymer in process is easily led to, material mechanical performance decline.
The preparation method of the polyphosphoric acid boric acid melamine salt, steps are as follows:
A. melamine is dispersed in water, is mixed after being warming up to 60~80 DEG C with phosphoric acid, after 70~100 DEG C of insulation reactions
Obtain intermediate；
B. boric acid is mixed with water, being warming up to 60~80 DEG C is completely dissolved boric acid, then mixed with the intermediate of step a preparation
It closes, is continuously heating to 80~100 DEG C, insulation reaction obtains intermediate product；
C. intermediate product prepared by step b is heat-treated to get the polyphosphoric acid boric acid three at 300~360 DEG C
Paracyanogen amine salt.
In step a, to make melamine be easy dispersion, avoids reuniting, phosphoric acid is preferably added dropwise to melamine aqueous solution
In, and guarantee to be added dropwise in 2h.It is found through experiment that being closed if being added dropwise to melamine after first mixing phosphoric acid with water again
It is easy to happen reunion at melamine phosphate in the process, and the solubility of the polyphosphoric acid melamine prepared is higher.
In step a, the phosphoric acid is selected from commercially available containing 85wt%H3PO4Thick concentrated solution, melamine as described below
With the phosphoric acid quality in the mass ratio of phosphoric acid, with the 85wt%H3PO4In Solute mass meter.
Preferably:
The mass ratio of the melamine and water is 1:2.5~5.0；The concentration of melamine aqueous solution is excessive, phosphoric acid drop
Product is easy conglomeration during adding, it is difficult to evenly dispersed；Concentration is too small, and solubility is excessive in water for finished product, reduces obtaining for product
Rate increases wastewater treatment capacity.
The mass ratio of the melamine and phosphoric acid is 1.1~1.42:1.
In step a, also need the aftertreatment technologies such as to be filtered, wash and dry after insulation reaction.The drying temperature is
120~140 DEG C, drying time is 2~4h.
In step b, first boric acid is completely dissolved in water to obtain boric acid aqueous solution, then be uniformly mixed with intermediate.The step
In rapid, the additional amount of strict control boric acid is needed, because boric acid is added excessively, the solubility of product is will increase, reduces product
Thermal stability；Boric acid additional amount is few, is difficult to form stable glassy continuous layer of charcoal on the surface of the material during material combustion, reach
Less than the purpose for improving flame retarding efficiency.Preferably, the mass ratio of the intermediate and boric acid is 9~12:1.
Preferably, the mass ratio of the boric acid and water is 1:25~55；The concentration of boric acid aqueous solution is excessive, and boric acid dissolves not
Sufficiently, the reaction time is long；Concentration is too small, and product yield is low, and subsequent wastewater treatment amount is big.
In step b, yet need the aftertreatment technologies such as to be filtered, wash and dry after insulation reaction.The drying temperature
It is 120~140 DEG C, drying time is 2~4h.
In step c, by being heat-treated at a specific temperature range, the thermal stability of product can be further improved,
The solubility of product in water is reduced, the water absorption resistance energy of product is improved.Preferably, the heat treatment temperature is 330~360
℃。
Using the polyphosphoric acid boric acid melamine salt water absorption resistance energy of above-mentioned technique preparation, char yield is high under good, high temperature.
After tested, the solubility at 25 DEG C is 0.03~0.10g/L, and the carbon left at 800 DEG C is 35.0~51.2%, more poly- phosphorus
Sour melamine improves about 5~10%.
There is no particular/special requirement for nylon base in formula system of the invention, can selected from common kind PA6, PA66,
One of PA11, PA12, PA46, PA610, PA612, PAl010 etc. and semi-aromatic nylon PA6T and extraordinary nylon etc.
Or at least two it is compound.It preferably is selected from least one of nylon 6, nylon66 fiber.
The reinforcement used in formula system of the invention is equally applicable to other types for the most common glass fibre
Reinforcement, such as carbon fiber, silicon carbide ceramic fiber, aramid fiber.
Organic hypophosphites, the carbon forming agent used in formula system of the invention is compounded with polyphosphoric acid boric acid melamine salt
Form compounding flame retardant.
Preferably:
Organic hypophosphites is selected from aluminum diethylphosphinate.
The carbon forming agent is selected from least one of zinc oxide, zinc borate, zinc stannate, basic zirconium phosphate.
Further preferably, based on raw material gross weight, the additional amount of the halogen-free flameproof compound system is 15~25%, described
By weight percentage, raw material composition includes: halogen-free flameproof compound system
Aluminum diethylphosphinate 64~80%；
Polyphosphoric acid boric acid melamine salt 15~30%；
Carbon forming agent 5~8%.
Still further preferably, the additional amount of the halogen-free flameproof compound system is 20%, the halogen-free flameproof compound system
By weight percentage, raw material composition includes:
Aluminum diethylphosphinate 67.5~77.5%；
Polyphosphoric acid boric acid melamine salt 15~25%；
Carbon forming agent 5~7.5%.
It is further preferred that the polyphosphoric acid boric acid melamine salt, m=3.1~3.9, the carbon left at 800 DEG C is higher,
About 41.0~50.2%.
Preferably, the average grain diameter D 50 of the aluminum diethylphosphinate is 20~50 μm, polyphosphoric acid boric acid melamine
Average grain diameter D50 be 20~50 μm, the average grain diameter D 50 of carbon forming agent is 20~50 μm.Three raw materials are all made of approximate partial size
Range, it is ensured that powder uniformly mixes.
Above-mentioned halogen-free flame-retardant glass fiber enhancing nylon the preparation method comprises the following steps:
(1) organic secondary phosphine acid salt, polyphosphoric acid boric acid melamine salt are mixed with carbon forming agent by above-mentioned weight proportion
It is even, obtain powder material；
(2) double screw extruder is used, substrate is added in hopper, glass is added from glass entrance, from powder charging aperture
The powder material of step (1) preparation is added, starts host and feeder, extruding pelletization, obtains halogen-free flame-retardant glass fiber enhancement engineering
Plastics.
Compared with prior art, the present invention has the advantage that
The invention discloses it is a kind of applied to halogen-free flame-retardant glass fiber enhancing nylon system in halogen-free flameproof compound system, by
Novel bittern-free phosphorous-nitrogen expansion type flame retardant polyphosphoric acid boric acid melamine salt compounds composition with organic hypophosphites and carbon forming agent.
The novel polyphosphoric acid boric acid melamine salt fire retardant have water absorption resistance can the high advantage of char yield under good, high temperature, then
After compounding with the organic hypophosphites and carbon forming agent of special ratios, the fire-retardant effect of glass fiber enhanced nylon system can be significantly improved
Rate has shorter burning time, can reach the flame-retardant standard of UL94-V0 (1.6mm), have both color inhibition and excellent mechanical property
Energy.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is furture elucidated.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after having read the content of the invention lectured, those skilled in the art
Member can make various changes and modification to the present invention, and such equivalent forms are equally fallen within defined by the application the appended claims
Range.
Embodiment 1
A. 500mL deionization is added into the 1000mL four-hole boiling flask equipped with blender, thermometer and reflux condensate device
Water, 186g melamine, heat temperature raising is simultaneously stirred to 80 DEG C, then the phosphoric acid of 199g 85% is slowly added dropwise, and is added dropwise in about one hour
Terminate.Then at 95 DEG C insulated and stirred 2 hours.Obtained slurry is filtered, is repeatedly washed with deionized water, is done at 120 DEG C
It is dry, obtain 323.7g intermediate.
B. 1000mL deionization is added into the 2000mL four-hole boiling flask equipped with blender, thermometer and reflux condensate device
Water, 27.1g boric acid, being heated to 80 DEG C is completely dissolved boric acid, and the 323.7g intermediate that step a is obtained is added, and keeps 80
DEG C temperature, is stirred to react 3 hours.Suspension is cooled down, is filtered, and repeatedly washed with deionized water, then at 120 DEG C
It is dried to obtain 316.4g intermediate product.
C. 316.4g intermediate product obtained in step b is heat-treated 4h at a temperature of 330 DEG C, it is cooling after the completion of heat treatment
Up to final product, weight 278.9g.
It carries out infrared spectroscopy respectively to final product manufactured in the present embodiment and elemental analysis test, infrared spectroscopy is mainly special
It is as follows to levy peak: 1680cm-1Place is C=N stretching vibration peak；1622cm-1For N-H flexural vibrations peak；1245cm-1It is flexible for P=O
Vibration peak, 1329cm-1For the stretching vibration peak of B-O；Elemental analysis is the results show that phosphorus content in product: 13.1%, boron content:
2.3%, nitrogen content: 35.5%, oxygen content: 25.0%；Contain the elements such as boron, phosphorus, nitrogen in polyphosphoric acid boric acid melamine, it was demonstrated that
The structural formula of the final product is as follows, in formula, m=3.9.
Through thermal weight loss and solubility test, be lauched at 25 DEG C in solubility 0.06g/L, the carbon left at 800 DEG C is
41.0%.
Polyphosphoric acid boric acid melamine salt manufactured in the present embodiment is answered with aluminum diethylphosphinate and carbon forming agent zinc oxide
With applied in glass fiber enhanced nylon 66, specific formula and flame retardant property are listed in the table below in 1.
Each raw material of (each raw material is by weight percentage) preparation is formulated by table 1 and is sufficiently dried, then in high-speed mixer
Middle that each component is uniformly mixed, double screw extruder extruding pelletization prepares standard batten (thickness 1.6mm) on injection molding machine, surveys
It tries flame retardant property (UL94), and records 5 test bars total burning times.
Comparative example 1
Compared with the preparation process of embodiment 1, step b is removed, intermediate prepared by step a is directly at 330 DEG C of warm
4h is managed, after tested, product is polyphosphoric acid melamine salt after cooling.
Polyphosphoric acid melamine salt prepared by this comparative example is compounded with aluminum diethylphosphinate with carbon forming agent zinc oxide and is answered
For in glass fiber enhanced nylon 66, specific formula and flame retardant property to be listed in the table below in 1.
Comparative example 2
Compared with the preparation process of embodiment 1, step c, i.e., intermediate product (the i.e. phosphoric acid directly prepared step b are removed
Boric acid melamine salt) with aluminum diethylphosphinate and carbon forming agent zinc oxide composite usage in glass fiber enhanced nylon 66, specifically
Formula and flame retardant property are listed in the table below in 1.
Comparative example 3
The preparation process of polyphosphoric acid boric acid melamine salt is in the same manner as in Example 1, and difference is only that, in step a, first will
500mL deionized water is uniformly mixed with the phosphoric acid of 199g 85wt%, is slow added into 186g melamine.
After tested, the polyphosphoric acid boric acid melamine salt of this comparative example preparation, through thermal weight loss and solubility test, 25
Solubility 0.18g/L at DEG C, the carbon left at 800 DEG C is 39.2%.
Polyphosphoric acid boric acid melamine salt prepared by this comparative example is answered with aluminum diethylphosphinate and carbon forming agent zinc oxide
With applied in glass fiber enhanced nylon 66, specific formula and flame retardant property are listed in the table below in 1.
Comparative example 4
The preparation process of polyphosphoric acid boric acid melamine salt is in the same manner as in Example 1, and difference is only that, in step b, is added
17.9g boric acid.
After tested, the polyphosphoric acid boric acid melamine salt of this comparative example preparation, m=6.3.It is surveyed through thermal weight loss and solubility
Examination, the solubility 0.06g/L at 25 DEG C, the carbon left at 800 DEG C is 33.6%.
Polyphosphoric acid boric acid melamine salt prepared by this comparative example is answered with aluminum diethylphosphinate and carbon forming agent zinc oxide
With applied in glass fiber enhanced nylon 66, specific formula and flame retardant property are listed in the table below in 1.
Comparative example 5
The preparation process of polyphosphoric acid boric acid melamine salt is in the same manner as in Example 1, and difference is only that, in step b, is added
36.9g boric acid.
After tested, the polyphosphoric acid boric acid melamine salt of this comparative example preparation, m=2.8.It is surveyed through thermal weight loss and solubility
Examination, the solubility 0.17g/L at 25 DEG C, the carbon left at 800 DEG C is 49.2%.
Polyphosphoric acid boric acid melamine salt prepared by this comparative example is answered with aluminum diethylphosphinate and carbon forming agent zinc oxide
With applied in glass fiber enhanced nylon 66, specific formula and flame retardant property are listed in the table below in 1.
Comparative example 6
Polyphosphoric acid boric acid melamine salt prepared by embodiment 1 only increases with aluminum diethylphosphinate composite usage in glass
In strong nylon66 fiber, specific formula and flame retardant property are listed in the table below in 1.
Embodiment 2
A. 500mL deionization is added into the 1000mL four-hole boiling flask equipped with blender, thermometer and reflux condensate device
Water, 186g melamine, heat temperature raising simultaneously stir to 60 DEG C, the phosphoric acid of 154g 85wt% are slowly added dropwise, is added dropwise in about one hour
Terminate.Then at 80 DEG C of insulated and stirreds, reaction was completed within 1 hour, and obtained slurry is filtered, and is repeatedly washed with deionized water,
Then dry at 120 DEG C, obtain 289.9g intermediate.
B. 800mL deionization is added into the 2000mL four-hole boiling flask equipped with blender, thermometer and reflux condensate device
Water, is added 31.7g boric acid, heat temperature raising and stirring is completely dissolved boric acid, is continuously heating to 90 DEG C, is added what step a was obtained
289.9g intermediate is stirred to react 3.5h then in 100 DEG C of temperature.Suspension is cooled down, is filtered, and use deionized water
Repeatedly washing, is then dried to obtain 289.5g intermediate product at 120 DEG C.
C. 289.5g intermediate product obtained in step b is heat-treated 2h at a temperature of 340 DEG C, it is cooling after the completion of heat treatment
Obtain polyphosphoric acid boric acid melamine salt, product weight 242.8g.
After tested, polyphosphoric acid boric acid melamine salt manufactured in the present embodiment, m=3.2.It is surveyed through thermal weight loss and solubility
Examination, the solubility 0.08g/L at 25 DEG C, the carbon left at 800 DEG C is 47.5%.
Polyphosphoric acid boric acid melamine salt manufactured in the present embodiment is answered with aluminum diethylphosphinate and carbon forming agent zinc borate
With applied in glass fiber enhanced nylon 66, specific formula and flame retardant property are listed in the table below in 1.
Embodiment 3
A. 500mL deionization is added into the 1000mL four-hole boiling flask equipped with blender, thermometer and reflux condensate device
Water, 186g melamine, heat temperature raising simultaneously stir to 100 DEG C, the phosphoric acid of 199g 85wt% are slowly added dropwise, drips in about one hour
Add end.Then at 90 DEG C of insulated and stirreds, reaction was completed within 2 hours, and obtained slurry is filtered, and is repeatedly washed with deionized water
It washs, it is then dry at 120 DEG C, obtain 332.1g intermediate.
B. 1000mL deionization is added into the 2000mL four-hole boiling flask equipped with blender, thermometer and reflux condensate device
Water, 31.1g boric acid, heat temperature raising and stirring are completely dissolved boric acid, are continuously heating to 100 DEG C, are added what step a was obtained
332.1g intermediate keeps 92 DEG C of temperature, is stirred to react 3h.Suspension is cooled down, is filtered, and repeatedly washed with deionized water
It washs, 313.9g intermediate product is then dried to obtain at 140 DEG C.
C. 313.9g intermediate product obtained in step b is heat-treated 3h at a temperature of 360 DEG C, it is cooling after the completion of heat treatment
Up to product polyphosphoric acid boric acid melamine salt, product weight 259.9g.
After tested, polyphosphoric acid boric acid melamine salt manufactured in the present embodiment, m=3.1.It is surveyed through thermal weight loss and solubility
Examination, the solubility 0.05g/L at 25 DEG C, the carbon left at 800 DEG C is 50.2%.
Polyphosphoric acid boric acid melamine salt manufactured in the present embodiment is answered with aluminum diethylphosphinate and carbon forming agent zinc stannate
With applied in glass fiber enhanced nylon 66, specific formula and flame retardant property are listed in the table below in 1.
Embodiment 4
A. 500mL deionized water is added into the 1000mL four-hole boiling flask equipped with blender, thermometer and reflux condensing tube,
186g melamine, heating stirring are warming up to 80 DEG C, and the phosphoric acid of 161g85% is slowly added dropwise, and about 1h is dripped off, persistently overheating to 90
DEG C, and insulated and stirred 2h.Gained slurry is filtered, and is repeatedly washed with deionized water, it is then dry at 120 DEG C, it obtains
296.5g intermediate.
B. to equipped with electric mixer, thermometer and reflux condensing tube 3000mL four-hole boiling flask in be added 1400mL go from
Sub- water, 25.6g boric acid, heat temperature raising and stirring are completely dissolved boric acid, are continuously heating to 80 DEG C, are added what step a was obtained
296.5g intermediate keeps 85 DEG C of temperature, is stirred to react 4.5h.Suspension is cooled down, is filtered, and multiple with deionized water
Washing, is then dried to obtain 285.4g intermediate product at 120 DEG C.
C. 285.4g intermediate product obtained in step b is heat-treated 2h at a temperature of 350 DEG C, it is cooling after the completion of heat treatment
Up to product polyphosphoric acid boric acid melamine salt, product weight 238.1g.
After tested, polyphosphoric acid boric acid melamine salt manufactured in the present embodiment, m=3.9.It is surveyed through thermal weight loss and solubility
Examination, the solubility 0.05g/L at 25 DEG C, the carbon left at 800 DEG C is 43.9%.
Polyphosphoric acid boric acid melamine salt manufactured in the present embodiment is answered with aluminum diethylphosphinate and carbon forming agent basic zirconium phosphate
With applied in glass fiber enhanced nylon 66, specific formula and flame retardant property are listed in Table 1 below.
Table 1
| Raw material composition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| PA66 | 50 | 50 | 50 | 50 |
| Glass | 30 | 30 | 30 | 30 |
| Polyphosphoric acid boric acid melamine salt | 4 | 3 | 5 | 4.5 |
| Aluminum diethylphosphinate | 14.5 | 15.5 | 13.5 | 14.5 |
| Zinc oxide | 1.5 | / | / | / |
| Zinc borate | / | 1.5 | / | / |
| Zinc stannate | / | / | 1.5 | / |
| Basic zirconium phosphate | / | / | / | 1.0 |
| Anti-flammability (UL94) | V-0 | V-0 | V-0 | V-0 |
| Solubility (g/L) | 0.06 | 0.08 | 0.05 | 0.05 |
Continued 1
Claims (10)
1. a kind of halogen-free flame-retardant glass fiber enhances nylon, which is characterized in that by weight percentage, raw material composition includes:
Nylon 30~60%；
Glass fibre 20~40%；
Halogen-free flameproof compound system 10~30%；
Wherein, the halogen-free flameproof compound system, by weight percentage, raw material composition includes:
Organic hypophosphites 60~85%；
Polyphosphoric acid boric acid melamine salt 13~35%；
Carbon forming agent 2~8%.
The polyphosphoric acid boric acid melamine salt, shown in structural formula such as following formula (I):
In formula, m is the molar ratio of polyphosphoric acid melamine and two structural unit of boric acid, m=3~6.
2. halogen-free flame-retardant glass fiber according to claim 1 enhances nylon, which is characterized in that the nylon is selected from nylon 6, Buddhist nun
At least one of dragon 66.
3. halogen-free flame-retardant glass fiber according to claim 1 enhances nylon, which is characterized in that organic hypophosphites is selected from
Aluminum diethylphosphinate.
4. halogen-free flame-retardant glass fiber according to claim 1 enhances nylon, which is characterized in that the polyphosphoric acid boric acid melamine
The preparation process of amine salt is as follows:
A. melamine is dispersed in water, is mixed after being warming up to 60~80 DEG C with phosphoric acid, obtained after 70~100 DEG C of insulation reactions
Intermediate；
B. boric acid is mixed with water, being warming up to 60~80 DEG C is completely dissolved boric acid, then mixes with the intermediate of step a preparation,
80~100 DEG C are continuously heating to, insulation reaction obtains intermediate product；
C. intermediate product prepared by step b is heat-treated to get the polyphosphoric acid boric acid melamine at 300~360 DEG C
Amine salt.
5. halogen-free flame-retardant glass fiber according to claim 4 enhances nylon, which is characterized in that in step a:
The mass ratio of the melamine and water is 1:2.5~5.0；
The mass ratio of the melamine and phosphoric acid is 1.1~1.42:1.
6. halogen-free flame-retardant glass fiber according to claim 4 enhances nylon, which is characterized in that in step b:
The mass ratio of the boric acid and water is 1:25~55；
The mass ratio of the intermediate and boric acid is 9~12:1.
7. halogen-free flame-retardant glass fiber according to claim 4 enhances nylon, which is characterized in that in step c, the heat treatment temperature
Degree is 330~360 DEG C.
8. halogen-free flame-retardant glass fiber according to claim 1 enhances nylon, which is characterized in that the carbon forming agent is selected from oxidation
At least one of zinc, zinc borate, zinc stannate, basic zirconium phosphate.
9. any halogen-free flame-retardant glass fiber enhances nylon according to claim 1~8, which is characterized in that the halogen-free flameproof
The additional amount of compound system is 15~25%, and by weight percentage, the raw material composition of halogen-free flameproof compound system includes:
Aluminum diethylphosphinate 64~80%；
Polyphosphoric acid boric acid melamine salt 15~30%；
Carbon forming agent 5~8%.
10. halogen-free flame-retardant glass fiber according to claim 9 enhances nylon, which is characterized in that the polyphosphoric acid boric acid trimerization
Cyanamide salt, m=3.1~3.9 in structural formula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811546453.9A CN109627758B (en) | 2018-12-18 | 2018-12-18 | Halogen-free flame-retardant glass fiber reinforced nylon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811546453.9A CN109627758B (en) | 2018-12-18 | 2018-12-18 | Halogen-free flame-retardant glass fiber reinforced nylon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109627758A true CN109627758A (en) | 2019-04-16 |
| CN109627758B CN109627758B (en) | 2021-01-08 |
Family
ID=66074969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811546453.9A Active CN109627758B (en) | 2018-12-18 | 2018-12-18 | Halogen-free flame-retardant glass fiber reinforced nylon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109627758B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591341A (en) * | 2019-10-09 | 2019-12-20 | 江苏万纳普新材料科技有限公司 | Special halogen-free flame-retardant synergistic functional master batch for nylon resin modification and preparation method thereof |
| CN111057367A (en) * | 2019-11-26 | 2020-04-24 | 浙江恒澜科技有限公司 | High-lasting flame-retardant nylon 6 and preparation method thereof |
| CN113563717A (en) * | 2021-07-27 | 2021-10-29 | 金旸（厦门）新材料科技有限公司 | Antibacterial low-precipitation flame-retardant polyamide material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781571A (en) * | 2009-12-18 | 2010-07-21 | 苏州科技学院 | Complex intumescent flame retardant |
| CN102127230A (en) * | 2010-01-19 | 2011-07-20 | 中化蓝天集团有限公司 | New process for preparing modified melamine polyphosphate |
| CN102690505A (en) * | 2012-05-29 | 2012-09-26 | 东莞市信诺橡塑工业有限公司 | Polybutylene terephthalate composite for laser structuring and method for preparing polybutylene terephthalate composite |
| CN103044912A (en) * | 2012-11-28 | 2013-04-17 | 江苏金发科技新材料有限公司 | Halogen-free flame retardant continuous long glass fiber reinforced polyamide 66 composite material and preparation method thereof |
| CN103214840A (en) * | 2013-04-16 | 2013-07-24 | 常熟市凯力达蜂窝包装材料有限公司 | Preparation method of glass-fiber-reinforced black halogen-free flame-retardant polyamide composite material |
| CN108084101A (en) * | 2018-01-18 | 2018-05-29 | 湖南工学院 | Melamine polyphosphate and preparation method thereof |
-
2018
- 2018-12-18 CN CN201811546453.9A patent/CN109627758B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781571A (en) * | 2009-12-18 | 2010-07-21 | 苏州科技学院 | Complex intumescent flame retardant |
| CN102127230A (en) * | 2010-01-19 | 2011-07-20 | 中化蓝天集团有限公司 | New process for preparing modified melamine polyphosphate |
| CN102690505A (en) * | 2012-05-29 | 2012-09-26 | 东莞市信诺橡塑工业有限公司 | Polybutylene terephthalate composite for laser structuring and method for preparing polybutylene terephthalate composite |
| CN103044912A (en) * | 2012-11-28 | 2013-04-17 | 江苏金发科技新材料有限公司 | Halogen-free flame retardant continuous long glass fiber reinforced polyamide 66 composite material and preparation method thereof |
| CN103214840A (en) * | 2013-04-16 | 2013-07-24 | 常熟市凯力达蜂窝包装材料有限公司 | Preparation method of glass-fiber-reinforced black halogen-free flame-retardant polyamide composite material |
| CN108084101A (en) * | 2018-01-18 | 2018-05-29 | 湖南工学院 | Melamine polyphosphate and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591341A (en) * | 2019-10-09 | 2019-12-20 | 江苏万纳普新材料科技有限公司 | Special halogen-free flame-retardant synergistic functional master batch for nylon resin modification and preparation method thereof |
| CN111057367A (en) * | 2019-11-26 | 2020-04-24 | 浙江恒澜科技有限公司 | High-lasting flame-retardant nylon 6 and preparation method thereof |
| CN111057367B (en) * | 2019-11-26 | 2022-09-06 | 浙江恒逸石化研究院有限公司 | High-lasting flame-retardant nylon 6 and preparation method thereof |
| CN113563717A (en) * | 2021-07-27 | 2021-10-29 | 金旸（厦门）新材料科技有限公司 | Antibacterial low-precipitation flame-retardant polyamide material and preparation method thereof |
| CN113563717B (en) * | 2021-07-27 | 2022-10-25 | 金旸（厦门）新材料科技有限公司 | Antibacterial low-precipitation flame-retardant polyamide material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109627758B (en) | 2021-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109942891B (en) | Phosphorus-nitrogen-zinc two-dimensional supermolecule coated molybdenum disulfide hybrid flame retardant and application thereof | |
| Wang et al. | Metal compound-enhanced flame retardancy of intumescent epoxy resins containing ammonium polyphosphate | |
| CN105348326B (en) | A kind of N P fire proofings and preparation method thereof and the application in textile | |
| WO2019100592A1 (en) | Halogen-free flame retardant compound system for glass fiber reinforced nylon and application thereof in halogen-free flame retardant glass fiber reinforced nylon material | |
| CN109627758A (en) | A kind of halogen-free flame-retardant glass fiber enhancing nylon | |
| CN107501329B (en) | A kind of phosphorus nitrogen silicon ternary synergistic flame retardant and its preparation method and purposes | |
| CN109438754A (en) | It a kind of phosphorous 3-triazole compounds preparation method and its is applied on flame-proof polylactic acid | |
| CN106519295A (en) | Novel phosphorus-based flame retardant and halogen-free intumescent anti-flaming ABS (Acrylonitrile Butadiene Styrene) resin containing same | |
| CN114806156A (en) | Nylon composite material with flame retardance, smoke suppression and reinforcement functions and preparation method thereof | |
| CN109679138B (en) | Halogen-free flame retardant melamine polyphosphate borate salt and preparation method and application thereof | |
| EP4215575A1 (en) | Halogen-free flame-retardant compounded system having resistance to high heat and high shear and high flame resistance, and application thereof | |
| Huang et al. | Synthesis of a phosphorus/silicon hybrid and its synergistic effect with melamine polyphosphates on flame retardant polypropylene system | |
| CN113637160B (en) | Triazine structure-containing phosphorus-nitrogen star flame retardant, and preparation method and application thereof | |
| CN111484520A (en) | Ethylene diamine tetramethylene aluminum phosphonate flame retardant and preparation method and application thereof | |
| Xu et al. | Synthesis of aluminum bis (hydroxy‐phenyl‐methyl) phosphinate and its synergistic flame retardant mechanism in PLA | |
| CN115322441B (en) | Method for producing aluminum hypophosphite flame retardant by utilizing sodium hypophosphite mother liquor | |
| CN101638421B (en) | Preparation method of o-diaminobenzene phosphorylchloride condensed pentaerythritol ester | |
| CN113956294B (en) | Special flame retardant for polyoxymethylene and preparation method thereof | |
| CN113185873B (en) | Preparation method of bio-based flame-retardant and anti-photoaging PVA composite material | |
| CN115850708A (en) | Preparation method and application of N-P-Si-containing cage polysilsesquioxane flame retardant | |
| CN105949509B (en) | A kind of six methylenephosphonic acid magnesium fire retardant of hybrid inorganic-organic and preparation method thereof | |
| CN105273308A (en) | Halogen-free flame retardant long glass fiber and PP (polypropylene) composite material and preparation method thereof | |
| CN105037433B (en) | The preparation method of fire retardant tris hydroxymethyl phosphine caged bi-ester of phosphite | |
| CN105175778B (en) | A kind of applications of organic metal phosphinic acid compounds ZnCPN in terms of synergistic flame retardant | |
| CN104926880B (en) | The preparation method of fire retardant trihydroxy methyl phosphine oxide caged bi-ester of phosphite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: No. 88, Zhonghua East Road, Guanzhuang, Houbao Community, Tianmushan Street, Jiangyan District, Taizhou City, Jiangsu Province 225529 Patentee after: Jiangsu LISIDE New Materials Co.,Ltd. Address before: 225529 Houbao village, Guanzhuang, Shengao Town, Jiangyan District, Taizhou City, Jiangsu Province Patentee before: Jiangsu Liside New Material Co.,Ltd. |