CN106751585A - A kind of flame retardant plastics using ionic liquid as fire retardant and preparation method thereof - Google Patents
A kind of flame retardant plastics using ionic liquid as fire retardant and preparation method thereof Download PDFInfo
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- CN106751585A CN106751585A CN201611235661.8A CN201611235661A CN106751585A CN 106751585 A CN106751585 A CN 106751585A CN 201611235661 A CN201611235661 A CN 201611235661A CN 106751585 A CN106751585 A CN 106751585A
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- Prior art keywords
- antioxidant
- flame retardant
- ring
- ionic liquid
- thermoplastic resin
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- 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
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
Abstract
The present invention provides a kind of thermoplastic resin composition, the flame retardant plastics that above-mentioned composition is prepared and preparation method thereof.Contain nitrogen, phosphorus (or boron), three kinds of inertia ignition-proof elements of fluorine (or chlorine) in the ionic liquid as shown in formula (I) simultaneously, combine the advantage of nitrogenated flame retardant, phosphorus flame retardant (or boron flame retardant) and halogen flame, phosphorus (or boron) content is suitable with phosphorus (or boron) content of existing phosphorus flame retardant (or boron flame retardant), is a kind of very efficient fire retardant.Meanwhile, the vapour pressure of the ionic liquid as shown in formula (I) is extremely low, will not be migrated to polymer surfaces substantially, it is to avoid precipitation problem.Also, the ionic liquid as shown in formula (I) is fabulous with the compatibility of polymer, has substantially no effect on the mechanical performance of matrix plastic.The flame retardant plastics discharges without halogen-containing gas in combustion, nontoxic, environmental protection.The fire-retardant rank of the flame retardant plastics prepared by above-mentioned composition can reach 0.4mm V0 grades.
Description
Technical field
The invention belongs to plastic applications, and in particular to a kind of flame retardant plastics and its preparation using ionic liquid as fire retardant
Method.
Background technology
Plastics are widely used in the industries such as building, indoor decoration, furniture, electric power, transport, electronic apparatus, but common plastics
Majority has inflammability, particularly terephthalate (PBT) engineering plastic, and PC, ABS, PPO and its alloy etc. are used to build, household electrical appliances, and electronic product is such as
During notebook computer etc., in the presence of having thermal source in use environment, there is the risk of burning, this application safety belt to its product
Many hidden danger.
In the prior art, people can add fire retardant in the preparation process of plastics, and fire retardant is divided into addition type and reaction
The major class of type two.Reactive flame retardant has reactivity, chemical bond can be synthesized on the strand of resin, to the performance of plastics
Influence it is smaller, but flame retardant effect is general, and easily smog is produced during burning, causes secondary hazards.And additive flame retardant is to adopt
Flame retardant treatment is carried out to material with the mode of outer addition fire retardant, its flame retarding efficiency is high, and technology maturation is cheap, but addition
The general halogen of fire retardant (such as chlorine, bromine) content it is higher, during burning, plastics are heated and discharge halogen flue gas, with toxicity, meeting
The health of harmful to human, or even cause personnel death；In addition, the addition of additive flame retardant is general all larger, easily influence
The performance of plastics, the influence to material post-production in itself is also larger, and fire retardant is easily separated out and can not for a long time keep anti-flammability,
Shorten service life.
It is fire-retardant that fire retardant can be divided into inorganic salts fire retardant, organic fire-retardant and organic and inorganic mixing by the difference of component
Three kinds of agent.The kind and consumption figure of domestic fire retardant the production of inorganic salts fire retardant and disappear still based on organic fire-retardant
The amount of expense is relatively fewer.Halogenated flame retardant is most commonly used that in organic fire-retardant, although this based flame retardant has other fire retardant systems
Unrivaled high efficiency is arranged, but its harm to environment and people is very important.Environmental issue is auxiliary agent exploitation and answers
Business's focus of attention is used, so adjusting the product structure of fire retardant always both at home and abroad, opening for Efficient environment-friendlyflame flame retardant is increased
Hair.Halogen (not having halogen-containing gas to discharge without halogen or during burning), low cigarette, low-poison and combustion-resisting agent are always the mesh that people pursue
Mark.The phosphorus flame retardant commonly used in recent years, such as BDP and RDP, although flame retarding efficiency is higher, but easily separate out, influence the later stage
Performance.
The content of the invention
In order to solve deficiency of the prior art, an object of the present invention is to provide a kind of combinations of thermoplastic resins
Thing, is using ionic liquid as fire retardant in the composition.
The second object of the present invention is to provide the flame retardant plastics that a kind of above-mentioned composition is prepared.
The third object of the present invention is to provide a kind of preparation method of above-mentioned flame retardant plastics.
The technical problems to be solved by the invention can be achieved through the following technical solutions：
A kind of thermoplastic resin composition, the composition includes the component of following mass fractions：Selected from ionic liquid
100 parts of 1~20 part of fire retardant, 0.1~2 part of composite antioxidant and thermoplastic resin,
Wherein, the ionic liquid is selected from one or more in the ionic liquid shown in formula (I) of mixture：
In ionic liquid shown in formula (I), cation is ring-type ammonium cationoid, in the ring of the ring-type ammonium cationoid
Hydrogen on nitrogen and/or carbon, at least one by C1-6Alkyl substitution；AnionSelected from BF4 -, PF6 -, Tf2N-, BCl4 -, PCl6 -
In one kind.
According to the present invention, the ring of the ring-type ammonium cationoid is five-membered ring, hexatomic ring, heptatomic ring or polynary condensed ring；It is excellent
Elect five-membered ring or hexatomic ring as.
Preferably, the ring of the ring-type ammonium cationoid includes 1~3 nitrogen and 3~6 carbon.It is further preferred that the ring-type
The ring of ammonium cationoid includes 1~2 nitrogen and 3~5 carbon.
It is more preferred still that cyclic amine in the ring-type ammonium cationoid is selected from imidazoles, and imidazoline, glyoxalidine, pyridine,
One kind in piperidines, and at least contain a C1-6The substitution base of alkyl.
According to the present invention, the anionPreferably PF6 -, Tf2N-Or PCl6 -。
Preferably, the anionIt is PF6 -。
Most preferably, the ionic liquid has the structure as shown in formula (II)：
According to the present invention, the thermoplastic resin is selected from polyolefin (such as polythene PE, polypropylene PP or its copolymer etc.),
Polyester (such as PBT, PET), makrolon (PC), acrylonitrile-butadiene-styrene copolymer (ABS), polystyrene (PS),
Polyphenylene oxide (PPE), one or more in polyamide (PA) of mixture or alloy.
According to the present invention, the primary antioxidant in the composite antioxidant is selected from aromatic amine antioxidant or phenolic antioxidant,
Auxiliary antioxidant is selected from phosphite ester or thioesters.Preferably, the phenolic antioxidant, such as antioxidant 1010 (four [β-(3,5- bis-
Tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester), antioxidant 1076 (β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid
Positive octadecanol ester), antioxidant 264 (2,6 di tert butyl 4 methyl phenol), one or more in vitamin E.It is preferred that
Ground, the aromatic amine antioxidant is selected from the one kind in the compounds such as diphenylamines, p-phenylenediamine and EEDQ or its polymer
Or it is various.Preferably, the phosphite ester is selected from irgasfos 168 (three [2.4- di-tert-butyl-phenyls] phosphite esters), trioctylphosphine
In phosphite ester, three decyl phosphite esters, three [12 carbon alkyl] phosphite esters and three [hexadecane base] phosphite esters one
Plant or various.Preferably, the thioesters is selected from thio-2 acid dibasic acid esters, such as selected from double Lauryl Alcohol esters of thio-2 acid, thio
One or more in the double ten four carbon alcohols esters of dipropionic acid or the double octadecanol esters of thio-2 acid.
It is further preferred that the primary antioxidant of the composite antioxidant is selected from phenolic antioxidant, auxiliary antioxidant is selected from phosphorous acid
The composite antioxidant of the composite antioxidant, antioxidant 1076 and irgasfos 168 of ester, for example, antioxidant 1010 and irgasfos 168.
According to the present invention, the composition can also include 0~70 part of glass fibre.
According to the present invention, the glass fibre can be any one glass fibre, e.g. chopped strand in the prior art,
Flat glass fiber etc..
According to the present invention, the composition includes the component of following mass fractions：Above-mentioned 100 parts of thermoplastic resin, on
40~60 parts of the glass fibre stated, above-mentioned 10~20 parts of the fire retardant selected from ionic liquid, above-mentioned composite antioxidant 0.1~
0.5 part.
Preferably, the composition includes the component of following mass fractions：It is above-mentioned 100 parts of thermoplastic resin, above-mentioned
50 parts of glass fibre, above-mentioned 17 parts of the fire retardant selected from ionic liquid, 0.17 part of above-mentioned composite antioxidant, wherein, it is described
Shown in ionic liquid such as formula (II)：
In the present invention, the ionic liquid of structure shown in formula (II) is a kind of ionic liquid of commercialization, referred to as 1- ethyls -3-
Methylimidazole hexafluorophosphoric acid ionic liquid (1-Ethyl-3-methylimidazolium hexafluorophosphate).
The present invention also provides a kind of flame retardant plastics prepared by above-mentioned composition.
According to the present invention, the fire-retardant rank of the flame retardant plastics can reach 0.4mm V0 grades.
The present invention also provides the preparation method of above-mentioned flame retardant plastics, and methods described comprises the following steps：
1) each component in composition is weighed by weight, and is well mixed, obtain mixed material；
2) by step 1) in the mixed material that obtains, carry out melt pelletization, prepare the flame retardant plastics.
According to the present invention, in step 1) in, described mixing can be sufficiently mixed in mixer.
According to the present invention, in step 2) in, described melt pelletization is specifically by step 1) in the mixture for preparing
Material, is added to double-screw extruding pelletizing unit and is melted, and the melt temperature is 150~300 DEG C (preferably 160~270
DEG C), carry out pelletizing through double-screw extruding pelletizing unit and be made single-size.
Beneficial effects of the present invention：
The present invention provides one or more flame retardant plastics as fire retardant in a kind of ionic liquid as shown in formula (I)
And preparation method thereof.Contain nitrogen, phosphorus (or boron), three kinds of inertia of fluorine (or chlorine) in the ionic liquid as shown in formula (I) simultaneously
Ignition-proof element, combines the advantage of nitrogenated flame retardant, phosphorus flame retardant (or boron flame retardant) and halogen flame, phosphorus (or boron)
Content is suitable with phosphorus (or boron) content of existing phosphorus flame retardant (or boron flame retardant), is a kind of very efficient fire-retardant
Agent.Meanwhile, the vapour pressure of the ionic liquid as shown in formula (I) is extremely low, will not be migrated to polymer surfaces substantially, it is to avoid separate out
Problem.Also, the ionic liquid as shown in formula (I) is fabulous with the compatibility of polymer, has substantially no effect on the machinery of matrix plastic
Performance.Flame retardant plastics containing the fire retardant discharges without halogen-containing gas in combustion, nontoxic, environmental protection.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.Furthermore, it is to be understood that after described content of the invention has been read, this area skill
Art personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within limited range of the present invention.
The flammable test of the flame retardant plastics that the present invention is prepared is according to Underwriter ' s Laboratory
Bulletin 94 is entitled《Plastics flammability test, UL94》Method carry out.
The composite antioxidant selected in following embodiments is the composite antioxidant of antioxidant 1010 and irgasfos 168, wherein,
The quality proportioning of the antioxidant 1010 and irgasfos 168 is 1:1；Or antioxidant 1076 and the compound of irgasfos 168 resist
Oxygen agent, wherein, the quality proportioning of the antioxidant 1076 and irgasfos 168 is 1:0.7.
Embodiment 1
1- ethyl-3-methylimidazole hexafluorophosphoric acid ionic liquids are used as fire retardant
Fraction weighs 17 parts of ionic liquid, 0.17 part of composite antioxidant, 100 parts of thermoplastic resin polyester (PBT) by weight,
It is together put into and be sufficiently mixed in mixer；Well mixed material is added into double-screw extruding pelletizing unit is carried out
Melting, the melt temperature is 260 DEG C, carries out pelletizing through double-screw extruding pelletizing unit and is made single-size.
Compared with the sample of comparative example 1 for being not added with ionic liquid, the flame retardant rating of the flame retardant plastics that embodiment 1 is prepared exists
Under 0.4mm, V0 grades is brought up to by HB grades.
Embodiment 2
1- ethyl-3-methylimidazole hexafluorophosphoric acid ionic liquids are used as fire retardant
Fraction weighs 17 parts of ionic liquid, 0.17 part of composite antioxidant, 100 parts of thermoplastic resin polyester (PBT) by weight,
17 parts of glass fibre, it is together put into and be sufficiently mixed in mixer；Well mixed material is added into twin-screw to squeeze
Go out to granulate unit and melted, the melt temperature is 260 DEG C, carries out pelletizing through double-screw extruding pelletizing unit and is made uniform
Grain.
Compared with the sample of comparative example 2 for being not added with ionic liquid, the flame retardant rating of the flame retardant plastics that embodiment 2 is prepared exists
Under 0.4mm, V0 grades is brought up to by V2 grades.
Comparative example 1
Fraction weighs 0.17 part of composite antioxidant, 100 parts of thermoplastic resin polyester (PBT) by weight, and it is together put into
It is sufficiently mixed in mixer；Well mixed material is added into double-screw extruding pelletizing unit to be melted, it is described molten
Melt temperature for 260 DEG C, carry out pelletizing through double-screw extruding pelletizing unit and be made single-size.
Under 0.4mm, fire-retardant rank is HB grades to the flame retardant rating of the flame retardant plastics that comparative example 1 is prepared.
Comparative example 2
Fraction by weight weighs 0.17 part of composite antioxidant, 100 parts of thermoplastic resin polyester (PBT), 17 parts of glass fibre,
It is together put into and be sufficiently mixed in mixer；Well mixed material is added into double-screw extruding pelletizing unit is carried out
Melting, the melt temperature is 260 DEG C, carries out pelletizing through double-screw extruding pelletizing unit and is made single-size.
Under 0.4mm, fire-retardant rank is V2 grades to the flame retardant rating of the flame retardant plastics that comparative example 2 is prepared.
More than, embodiments of the present invention are illustrated.But, the present invention is not limited to above-mentioned implementation method.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of thermoplastic resin composition, it is characterised in that the composition includes the component of following mass fractions：Selected from from
100 parts of 1~20 part of the fire retardant of sub- liquid, 0.1~2 part of composite antioxidant and thermoplastic resin,
Wherein, the ionic liquid is selected from one or more in the ionic liquid shown in formula (I) of mixture：
In ionic liquid shown in formula (I), cation is ring-type ammonium cationoid, the nuclear nitrogen of the ring-type ammonium cationoid
And/or the hydrogen on carbon, at least one by C1-6Alkyl substitution；AnionSelected from BF4 -, PF6 -, Tf2N-, BCl4 -, PCl6 -In
One kind.
2. thermoplastic resin composition according to claim 1, it is characterised in that the ring of the ring-type ammonium cationoid is
Five-membered ring, hexatomic ring, heptatomic ring or polynary condensed ring；Preferably five-membered ring or hexatomic ring.
Preferably, the ring of the ring-type ammonium cationoid includes 1~3 nitrogen and 3~6 carbon.
Preferably, the ring of the ring-type ammonium cationoid includes 1~2 nitrogen and 3~5 carbon.
3. thermoplastic resin composition according to claim 1 and 2, it is characterised in that in the ring-type ammonium cationoid
Cyclic amine be selected from imidazoles, imidazoline, glyoxalidine, pyridine, the one kind in piperidines, and at least contain a C1-6Alkyl takes
Dai Ji.
4. the thermoplastic resin composition according to any one of claim 1-3 claim, it is characterised in that described the moon
IonIt is PF6 -, Tf2N-Or PCl6 -。
Preferably, the anionIt is PF6 -。
5. the thermoplastic resin composition according to any one of claim 1-4 claim, it is characterised in that it is described from
Sub- liquid has the structure as shown in formula (II)：
6. the thermoplastic resin composition according to any one of claim 1-5 claim, it is characterised in that the heat
Plastic resin is selected from polyolefin (such as polythene PE, polypropylene PP or its copolymer etc.), polyester (such as PBT, PET), poly- carbonic acid
Ester (PC), acrylonitrile-butadiene-styrene copolymer (ABS), polystyrene (PS), polyphenylene oxide (PPE), in polyamide (PA)
One or more of mixture or alloy.
Preferably, the primary antioxidant in the composite antioxidant is selected from aromatic amine antioxidant or phenolic antioxidant, aids in antioxygen
Agent is selected from phosphite ester or thioesters.Preferably, the phenolic antioxidant, such as antioxidant 1010 (four [β-(3,5- di-t-butyl -4-
Hydroxy phenyl) propionic acid] pentaerythritol ester), antioxidant 1076 (β-positive 18 carbon of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid
Alcohol ester), antioxidant 264 (2,6 di tert butyl 4 methyl phenol), one or more in vitamin E.Preferably, the virtue
Fragrant amine antioxidants are selected from one or more in the compounds such as diphenylamines, p-phenylenediamine and EEDQ or its polymer.It is excellent
Selection of land, the phosphite ester be selected from irgasfos 168 (three [2.4- di-tert-butyl-phenyls] phosphite esters), trioctylphosphite,
One or more in three decyl phosphite esters, three [12 carbon alkyl] phosphite esters and three [hexadecane base] phosphite esters.
Preferably, the thioesters is selected from thio-2 acid dibasic acid esters, such as selected from the double Lauryl Alcohol esters of thio-2 acid, thio-2 acid double ten
One or more in four carbon alcohols ester or the double octadecanol esters of thio-2 acid.
Preferably, the primary antioxidant of the composite antioxidant is selected from phenolic antioxidant, auxiliary antioxidant and is selected from phosphite ester, for example
It is the composite antioxidant of the composite antioxidant, antioxidant 1076 and irgasfos 168 of antioxidant 1010 and irgasfos 168.
Preferably, the composition can also include 0~70 part of glass fibre.
Preferably, the glass fibre can be any one glass fibre, e.g. chopped strand, flat glass in the prior art
Deng.
7. the thermoplastic resin composition according to any one of claim 1-6 claim, it is characterised in that described group
Compound includes the component of following mass fractions：Above-mentioned 100 parts of thermoplastic resin, 40~60 parts above-mentioned of glass fibre, it is above-mentioned
10~20 parts of the fire retardant selected from ionic liquid, 0.1~0.5 part of above-mentioned composite antioxidant.
Preferably, the composition includes the component of following mass fractions：Above-mentioned 100 parts of thermoplastic resin, above-mentioned glass
50 parts of fiber, above-mentioned 17 parts of the fire retardant selected from ionic liquid, 0.17 part of above-mentioned composite antioxidant, wherein, the ion
Shown in liquid such as formula (II)：
8. the flame retardant plastics that the composition described in any one of claim 1-7 claims is prepared.
Preferably, the fire-retardant rank of the flame retardant plastics can reach 0.4mm V0 grades.
9. the preparation method of the flame retardant plastics described in claim 8, it is characterised in that methods described comprises the following steps：
1) each component in composition is weighed by weight, and is well mixed, obtain mixed material；
2) by step 1) in the mixed material that obtains, carry out melt pelletization, prepare the flame retardant plastics.
10. preparation method according to claim 9, it is characterised in that in step 1) in, described mixing can be in mixing
It is sufficiently mixed in machine.
Preferably, in step 2) in, described melt pelletization is specifically by step 1) in the mixed material for preparing, be added to
Double-screw extruding pelletizing unit is melted, and the melt temperature is 150~300 DEG C (preferably 160~270 DEG C), through double spiral shells
Bar extruding pelletization unit carries out pelletizing and is made single-size.
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| CN201611235661.8A CN106751585A (en) | 2016-12-28 | 2016-12-28 | A kind of flame retardant plastics using ionic liquid as fire retardant and preparation method thereof |
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| CN201611235661.8A CN106751585A (en) | 2016-12-28 | 2016-12-28 | A kind of flame retardant plastics using ionic liquid as fire retardant and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108517577A (en) * | 2018-04-20 | 2018-09-11 | 绍兴市汉诺纺织科技有限公司 | A kind of antibacterial flame-retardant acrylic fiber and its antibacterial flame-retardant acrylic fabric of preparation |
| CN109054306A (en) * | 2018-07-17 | 2018-12-21 | 安徽长淮新材料有限公司 | A kind of flame-retardant and anti-static polyester material and preparation method thereof |
| CN110358276A (en) * | 2018-04-11 | 2019-10-22 | 南通诺为新材料科技有限公司 | A kind of transparent flame-retardant polycarbonate, fire retardant and application |
| CN110387117A (en) * | 2018-04-16 | 2019-10-29 | 南通诺为新材料科技有限公司 | A kind of high fluidity polycarbonate, flowable and application |
| CN110387116A (en) * | 2018-04-16 | 2019-10-29 | 南通诺为新材料科技有限公司 | High-performance refractory polycarbonate alloy, fire retardant, expanding material and application |
| CN111040245A (en) * | 2019-12-18 | 2020-04-21 | 江苏集萃先进高分子材料研究所有限公司 | Pyropolyphosphoric acid imidazole flame retardant and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110358276A (en) * | 2018-04-11 | 2019-10-22 | 南通诺为新材料科技有限公司 | A kind of transparent flame-retardant polycarbonate, fire retardant and application |
| CN110387117A (en) * | 2018-04-16 | 2019-10-29 | 南通诺为新材料科技有限公司 | A kind of high fluidity polycarbonate, flowable and application |
| CN110387116A (en) * | 2018-04-16 | 2019-10-29 | 南通诺为新材料科技有限公司 | High-performance refractory polycarbonate alloy, fire retardant, expanding material and application |
| CN108517577A (en) * | 2018-04-20 | 2018-09-11 | 绍兴市汉诺纺织科技有限公司 | A kind of antibacterial flame-retardant acrylic fiber and its antibacterial flame-retardant acrylic fabric of preparation |
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| CN109054306A (en) * | 2018-07-17 | 2018-12-21 | 安徽长淮新材料有限公司 | A kind of flame-retardant and anti-static polyester material and preparation method thereof |
| CN111040245A (en) * | 2019-12-18 | 2020-04-21 | 江苏集萃先进高分子材料研究所有限公司 | Pyropolyphosphoric acid imidazole flame retardant and preparation method thereof |
| CN111040245B (en) * | 2019-12-18 | 2022-05-31 | 江苏集萃先进高分子材料研究所有限公司 | Pyropolyphosphoric acid imidazole flame retardant and preparation method thereof |
| CN115011113A (en) * | 2019-12-18 | 2022-09-06 | 江苏集萃先进高分子材料研究所有限公司 | Flame-retardant material and preparation method thereof |
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