CN106905609A - The halogen-free flame-retardant polypropylene composition of the expanding fire retardant of system containing triazine and its preparation - Google Patents
The halogen-free flame-retardant polypropylene composition of the expanding fire retardant of system containing triazine and its preparation Download PDFInfo
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- CN106905609A CN106905609A CN201710137239.7A CN201710137239A CN106905609A CN 106905609 A CN106905609 A CN 106905609A CN 201710137239 A CN201710137239 A CN 201710137239A CN 106905609 A CN106905609 A CN 106905609A
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C08L23/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
Halogen-free flame-retardant polypropylene composition and its preparation the present invention relates to a kind of expanding fire retardant of system containing triazine, described halogen-free flame-retardant polypropylene composition are made in accordance with the following methods：65 90 parts of polypropylene is weighed by formula, 15 35 parts of triazine system expanding fire retardant, mixing is then added in double screw extruder, the melting mixing at a temperature of 190 220 DEG C, extrudes, and granulation obtains the halogen-free flame-retardant polypropylene composition.Compared with prior art, the present invention uses expansion type flame retardant, polypropylene is carried out as carbon forming agent with triazine system derivative it is flame-retardant modified, fire retardant addition amount it is fewer, there is provided a kind of good mechanical property, flame retarding efficiency halogen-free flame-retardant polypropylene composition high.
Description
Technical field
It is poly- more particularly, to a kind of halogen-free flameproof of the expanding fire retardant of system containing triazine the present invention relates to polymeric material field
Propylene compositions and its preparation.
Background technology
Polypropylene has the thermoplastic of extensive use, and its Limiting Oxygen Value LOI only has 18% or so, easily burning, and
There is molten drop phenomenon during burning, the application in many fields is restricted, so needing to carry out it flame-retardant modified.Halogenated flame retardant
It is few with addition, the characteristics of flame retardant effect is obvious and moderate, but due to halogenated flame retardant generated in burning it is poisonous,
Mordant dense smoke, pollutes environment, does not meet the theory of present environmental protection, so the use of halogenated flame retardant receives a large amount of limits
System.Therefore, development environment friendly halogen-free fireproof agent has been trend of the times.
In current high polymer material flame-retarded technology, expansion type flame retardant (IFR) is because with Halogen, flame retarding efficiency be high, combustion
Heat release is few during burning and the advantages of not producing poisonous, mordant gas, has become the important of plastic flame research and development
Direction.Expansion type flame retardant is mainly made up of three parts：Carbon source, acid source and source of the gas.Due to traditional phosphorus-nitrogen type expanding fire retardant
With pentaerythrite as carbon forming agent, but pentaerythrite (PER) is small molecule polar substances, and it has and is easily moved in polymer matrix
The shortcomings of moving and easily reacted with APP in process, causes the reduction of polypropylene flame redardant mechanical performance.Expansion at present
One critically important research direction of type fire retardant is exactly the research and development of new carbon forming agent.
The content of the invention
The purpose of the present invention is exactly to provide a kind of system containing triazine for the defect for overcoming above-mentioned prior art to exist to expand
The halogen-free flame-retardant polypropylene composition of fire retardant and its preparation.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of halogen-free flame-retardant polypropylene composition of the expanding fire retardant of system containing triazine, including following parts by weight component：
65-90 parts of polypropylene (PP), 15-35 parts, antioxidant 0.1-0.5 parts of triazine system expanding fire retardant (IFR).
Preferably, described polypropylene is the one kind in impact copolymer polypropylene or HOPP.Preferably, polypropylene
From the PP 1215C of Yang Zi petrochemical industry.
Preferably, described triazine system expanding fire retardant is poly- 2- ethanol amido -4,6- ethylenediamines base -1,3,5-triazines
(CFA), the mixture of APP (APP) and melamine (MEL), wherein, the weight ratio of three is (10-80)：(10-
80)：(10-80).
Preferably, antioxidant 0.1-0.5 parts is also included in described halogen-free flame-retardant polypropylene composition.
It is furthermore preferred that described antioxidant be phenols, phosphorous acid esters, sulfur-bearing esters in the mixing of one or more
Thing.
Even more preferably, described phenolic antioxidant is four [methyl-β-(3,5- di-tert-butyl-hydroxy phenyls)
Propionic ester] pentaerythritol ester, described phosphorous acid esters are phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, described containing thioesters
Class is thio-2 acid two (18) ester.
A kind of preparation method of the halogen-free flame-retardant polypropylene composition of the expanding fire retardant of system containing triazine, comprises the following steps：
Polypropylene, triazine system expanding fire retardant and antioxidant are weighed by formula, is mixed, be then added to double screw extruder
In, the melting mixing at a temperature of 190-220 DEG C, extrusion, granulation obtains the halogen-free flame-retardant polypropylene composition.
Expansion type flame retardant of the invention is made up of three parts：Carbonized agent (charcoal source), charing catalyst (acid source), swelling agent
(source of the gas), wherein, CFA is carbonized agent (charcoal source), and APP is charing catalyst (acid source), and MEL is swelling agent (source of the gas).
When expansion type flame retardant is heated, carbonized agent CFA is dehydrated into charcoal under charing catalyst APP effects, and carbide is swollen
Formed under the gas effect that swollen dose (MEL) is decomposed it is fluffy have the layer of charcoal of hole enclosed construction, as shown in figure 1, once formed, itself
It is non-ignitable, and the heat transfer between polymer and thermal source can be weakened, and prevent gas diffusion, once burning cannot get enough fuel and
Oxygen, the polymer of burning will self-extinguishment.This layer of charcoal experiences the following steps and is formed：(1) released by acid source APP at a lower temperature
Can esterification polyol and can be used as the inorganic acid of dehydrating agent.(2) at the temperature of a little higher than release acid, there is esterification, and
Amine in system can be used as the catalyst of esterification.(3) system melts before esterification or in esterification process.(4) water that reaction is produced
Steam and by source of the gas produce non-flammable gases make molten system expand bubble.(5) reaction is when being nearly completed, system gel and solid
Change, eventually form porous foam layer of charcoal, in order to foam, the reaction of each step almost must occur simultaneously, but must be according to strict
Order is carried out.
The triazine derivative compound rich in tertiary carbon structure that is a major class, with good incarbonization and thermally-stabilised
Property, there is good cooperative effect both when CFA (charcoal source) and APP (APP) are compounded, it is difficult and APP (APP) hair
Raw reaction, is expanded into the effect of charcoal substantially, and preferable with the compatibility of PP, the composition good mechanical property for obtaining.Traditional phosphorus
Nitrogen type expanding fire retardant is with pentaerythrite as carbon forming agent, but pentaerythrite (PER) is small molecule polar substances, and it has poly- in height
The shortcomings of easily migrating and easily reacted with APP (APP) in process in thing matrix, certainly will cause flame-retardant polypropylene
The reduction of alkene mechanical performance.
It is important to note that the addition of fire retardant can cause the material mechanical performance of composition and processing characteristics to drop
Low, amount of flame-retardant agent is too high to make its performance be unable to reach use requirement, and amount of flame-retardant agent is too low, fire-retardant needed for can not reaching
Effect.Total consumption of fire retardant is more suitable in 15-35wt%.
Flame-retardant system of the invention is, it is necessary to CFA carbonized agents (charcoal source), APP charing catalysts (acid source), MEL swelling agent (gas
Source) acting synergistically can be only achieved fire-retardant effect, and any one is used alone can not all reach fire-retardant purpose.When in system：
1) when CFA carbonized agents (charcoal source) content is higher, the content of corresponding APP charing catalysts (acid source) and MEL swelling agents (source of the gas) is low,
Resulting halogen-free flame-retardant polypropylene composition have when fire burning is met it is higher into charcoal speed with into carbon amounts, but due to shortcoming gas
Source and acid source, layer of charcoal inflation degree are relatively low, do not have enough consistency, and the layer of charcoal for ultimately forming is of poor quality, has seriously undermined nothing
Halogen flame-proof polypropelene composition fire resistance；2) CFA carbonized agents (charcoal source) content is low, corresponding APP charing catalysts (acid source) and
The content of MEL swelling agents (source of the gas) is high, and layer of charcoal has enough gas by inflation, easily blows brokenly layer of charcoal, the expansion charcoal for being formed
Layer degradation, weakens halogen-free flame-retardant polypropylene composition fire resistance.Therefore the proportioning of charcoal source, acid source and source of the gas needs
Preferable flame retardant effect is can be only achieved in suitable scope, the weight ratio of three is (10-80)：(10-80)：(10-80) more
Properly.
Compared with prior art, the present invention has advantages below：
(1) present invention uses expansion type flame retardant, polypropylene is carried out as carbon forming agent with triazine system derivative it is flame-retardant modified,
The amount of fire retardant addition is fewer, there is provided a kind of good mechanical property, flame retarding efficiency halogen-free flame-retardant polypropylene composition high.
(2) at present in high polymer material flame-retarded technology, expansion type flame retardant (IFR) is because having that Halogen, flame retarding efficiency are high, firing
Heat release is few during burning and the advantages of not producing poisonous, mordant gas, has become the important of plastic flame research and development
Direction.
(3) traditional phosphorus-nitrogen type expanding fire retardant is with pentaerythrite as carbon forming agent, but pentaerythrite (PER) is small molecule pole
Property material, it has the shortcomings that in polymer matrix easily migration and is easily reacted with APP in process, makes
Into the reduction of polypropylene flame redardant mechanical performance.Triazine derivative is compound of the major class rich in tertiary carbon structure, with excellent
Charred effect, compared with pentaerythrite, triaizine compounds have into charcoal and heat endurance is good, suction good with polypropylene compatible
It is moist it is small, the advantages of flame retarding efficiency is high
(4) halogen-free flameproof of PP resins is realized, uses triazine system derivative to carry out fire-retardant changing to polypropylene for carbon forming agent
Property, more traditional pentaerythrite improves dispersion of the fire retardant in resin, and the consumption of halogen-free flame retardants will lack, and greatly improve
The flame retarding efficiency and the mechanical performance of resin of system.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Raw material employed in following each embodiments is specially：PP：1215C Yang Zi petrochemical industry, PP：Z30S Daqing petrochemicals, gather
2- ethanol amido -4,6- ethylenediamines base -1,3,5-triazines (CFA)：Defend triumphant chemical industry, APP (APP) in Quzhou：Zhejiang dragon tripization
Work, melamine (MEL)：The bright sharp chemical industry in Henan, pentaerythrite (PER)：Shandong Feng Tai chemical industry, antioxidant：Four [methyl-β-
(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester Germany BASF.
Embodiment 1
To mix 2 minutes in 73 parts of PP 1215C, 9 parts of CFA, 9 parts of MEL and 9 part of APP high-speed mixers by weight
Afterwards, it is added in the main hopper of equidirectional parallel double-screw extruder, the melting mixing at a temperature of 190-220 DEG C, gained melt
Cooled down through tank after being extruded by Twin screw extruder, introducing pelleter carries out pelletizing operation, and gained pellet is the high-performance
Halogen-free flameproof PP compositions.
Embodiment 2
To mix 2 minutes in 76 parts of PP 1215C, 8 parts of CFA, 8 parts of MEL and 8 part of APP high-speed mixers by weight
Afterwards, it is added in the main hopper of equidirectional parallel double-screw extruder, the melting mixing at a temperature of 190-220 DEG C, gained melt
Cooled down through tank after being extruded by Twin screw extruder, introducing pelleter carries out pelletizing operation, and gained pellet is the high-performance
Halogen-free flameproof PP compositions.
Embodiment 3
To mix 2 minutes in 79 parts of PP 1215C, 7 parts of CFA, 7 parts of MEL and 7 part of APP high-speed mixers by weight
Afterwards, it is added in the main hopper of equidirectional parallel double-screw extruder, the melting mixing at a temperature of 190-220 DEG C, gained melt
Cooled down through tank after being extruded by Twin screw extruder, introducing pelleter carries out pelletizing operation, and gained pellet is the high-performance
Halogen-free flameproof PP compositions.
Embodiment 4
It is by weight that 78.7 parts of PP 1215C, 7 parts of CFA, 7 parts of MEL, 7 parts of APP and 0.3 part of antioxidants are mixed with high speed
After mixing 2 minutes in conjunction machine, it is added in the main hopper of equidirectional parallel double-screw extruder, is melted at a temperature of 190-220 DEG C
Melt mixing, gained melt is cooled down after being extruded by Twin screw extruder through tank, and introducing pelleter carries out pelletizing operation, gained pellet
As described high-performance halogen-free flame retardant PP compositions.
Embodiment 5
After mixing 2 minutes in 76 parts of PP Z30S, 8 parts of CFA, 8 parts of MEL and 8 part of APP high-speed mixers by weight,
It is added in the main hopper of equidirectional parallel double-screw extruder, the melting mixing at a temperature of 190-220 DEG C, gained melt is by double
Cooled down through tank after extruser extrusion, introducing pelleter carries out pelletizing operation, and gained pellet is the high-performance halogen-free
Fire-retardant PP compositions.
In order to further embody beneficial effects of the present invention, using unified measuring method, to above-mentioned five embodiments with
Four comparative examples using prior art are relatively measured, compared.
Measuring method is：Limited oxygen index (L0I) is combined the test of thing limited oxygen index according to standard ASTM D286.
Anti-flammability is combined the test of thing fire resistance according to standard UL94.Tensile strength and elongation at break are according to standard GB/
T1843-2008 is combined the test for stretching intensity and elongation at break of thing.Izod notched impact strength is according to standard GB/
T1843-2008 measures the Izod notched impact strength of composition.
Comparative example 1~4
Comparative example 1
After mixing 2 minutes in 100 parts of PP 1215C high-speed mixers by weight, it is added to corotating twin-screw and squeezes
Go out in the main hopper of machine, the melting mixing at a temperature of 190-220 DEG C, gained melt by Twin screw extruder extrude after through tank
Cooling, introducing pelleter carries out pelletizing operation, and gained pellet is the PP compositions.
Comparative example 2
To mix 2 minutes in 73 parts of PP 1215C, 9 parts of PER, 9 parts of MEL and 9 part of APP high-speed mixers by weight
Afterwards, it is added in the main hopper of equidirectional parallel double-screw extruder, the melting mixing at a temperature of 190-220 DEG C, gained melt
Cooled down through tank after being extruded by Twin screw extruder, introducing pelleter carries out pelletizing operation, and gained pellet is the high-performance
Halogen-free flameproof PP compositions.
Comparative example 3
To mix 2 minutes in 76 parts of PP 1215C, 8 parts of PER, 8 parts of MEL and 8 part of APP high-speed mixers by weight
Afterwards, it is added in the main hopper of equidirectional parallel double-screw extruder, the melting mixing at a temperature of 190-220 DEG C, gained melt
Cooled down through tank after being extruded by Twin screw extruder, introducing pelleter carries out pelletizing operation, and gained pellet is the high-performance
Halogen-free flameproof PP compositions.
Comparative example 4
After mixing 2 minutes in 100 parts of PP Z30S high-speed mixers by weight, corotating twin-screw is added to
In the main hopper of extruder, the melting mixing at a temperature of 190-220 DEG C, gained melt by Twin screw extruder extrude after through water
Groove is cooled down, and introducing pelleter carries out pelletizing operation, and gained pellet is the PP compositions.
Measurement, comparative result are as shown in table 1：
The halogen-free flame-retardant polypropylene composition of table 1. matches (wt%) and its performance
As known from Table 1, the halogen-free flame-retardant polypropylene composition uses expansion type flame retardant, and charcoal is into triazine system derivative
Agent polypropylene is carried out it is flame-retardant modified, fire retardant addition amount it is few compared with by carbon forming agent of pentaerythrite, there is provided a kind of mechanical performance
It is good, flame retarding efficiency halogen-free flame-retardant polypropylene composition high.
Embodiment 6
2 points will be mixed in 90 parts of PP 1215C, 12 parts of CFA, 12 parts of MEL and 11 part of APP high-speed mixers by weight
Zhong Hou, is added in the main hopper of equidirectional parallel double-screw extruder, the melting mixing at a temperature of 190-220 DEG C, and gained melts
Body is cooled down after being extruded by Twin screw extruder through tank, and introducing pelleter carries out pelletizing operation, and gained pellet is the property high
Can halogen-free flameproof PP compositions.
Embodiment 7
To mix 2 minutes in 65 parts of PP 1215C, 5 parts of CFA, 5 parts of MEL and 5 part of APP high-speed mixers by weight
Afterwards, it is added in the main hopper of equidirectional parallel double-screw extruder, the melting mixing at a temperature of 190-220 DEG C, gained melt
Cooled down through tank after being extruded by Twin screw extruder, introducing pelleter carries out pelletizing operation, and gained pellet is the high-performance
Halogen-free flameproof PP compositions.
Embodiment 8
To mix 2 minutes in 70 parts of PP 1215C, 24 parts of CFA, 3 parts of MEL and 3 part of APP high-speed mixers by weight
Afterwards, it is added in the main hopper of equidirectional parallel double-screw extruder, the melting mixing at a temperature of 190-220 DEG C, gained melt
Cooled down through tank after being extruded by Twin screw extruder, introducing pelleter carries out pelletizing operation, and gained pellet is the high-performance
Halogen-free flameproof PP compositions.
Embodiment 9
To mix 2 minutes in 70 parts of PP 1215C, 3 parts of CFA, 24 parts of MEL and 3 part of APP high-speed mixers by weight
Afterwards, it is added in the main hopper of equidirectional parallel double-screw extruder, the melting mixing at a temperature of 190-220 DEG C, gained melt
Cooled down through tank after being extruded by Twin screw extruder, introducing pelleter carries out pelletizing operation, and gained pellet is the high-performance
Halogen-free flameproof PP compositions.
Embodiment 10
To mix 2 minutes in 70 parts of PP 1215C, 3 parts of CFA, 3 parts of MEL and 24 part of APP high-speed mixers by weight
Afterwards, it is added in the main hopper of equidirectional parallel double-screw extruder, the melting mixing at a temperature of 190-220 DEG C, gained melt
Cooled down through tank after being extruded by Twin screw extruder, introducing pelleter carries out pelletizing operation, and gained pellet is the high-performance
Halogen-free flameproof PP compositions.
Embodiment 11
By weight by 73 parts of PP 1215C, 9 parts of CFA, 9 parts of MEL and 9 part of APP, and 0.1 part of phosphorous acid three (2,4- bis-
Tert-butyl-phenyl) in ester high-speed mixer after mixing 2 minutes, it is added in the main hopper of equidirectional parallel double-screw extruder,
The melting mixing at a temperature of 190-220 DEG C, gained melt is cooled down after being extruded by Twin screw extruder through tank, introduces pelleter
Pelletizing operation is carried out, gained pellet is the high-performance halogen-free flame retardant PP compositions.
Embodiment 12
By weight by 73 parts of PP 1215C, 9 parts of CFA, 9 parts of MEL and 9 part of APP, and 0.5 part of thio-2 acid two (ten
Eight) after mixing 2 minutes in ester high-speed mixer, it is added in the main hopper of equidirectional parallel double-screw extruder, in 190-220
Melting mixing at a temperature of DEG C, gained melt is cooled down after being extruded by Twin screw extruder through tank, and introducing pelleter carries out pelletizing
Operation, gained pellet is the high-performance halogen-free flame retardant PP compositions.
The above-mentioned description to embodiment is to be understood that and use invention for ease of those skilled in the art.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel announcement of the invention, does not depart from improvement that scope made and modification all should be of the invention
Within protection domain.
Claims (7)
1. a kind of halogen-free flame-retardant polypropylene composition of the expanding fire retardant of system containing triazine, it is characterised in that including following weight portion
Several components：Polypropylene 65-90 parts, 15-35 parts of triazine system expanding fire retardant.
2. a kind of halogen-free flame-retardant polypropylene composition of expanding fire retardant of system containing triazine according to claim 1, its feature
It is that described polypropylene is the one kind in impact copolymer polypropylene or HOPP.
3. a kind of halogen-free flame-retardant polypropylene composition of expanding fire retardant of system containing triazine according to claim 1, its feature
Be that described triazine system expanding fire retardant is poly- 2- ethanol amido -4,6- ethylenediamines base -1,3,5-triazines, APP and
The mixture of melamine, wherein, the weight ratio of three is (10-80)：(10-80)：(10-80).
4. a kind of halogen-free flame-retardant polypropylene composition of expanding fire retardant of system containing triazine according to claim 1, its feature
It is also to include antioxidant 0.1-0.5 parts in described halogen-free flame-retardant polypropylene composition.
5. a kind of halogen-free flame-retardant polypropylene composition of expanding fire retardant of system containing triazine according to claim 4, its feature
It is that described antioxidant is the ground mixture of one or more in phenols, phosphorous acid esters, sulfur-bearing esters.
6. a kind of halogen-free flame-retardant polypropylene composition of expanding fire retardant of system containing triazine according to claim 5, its feature
It is that described phenolic antioxidant is four [methyl-β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol esters,
Described phosphorous acid esters are phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, and described sulfur-bearing esters are thio-2 acid two
(18) ester.
7. the preparation of the halogen-free flame-retardant polypropylene composition of the expanding fire retardant of system containing triazine as described in claim 1~6 is any
Method, it is characterised in that comprise the following steps：
Each raw material components are weighed by formula, is mixed, be then added in double screw extruder, melted at a temperature of 190-220 DEG C
Mixing, extrusion, granulation obtains the halogen-free flame-retardant polypropylene composition.
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| CN109401224A (en) * | 2018-10-08 | 2019-03-01 | 东莞市创之源新材料科技有限公司 | A kind of halogen-free expansion fire retardant and preparation method thereof |
| CN110041612A (en) * | 2019-04-01 | 2019-07-23 | 四川大学 | Oligomeric silsesquioxane increase-volume and synergistic halogen-free flame retardant polypropylene composite material and preparation method thereof |
| CN110128362A (en) * | 2019-05-24 | 2019-08-16 | 华北理工大学 | A kind of triazine series expansion type anti-flaming carbon forming agent and preparation method thereof and flame retardant composite material |
| CN110746692A (en) * | 2019-10-30 | 2020-02-04 | 南京聚隆科技股份有限公司 | Airport transfer tray material and preparation method thereof |
| CN113817263A (en) * | 2021-08-17 | 2021-12-21 | 金发科技股份有限公司 | Halogen-free flame-retardant polypropylene composition and preparation method and application thereof |
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| CN109401224A (en) * | 2018-10-08 | 2019-03-01 | 东莞市创之源新材料科技有限公司 | A kind of halogen-free expansion fire retardant and preparation method thereof |
| CN110041612A (en) * | 2019-04-01 | 2019-07-23 | 四川大学 | Oligomeric silsesquioxane increase-volume and synergistic halogen-free flame retardant polypropylene composite material and preparation method thereof |
| CN110041612B (en) * | 2019-04-01 | 2021-03-30 | 四川大学 | Halogen-free flame-retardant polypropylene composite material compatibilized by oligomeric silsesquioxane and synergistic effect and preparation method thereof |
| CN110128362A (en) * | 2019-05-24 | 2019-08-16 | 华北理工大学 | A kind of triazine series expansion type anti-flaming carbon forming agent and preparation method thereof and flame retardant composite material |
| CN110746692A (en) * | 2019-10-30 | 2020-02-04 | 南京聚隆科技股份有限公司 | Airport transfer tray material and preparation method thereof |
| CN113817263A (en) * | 2021-08-17 | 2021-12-21 | 金发科技股份有限公司 | Halogen-free flame-retardant polypropylene composition and preparation method and application thereof |
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