CN105419106B - A kind of halogen-free flame-retardant resin and preparation method thereof - Google Patents
A kind of halogen-free flame-retardant resin and preparation method thereof Download PDFInfo
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- CN105419106B CN105419106B CN201610013434.4A CN201610013434A CN105419106B CN 105419106 B CN105419106 B CN 105419106B CN 201610013434 A CN201610013434 A CN 201610013434A CN 105419106 B CN105419106 B CN 105419106B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- C08L2201/22—Halogen free composition
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Abstract
The present invention provides a kind of halogen-free flame-retardant resin and preparation method thereof, component and its weight percent that the halogen-free flame-retardant resin includes are：Thermoplastic matrix resin 50 ~ 80%, expanding fire retardant 15 ~ 35%, the toughener 3 ~ 15% containing vinyl, crosslinking agent 0.01 ~ 0.1%, assistant crosslinking agent 0.5 ~ 1%, antioxidant 0.2 ~ 1%, dispersed lubricant 0.2 ~ 1%.The halogen-free flame-retardant resin of technical solution of the present invention, compared with uncrosslinked flame-retarded resin of the same race,Due to micro- cross-linked structure, with can also be with good anti-flammability in the case where amount of flame-retardant agent is few；And when amount of flame-retardant agent is larger, remain to keep good mechanical property, has many advantages, such as that resistance to migration, stability are high.
Description
Technical field
The invention belongs to bittern-free flame-proof material technical fields more particularly to a kind of halogen-free flame-retardant resin and preparation method thereof.
Background technology
Plastics and plastic products in the evolution of last 100 years, for the mankind production and life bring it is huge contribution and
Unlimited convenience, but since plastics belong to inflammable product mostly, to there is the production of the plastic part of fire-retardant requirement to receive
Limitation.In order to adapt to flame-retardancy requirements, domestic market is mainly using the resistance compounded containing halogen organic and antimony oxide
Agent production flame retardant plastics is fired to prepare.In recent years, bromide fire retardant is perplexed by dioxin problem, while being hindered with bromine-antimony system
The high molecular material of combustion can generate a large amount of flue dust and corrosive gas in thermal cracking and burning, and foreign countries are largely with nothing at present
Halogen fire retardant is substituted.
The high polymer of nitrogen phosphorus expansion type flame retardant filling is formed one layer of uniform porous carbon by surface when heat-flash or burning
Froth bed can play the role of heat-insulated, oxygen barrier, suppression cigarette, prevent melting drop, and Halogen, low cigarette, non-corrosive gas generate, and have good
Good fire-retardant and suppression hood.There are three fundamentals, i.e. acid source, charcoal source and air source for expansion type flame retardant.Its fire retardation master
If relying on material surface forms porous foam coke layer.
However, the melt strength of the plastics such as polypropylene is relatively low, the gas generated in foaming process is easy escape, leads to foam
It is formed difficult.Therefore when the fire-retardant PP of expansion type flame retardant, the utilization rate of gas is not high, reach fire-retardant V-0 grades it is required fire-retardant
Agent content is higher, and can cause the reduction of the mechanical property of material again simultaneously.Such as use ammonium polyphosphate class expanding fire retardant direct
When polypropylene flame redardant, amount of flame-retardant agent about needs 30% can just be fully achieved UL94V-0 grades.Since amount of flame-retardant agent is big, plastics are multiple
With more difficult, products obtained therefrom mechanical property is poor, also results in that gained plastic product stability is poor, and fire retardant has precipitation, surface
The problems such as being easy water suction.
Invention content
For the above technical problem, the invention discloses a kind of halogen-free flame-retardant resins and preparation method thereof, solve existing adopt
The polypropylene flame redardant obtained with expanding fire retardant, amount of flame-retardant agent is more, the problem of simultaneously resulting in mechanical properties decrease, adopts
There is good flame resistance, good mechanical performance, the high advantage of stability with the halogen-free fire retardant plastic of technical scheme of the present invention.
In this regard, the technical scheme is that：
A kind of halogen-free flame-retardant resin, it includes component and its weight percent be：Thermoplastic matrix resin 50~80%,
Expanding fire retardant 15~35%, the toughener 3~15% containing vinyl, crosslinking agent 0.01~0.1%, assistant crosslinking agent 0.5~
1%, antioxidant 0.2~1%, dispersed lubricant 0.2~1%.
As a further improvement on the present invention, it includes component and its weight percent be：Thermoplastic matrix resin 55
~75%, expanding fire retardant 18~30%, the toughener 4~12% containing vinyl, crosslinking agent 0.05~0.08%, assistant crosslinking agent
0.6~0.8%, antioxidant 0.5~0.8%, dispersed lubricant 0.5~0.8%.
Using this technical solution, introducing crosslinked agent and the toughener containing vinyl in formula so that produced in resin system
Raw cross-linked structure, increases melt strength；But in order to avoid generating excessive degradation reaction when crosslinked polymer, stringent control again
The dosage of crosslinking agent processed, while reducing degradation reaction by the way that assistant crosslinking agent and antioxidant is added so that it is generated in resin system
Cross-linked structure is micro- cross-linked structure.The halogen-free flame-retardant resin of technical solution using the present invention, with uncrosslinked fire-retardant tree of the same race
Lipid phase ratio, due to micro- cross-linked structure, with can also be with good anti-flammability in the case where amount of flame-retardant agent is few, and power
The advantages that performance is more preferable, resistance to migration, stability is high.
As a further improvement on the present invention, the halogen-free flame-retardant resin is prepared using following steps：It first will expansion
Fire retardant, the toughener containing vinyl, crosslinking agent and assistant crosslinking agent are kneaded uniformly in two-roll mill, and particle is caused to be hindered
Fire agent master batch；Fire retardant master batch is uniformly mixed with thermoplastic matrix resin, antioxidant, dispersed lubricant again, is squeezed in twin-screw
Go out extruding pelletization in machine, obtains halogen-free flame-retardant resin.
As a further improvement on the present invention, the expanding fire retardant includes fire retardant acid source, fire retardant air source and fire-retardant
The weight ratio of agent carbon source, the fire retardant acid source, fire retardant air source and fire retardant carbon source is (2~4):1:(0.3~0.8).
As a further improvement on the present invention, the weight ratio of the fire retardant acid source, fire retardant air source and fire retardant carbon source
Example is 3:1:0.5.
As a further improvement on the present invention, the fire retardant carbon source is pentaerythrite, dipentaerythritol, three seasons penta 4
At least one of alcohol, starch, sorbierite, polyphenylene oxide, phenolic resin.The fire retardant acid source is ammonium polyphosphate, silane cladding
At least one of ammonium polyphosphate, melamine resin coated ammonium polyphosphate or melamine-formaldehyde resin coated ammonium polyphosphate.It is described fire-retardant
Agent air source is at least one in melamine, melamine pyrophosphate, melamine polyphosphate, melamine cyanurate
Kind.
As a further improvement on the present invention, the toughener containing vinyl is ethylene propylene diene rubber (EPDM), high glue
Powder, butadiene rubber, natural rubber, the block copolymer (SBS) of s-B-S, styrene-ethylene-fourth two
In the block copolymer (SEBS) or methyl methacrylate-butadiene-styrene terpolymer (MBS) of alkene-styrene
A kind of or arbitrary two or more mixture.
As a further improvement on the present invention, the thermoplastic matrix resin is polyethylene, polypropylene, polystyrene, third
Alkene nitrile-at least one of butadiene-styrene copolymer (ABS) or high impact polystyrene.
As a further improvement on the present invention, the dispersed lubricant is ethylene bis-fatty acid amides, ethylene bis-fatty acid
It is the derivative of amide, diffusing oil, atoleine, PE waxes, oxidation PE waxes, spermaceti, stearic acid, butyl stearate, zinc stearate, hard
At least one of resin acid calcium.
As a further improvement on the present invention, the crosslinking agent is cumyl peroxide (DCP), and the assistant crosslinking agent is
Acrylic.
As a further improvement on the present invention, the assistant crosslinking agent is methyl methacrylate, methyl acrylate, acrylic acid
Ethyl ester, ethyl methacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, double trimethylolpropane
Triacrylate, 1,4 cyclohexane dimethanol diacrylate, polyethyleneglycol diacrylate (n=4~23), polypropylene glycol two
Acrylate, polypropyleneglycol diacrylate, 1,4 butanediol diacrylate, polytetramethylene glycol diacrylate, neopentyl glycol
Diacrylate, the third oxidation neopentylglycol diacrylate, 3- methyl-1s, 5- Diacrylates, 2- butyl -2- second
Base -1,3-PD diacrylate, 1,6- hexylene glycols acrylate monomer, ethoxyquin -1,6- hexanediyl ester, hydroxyl
Base pivalic acid neopentyl glycol ester diacrylate, 1,9- nonanediols diacrylate, 1,10-decanediol diacrylates, ethoxy
Change bisphenol a diacrylate, ethoxyquin trimethylolpropane methyl ether diacrylate, three acrylic acid of ethoxyquin trimethylol propane
Ester, glycerol propoxylate triacrylate, the third oxidation trimethylol propane triacrylate, three (2- ethoxys) isocyanuric acids, three propylene
Acid esters, pentaerythritol tetraacrylate, ethoxyquin pentaerythritol tetraacrylate, third oxidation pentaerythritol tetraacrylate, it is double-
In trimethylolpropane tetra-acrylate, ethoxyquin double pentaerythritol methacrylate, five/six acrylate of dipentaerythritol
It is at least one.
Preferably, composition intumescent resistance is blended using ammonium polyphosphate (APP), melamine (MA) and pentaerythrite (PER)
Agent is fired, uses ethylene propylene diene rubber (EPDM), SBS, SEBS as toughener, using cumyl peroxide (DCP) as crosslinking
Agent, acrylate substance carries out micro- crosslinking as crosslinking agent, to EPDM and PP, improves the melt strength of PP, when promoting burning
The formation of foams to reduce the dosage of expanding fire retardant, while improving the mechanical property of plastic material, while reducing fire-retardant
The migration of agent.
Based on foam theory, improving the melt strength of the plastics such as polypropylene can promote polypropylene etc. plastic foamed.Therefore,
Composition intumescent resistance is blended using ammonium polyphosphate (APP), melamine (MA) and pentaerythrite (PER) in technical scheme of the present invention
Agent is fired, uses ethylene propylene diene rubber (EPDM), SBS, SEBS etc. as toughener, using cumyl peroxide (DCP) as friendship
Join agent, acrylate substance carries out micro- crosslinking as crosslinking agent, to EPDM and PP, improves the melt strength of PP, promotes burning
When foams formation, to reduce the dosage of expanding fire retardant, while improving the mechanical property of plastic material, such as stretch strong
Degree, bending strength etc..The migration for reducing fire retardant simultaneously, avoids fire proofing bad order.
The invention also discloses a kind of preparation methods of halogen-free flame-retardant resin as described above, include the following steps：First will
Expanding fire retardant, the toughener containing vinyl, crosslinking agent and assistant crosslinking agent are kneaded uniformly in two-roll mill, and particle is caused to obtain
To fire retardant master batch；Fire retardant master batch is uniformly mixed with thermoplastic matrix resin, antioxidant, dispersed lubricant again, in double spiral shells
Extruding pelletization in bar extruder obtains halogen-free flameproof particulate material.
Compared with prior art, beneficial effects of the present invention are：
The halogen-free flame-retardant resin of technical solution using the present invention, compared with uncrosslinked flame-retarded resin of the same race, due to tool
There is micro- cross-linked structure, with can also be with good anti-flammability in the case where amount of flame-retardant agent is few；And amount of flame-retardant agent compared with
It when big, remains to keep good mechanical property, has many advantages, such as that resistance to migration, stability are high.
Specific implementation mode
The preferably embodiment of the present invention is described in further detail below.
Embodiment 1
A kind of halogen-free polypropylene flame redardant resin, it includes component and its weight percent content be：Polypropylene
67.95%, expanding fire retardant 25%, EPDM toughener 5%, crosslink agent DCP 0.05%, assistant crosslinking agent methyl methacrylate
0.5%, antioxidant 0.5%, dispersed lubricant EBS (N, N'- ethylene bis stearamide) 0.5%, dispersed lubricant PE waxes
0.5%；Wherein, the group of the expanding fire retardant becomes ammonium polyphosphate, melamine and pentaerythrite, ammonium polyphosphate, melamine
The weight ratio of amine and pentaerythrite is 3:1:0.5.
The halogen-free polypropylene flame redardant resin is prepared using following steps：
Step A：EPDM is first kneaded to packet roller in two-roll mill, expanding fire retardant, crosslinking agent and crosslinking is then added
Auxiliary agent is kneaded uniformly together, and it is spare to be cut into particle for then blanking.
Step B：The flame retardant masterbatch being kneaded is uniformly mixed with other components in formula, squeezes out and makes in twin-screw
Grain is to get halogen-free polypropylene flame redardant resin.
The halogen-free polypropylene flame redardant resin of gained is tested with injection molding machine sample preparation, it is UL94V0 to measure flame retardant rating
Grade.After sample is placed 30 days, surface smoothness does not change too much, shows that sample stability is good.Other performances are shown in Table 1.
Embodiment 2
A kind of halogen-free polypropylene flame redardant resin, it includes component and its weight percent content be：Polypropylene
62.95%, expanding fire retardant 30%, butadiene rubber 5%, crosslink agent DCP 0.05%, assistant crosslinking agent ethyl methacrylate
0.5%, antioxidant 0.5%, dispersed lubricant EBS0.5%, dispersed lubricant PE waxes 0.5%.Wherein, the expanding fire retardant
Group become silane coated ammonium polyphosphate, melamine pyrophosphate and dipentaerythritol, silane coated ammonium polyphosphate, melamine
Amine pyrophosphate and the weight ratio of dipentaerythritol are 2:1:0.8.
The halogen-free polypropylene flame redardant resin is prepared using following steps：
Step A：Butadiene rubber is first kneaded to packet roller in two-roll mill, then be added expanding fire retardant, crosslinking agent and
Crosslinking coagent is kneaded uniformly together, and it is spare to be cut into particle for then blanking.
Step B：The flame retardant masterbatch being kneaded is uniformly mixed with other components in formula, squeezes out and makes in twin-screw
Grain is to get halogen-free polypropylene flame redardant resin.
By the halogen-free polypropylene flame redardant resin injection molding machine sample preparation of gained, it is UL94V0 grades to measure flame retardant rating.Sample is put
After setting 30 days, surface smoothness does not change too much, shows that sample stability is good.Other performances are shown in Table 1.
Embodiment 3：
A kind of halogen-free polypropylene flame redardant resin, it includes component and its weight percent content be：Polypropylene
57.95%, expanding fire retardant 35%, SEBS 5%, crosslink agent DCP 0.05%, assistant crosslinking agent ethyl acrylate 0.5%, antioxygen
Agent 0.5%, dispersed lubricant EBS0.5%, dispersed lubricant atoleine 0.5%.Wherein, the composition of the expanding fire retardant
For melamine resin coated ammonium polyphosphate, the weight ratio of melamine polyphosphate and tripentaerythritol, three is 4:1:0.3.
The halogen-free polypropylene flame redardant resin is prepared using following steps：
Step A：Natural rubber is first kneaded to packet roller in two-roll mill, then be added expanding fire retardant, crosslinking agent and
Crosslinking coagent is kneaded uniformly together, and it is spare to be cut into particle for then blanking.
Step B：The flame retardant masterbatch being kneaded is uniformly mixed with other components in formula, squeezes out and makes in twin-screw
Grain is to get halogen-free polypropylene flame redardant resin.
The injection molding machine sample preparation of obtained flame-retardant material, it is UL94V0 grades to measure flame retardant rating.After sample is placed 30 days, surface
Finish does not change too much, shows that sample stability is good.Other performances are shown in Table 1.
Embodiment 4：
A kind of halogen-free polypropylene flame redardant resin, it includes component and its weight percent content be：Polypropylene
72.95%, expanding fire retardant 20%, methyl methacrylate-butadiene-styrene terpolymer 5%, crosslink agent DCP
0.05%, assistant crosslinking agent pentaerythritol triacrylate 0.5%, antioxidant 0.5%, dispersed lubricant EBS 0.5%, dispersion profit
Lubrication prescription PE waxes 0.5%.Wherein, the group of the expanding fire retardant becomes ammonium polyphosphate, melamine and pentaerythrite, the weight of three
Amount ratio is 3:1:0.6.
The halogen-free polypropylene flame redardant resin is prepared using following steps：
Step A：EPDM is first kneaded to packet roller in two-roll mill, expanding fire retardant, crosslinking agent and crosslinking is then added
Auxiliary agent is kneaded uniformly together, and it is spare to be cut into particle for then blanking.
Step B：The flame retardant masterbatch being kneaded is uniformly mixed with other components in formula, squeezes out and makes in twin-screw
Grain is to get halogen-free polypropylene flame redardant resin.
By the injection molding machine sample preparation of gained halogen-free polypropylene flame redardant resin, it is UL94V1 grades to measure flame retardant rating.
Embodiment 5
A kind of halogen-free polypropylene flame redardant resin, it includes component and its weight percent content be：Polypropylene
52.95%, expanding fire retardant 30%, EPDM toughener 15%, crosslink agent DCP 0.05%, assistant crosslinking agent methyl methacrylate
0.5%, antioxidant 0.5%, dispersed lubricant EBS 0.5%, dispersed lubricant PE waxes 0.5%.Wherein, the expanding fire retardant
Group become ammonium polyphosphate, melamine and pentaerythrite, the weight ratio of three is 3:1:0.5.
The halogen-free polypropylene flame redardant resin is prepared using following steps：
Step A：EPDM is first kneaded to packet roller in two-roll mill, expanding fire retardant, crosslinking agent and crosslinking is then added
Auxiliary agent is kneaded uniformly together, and it is spare to be cut into particle for then blanking.
Step B：The flame retardant masterbatch being kneaded is uniformly mixed with other components in formula, squeezes out and makes in twin-screw
Grain is to get halogen-free polypropylene flame redardant resin.
By the injection molding machine sample preparation of gained halogen-free polypropylene flame redardant resin, it is UL94V0 grades to measure its flame retardant rating.Sample is put
After setting 30 days, surface smoothness does not change too much, shows that sample stability is good.Other performances are shown in Table 1.
Embodiment 6
A kind of halogen-free flame-proof highly anti-flush polyphenylacetylene resin, it includes component and its weight percent content be：Highly resistance
Rush polystyrene 67.95%, expanding fire retardant 25%, SBS toughener 5%, crosslink agent DCP 0.05%, assistant crosslinking agent methyl-prop
E pioic acid methyl ester 0.5%, antioxidant 0.5%, dispersed lubricant EBS 0.5%, dispersed lubricant PE waxes 0.5%；Wherein, described swollen
The group of swollen fire retardant becomes ammonium polyphosphate, melamine and pentaerythrite, ammonium polyphosphate, the weight of melamine and pentaerythrite
Than being 3:1:0.5.
The halogen-free polypropylene flame redardant resin is prepared using following steps：
Step A：SBS is first kneaded to packet roller in two-roll mill, expanding fire retardant, crosslinking agent and crosslinking is then added and helps
Agent is kneaded uniformly together, and it is spare to be cut into particle for then blanking.
Step B：The flame retardant masterbatch being kneaded is uniformly mixed with other components in formula, squeezes out and makes in twin-screw
Grain is to get halogen-free flameproof polystyrene resin.
The halogen-free flameproof polystyrene resin of gained is tested with injection molding machine sample preparation, it is UL94V0 to measure flame retardant rating
Grade.After sample is placed 30 days, surface smoothness does not change too much, shows that sample stability is good.Other performances are shown in Table 1.Its
He is shown in Table 1 at performance.
Comparative example 1
With the difference of embodiment 1, it is that it is free of crosslink agent DCP and assistant crosslinking agent methyl methacrylate, it includes
Component and its weight percent content are：Polypropylene 68.5%, expanding fire retardant 25%, EPDM toughener 5%, antioxidant
0.5%, dispersed lubricant EBS 0.5%, dispersed lubricant PE wax 0.5%；Wherein, the group of the expanding fire retardant becomes poly- phosphorus
The weight ratio of sour ammonium, melamine and pentaerythrite, ammonium polyphosphate, melamine and pentaerythrite is 3:1:0.5.
The halogen-free polypropylene flame redardant resin is prepared using following steps：
Step A：EPDM is first kneaded to packet roller in two-roll mill, expanding fire retardant is then added and is kneaded together uniformly,
Then it is spare to be cut into particle for blanking.
Step B：The flame retardant masterbatch being kneaded is uniformly mixed with other components in formula, squeezes out and makes in twin-screw
Grain is to get halogen-free polypropylene flame redardant resin.
The halogen-free polypropylene flame redardant resin of gained is tested with injection molding machine sample preparation, it is not fire-retardant to measure flame retardant property.
After sample is placed 30 days, surface smoothness changes, and performance is dimer, shows that fire retardant has certain precipitation.Other property
It can be shown in Table 1.
Comparative example 2
With the difference of embodiment 2, it is that it is free of crosslink agent DCP and assistant crosslinking agent methyl methacrylate, it includes
Component and its weight percent content are：Polypropylene 63.5%, expanding fire retardant 30%, butadiene rubber 5%, antioxidant 0.5%,
Dispersed lubricant EBS 0.5%, dispersed lubricant PE wax 0.5%；Wherein, the group of the expanding fire retardant becomes ammonium polyphosphate,
The weight ratio of melamine and pentaerythrite, ammonium polyphosphate, melamine and pentaerythrite is 3:1:0.5.
The halogen-free polypropylene flame redardant resin is prepared using following steps：
Step A：EPDM is first kneaded to packet roller in two-roll mill, expanding fire retardant is then added and is kneaded together uniformly,
Then it is spare to be cut into particle for blanking.
Step B：The flame retardant masterbatch being kneaded is uniformly mixed with other components in formula, squeezes out and makes in twin-screw
Grain is to get halogen-free polypropylene flame redardant resin.
The halogen-free polypropylene flame redardant resin of gained is tested with injection molding machine sample preparation, flame retardant rating is UL94V1 grades.Sample
After product are placed 30 days, surface smoothness changes, and performance is dimer, shows that fire retardant has certain precipitation.Other performances
It is shown in Table 1.
Comparative example 3
With the difference of embodiment 3, it is that it is free of toughener, crosslink agent DCP, assistant crosslinking agent methyl methacrylate,
Including component and its weight percent content be：Polypropylene 63.5%, expanding fire retardant 35%, antioxidant 0.5%, dispersion profit
Lubrication prescription EBS 0.5%, lubricant PE wax 0.5%；Wherein, the group of the expanding fire retardant become ammonium polyphosphate, melamine and
The weight ratio of pentaerythrite, ammonium polyphosphate, melamine and pentaerythrite is 3:1:0.5.
It is prepared using following steps：
After mixing by each component in formula, in twin-screw extruding pelletization to get halogen-free polypropylene flame redardant resin.
The halogen-free polypropylene flame redardant resin of gained is tested with injection molding machine sample preparation, flame retardant rating is UL94V0 grades.Sample
After product are placed 30 days, surface smoothness changes, and performance is dimer, shows that fire retardant has certain precipitation.Other performances
It is shown in Table 1.
1 Examples 1 to 6 of table and the performance comparison table for comparing comparative example 1~3
It is and uncrosslinked same by the data comparison in table 1 as it can be seen that the halogen-free flame-retardant resin of technical solution using the present invention
Kind of flame-retarded resin is compared, since with micro- cross-linked structure, good hinder can also be had in the case where amount of flame-retardant agent is few by having
Combustion property；In the case of same amount fire retardant, mechanical property is more excellent；When especially and amount of flame-retardant agent is larger, remain to keep fine
Mechanical property.Compared with the comparative example 3 for being not added with toughener, to reach identical flame retardant effect, be not added with the comparative example 3 of toughener
It needs to increase more fire retardants and can be only achieved UL94V0 grades, and mechanical property deterioration is very serious worse, and it is using the present invention
Technical solution, it is only necessary to which can both be reached by adding less fire retardant by UL94V0 grades, and mechanical property is more excellent.In addition to this, also
Have many advantages, such as that resistance to migration, stability are high.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
The specific implementation of the present invention is confined to these explanations.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the present invention's
Protection domain.
Claims (6)
1. a kind of halogen-free flame-retardant resin, which is characterized in that it includes component and its weight percent be：Thermoplastic matrix resin
50 ~ 80%, expanding fire retardant 15 ~ 35%, the toughener 3 ~ 15% containing vinyl, crosslinking agent 0.01 ~ 0.1%, assistant crosslinking agent 0.5 ~ 1%,
Antioxidant 0.2 ~ 1%, dispersed lubricant 0.2 ~ 1%；The expanding fire retardant includes fire retardant acid source, fire retardant air source and fire retardant
The weight ratio of carbon source, the fire retardant acid source, fire retardant air source and fire retardant carbon source is (2 ~ 4):1:(0.3~0.8)；It is described
Fire retardant carbon source be pentaerythrite, dipentaerythritol, tripentaerythritol, starch, sorbierite, polyphenylene oxide, in phenolic resin extremely
Few one kind；The fire retardant acid source is ammonium polyphosphate, silane coated ammonium polyphosphate, melamine resin coated ammonium polyphosphate or melamine-
At least one of formaldehyde resin coated ammonium polyphosphate；The fire retardant air source is melamine, melamine pyrophosphate, three
At least one of poly cyanamid Quadrafos, melamine cyanurate；The thermoplastic matrix resin is polypropylene；The friendship
Connection agent is cumyl peroxide, and the assistant crosslinking agent is acrylic.
2. halogen-free flame-retardant resin according to claim 1, which is characterized in that it includes component and its weight percent
For：Thermoplastic matrix resin 55 ~ 75%, expanding fire retardant 18 ~ 30%, the toughener 4 ~ 12% containing vinyl, and crosslinking agent 0.05 ~
0.08%, assistant crosslinking agent 0.6 ~ 0.8%, antioxidant 0.5 ~ 0.8%, dispersed lubricant 0.5 ~ 0.8%.
3. halogen-free flame-retardant resin according to claim 1, it is characterised in that：The fire retardant acid source, fire retardant air source and
The weight ratio of fire retardant carbon source is 3:1:0.5.
4. halogen-free flame-retardant resin according to claim 1 or 2, it is characterised in that：The toughener containing vinyl is three
First EP rubbers, high glue powder, butadiene rubber, natural rubber, the block copolymer of s-B-S, styrene-
The block copolymer of ethylene-butadiene-styrene or one in methyl methacrylate-butadiene-styrene terpolymer
Kind or arbitrary two or more mixture.
5. halogen-free flame-retardant resin according to claim 1, it is characterised in that：The assistant crosslinking agent is methyl methacrylate
Ester, methyl acrylate, ethyl acrylate, ethyl methacrylate, trimethylolpropane diacrylate, three propylene of pentaerythrite
Acid esters, double trimethylolpropane triacrylate, 1,4 cyclohexane dimethanol diacrylate, polyethyleneglycol diacrylate,
Polypropyleneglycol diacrylate, 1,4 butanediol diacrylate, polytetramethylene glycol diacrylate, neopentyl glycol diacrylate
Ester, the third oxidation neopentylglycol diacrylate, 3- methyl-1s, 5- Diacrylates, 2- butyl -2- ethyls -1,3- third
Omega-diol diacrylate, 1,6- hexylene glycols acrylate monomer, ethoxyquin -1,6- hexanediyl ester, 3-hydroxypivalic acid
Neopentyl glycol ester diacrylate, 1,9- nonanediols diacrylate, 1,10- decanediols diacrylate, ethoxylated bisphenol A bis-
Acrylate, ethoxyquin trimethylolpropane methyl ether diacrylate, ethoxyquin trimethylol propane triacrylate, the third oxidation are sweet
Oily triacrylate, the third oxidation trimethylol propane triacrylate, three (2- ethoxys) isocyanuric acid triacrylates, Ji Wusi
Alcohol tetraacrylate, ethoxyquin pentaerythritol tetraacrylate, the third oxidation pentaerythritol tetraacrylate, double-trihydroxy methyl third
At least one of alkane tetraacrylate, ethoxyquin double pentaerythritol methacrylate, five/six acrylate of dipentaerythritol.
6. a kind of preparation method of halogen-free flame-retardant resin as described in claim 1 ~ 5 any one, which is characterized in that including with
Lower step：First expanding fire retardant, the toughener containing vinyl, crosslinking agent and assistant crosslinking agent are kneaded in two-roll mill
It is even, cause particle to obtain fire retardant master batch；Fire retardant master batch and thermoplastic matrix resin, antioxidant, dispersed lubricant are mixed again
It closes uniformly, the extruding pelletization in double screw extruder obtains halogen-free flameproof particulate material.
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| CN111548696B (en) * | 2020-06-12 | 2022-01-07 | 中国铁道科学研究院集团有限公司金属及化学研究所 | Fireproof coating for steel structure surface and application thereof |
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| CN113480803B (en) * | 2021-07-13 | 2024-01-12 | 韩山师范学院 | Flame-retardant polyolefin composite material and preparation method and application thereof |
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| CN115322485A (en) * | 2022-09-15 | 2022-11-11 | 芜湖聚发新材料有限公司 | Halogen-free flame-retardant polypropylene material and preparation method thereof |
| CN116496576A (en) * | 2023-04-23 | 2023-07-28 | 江苏思可达塑业有限公司 | Anti-aging flame-retardant polypropylene material and preparation method thereof |
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