CN102250383A - Halogen-free fire retardant containing benzoxazine and polymer material comprising same - Google Patents
Halogen-free fire retardant containing benzoxazine and polymer material comprising same Download PDFInfo
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- CN102250383A CN102250383A CN 201110176175 CN201110176175A CN102250383A CN 102250383 A CN102250383 A CN 102250383A CN 201110176175 CN201110176175 CN 201110176175 CN 201110176175 A CN201110176175 A CN 201110176175A CN 102250383 A CN102250383 A CN 102250383A
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- flame retardants
- free flame
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- red phosphorus
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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
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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
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/357—Six-membered rings
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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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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a halogen-free fire retardant containing benzoxazine and polymer material comprising same. A small quantity of metallic oxide or hydroxide can be simultaneously added to serve as a fire-retardant synergy agent. Phosphorus oxide, phosphoric acid, metaphosphoric acid, polyphosphoric acid and the like generated by burning red phosphorus is dewatered through reacting with a great quantity of phenolic hydroxyl generated by solidifying benzoxazine resin to produce an inorganic-organic hybridized barrier layer, the barrier layer has good wettability to a matrix polymer, and barrier property is improved. Meanwhile, an organic part has an adsorption function on organic smoke gas so as to greatly improve fire-retardant efficiency. A small quantity of metallic oxide or hydroxide can enhance the stability of the barrier layer to further improve fire-retardant effect. The composite is applied to polymers, polymer based composites and products of the polymers and the polymer based composites, and fire-retardant effect is good. The halogen-free fire retardant disclosed by the invention has the characteristics of low cost, wide application range and good fire-retardant property.
Description
Technical field
The present invention relates to a kind of polymer materials that is used for the fire-retardant halogen-free flame retardants of polymkeric substance and contains this halogen-free flame retardants.
Background technology
A large amount of polymer materials great majority that use very easily burn in our daily life.Such as the ABS limiting oxygen index(LOI) is 18.3-20, and the limiting oxygen index(LOI) of high-impact polystyrene (HIPS) is 18, belongs to very easily combustible material, and the polyolefins material is inflammable in air equally.In actual applications, it is fire-retardant to it all to need to add fire retardant.
Mainly adopt traditional halogenated flame retardant at present on the domestic market, wherein the flame retardant effect of brominated organic compound is best.Though the good flame retardation effect of halogenated flame retardant produces more cigarette, obnoxious flavour and corrosive gases when burning, work the mischief for environment and human body.Therefore, the exploitation of bittern-free flame-proof material is the research and development focus in this field.A kind of Halogen isolation-type with acid source, carbon source and source of the gas element formation is fire-retardant, and to specific polymkeric substance good flame retardation effect, its representative is ammonium polyphosphate, tetramethylolmethane and Melamine.This system is bigger than normal because of addition, and water tolerance problem difference and the few difficult large-scale popularization of the polymkeric substance that is suitable for are used.Though the modified phosphate based on this is good with the matrix polymer consistency, flame retardant resistance is better, the cost height, and addition is big.Wherein the halogen-free flameproof goods with PC and the preparation of ABS blend interpolation phosphoric acid ester fire retardant have good commercial to use.Publication number is that a kind of halogen-free phosphorus-free inflaming retarding PC/ABS alloy material of CN101089045A and a kind of halogen-free flame retardant PC/ABS Alloy And Preparation Method that publication number is CN101418118B all are the representatives of this respect.
Red phosphorus combustion inhibitor is owing to the phosphorus content height, and good flame retardation effect is the principal item of present halogen-free flameproof.Publication number is that CN101200576A has announced a kind of polybutylene terephthalate moulding compound that contains red phosphorus combustion inhibitor, and CN101235174A has announced a kind of environmental protection halogen-free anti-flaming polypropylene composite material.These two patents are composite fire-retardant to polymkeric substance with red phosphorus combustion inhibitor and inorganic combustion inhibitor, and the inorganic combustion inhibitor addition is big, are unfavorable for processing.
The efficient flame-retarding agent that uses on electronic product at present is a phosphinates.The composition of a kind of halogen-free and flame-retardant polycarbonate of United States Patent (USP) 7608654 reports is based on phosphinates; United States Patent (USP) 7,803,856 disclose a kind of Flameproof polyamide, and it is made up of phosphonate, nitrogenous compound and untreated nanoclay.Phosphinates is owing to have organic and inorganic part simultaneously in a molecule, have extensively, flame retardant effect efficiently.Yet its production cost height.
This area lacks low, the easy processing of a kind of cost, good flame resistance, the halogen-free flame-retardant system that suitability is wide.
Summary of the invention
The objective of the invention is to overcome the prior art defective, a kind of applied widely, low-cost, halogen-free flame retardants and contain the polymer materials of this halogen-free flame retardants efficiently is provided.
The object of the invention is achieved through the following technical solutions:
The halogen-free flame retardants that contains benzoxazine and red phosphorus is made up of benzoxazine colophony, red phosphorus and metal oxide or metal hydroxides;
Wherein the weight ratio of benzoxazine colophony and red phosphorus is 0.25 ~ 4; Preferred 0.5 ~ 2.
Metal oxide or metal hydroxides account for 0 ~ 10% weight percentage of benzoxazine colophony and red phosphorus gross weight.
Described benzoxazine colophony Shi mono-oxazines ring benzoxazine colophony, its structural formula is:
R wherein
1Be H, alkyl or aryl; R
2Be alkyl or aryl.
Preferred R
1Be H, or the tertiary butyl; R
2Be the phenyl or the tertiary butyl.
Preferred again R
1Be H; R
2Be phenyl.
Being more preferably described mono-oxazines ring benzoxazine colophony is phenol type benzoxazine, and its structural formula is as follows:
The all right Shi bisoxazines ring benzoxazine colophony of described benzoxazine colophony, its structural formula is:
Described benzoxazine colophony can also be bisphenol type bisoxazines ring benzoxazine colophony or diamines Xing bisoxazines ring benzoxazine colophony; The bisphenol type structural formula is as follows:
R wherein
1Be alkyl or aryl; R
2Be alkyl or aryl;
Diamines type structural formula is as follows:
R wherein
1Be alkyl or aryl; R
2Be H, alkyl or aryl.
Preferred bisphenol type bisoxazines ring benzoxazine colophony, structural formula is:
R wherein
1Be CH
2, C (CH
3)
2Or negative phenyl (be Resorcinol Xing bisoxazines ring benzoxazine colophony this moment); R
2Be phenyl, tert-butyl-phenyl or other aryl and C
4～C
18The straight or branched alkyl.
Being more preferably described bisphenol type bisoxazines ring benzoxazine colophony is the bisphenol A-type benzoxazine colophony, and its structural formula is as follows:
?。
Described red phosphorus is pure red phosphorus or micro encapsulation red phosphorus.Described micro encapsulation red phosphorus is to coat one deck Melamine formaldehyde resin on the red phosphorus surface to have realized the red phosphorus microcapsule processing.
Described metal hydroxides is aluminium hydroxide or magnesium hydroxide; Metal oxide is magnesium oxide or zinc oxide.
The polymer materials that contains described halogen-free flame retardants comprises described halogen-free flame retardants and polymkeric substance; Described polymkeric substance is selected from styrenic polymer, contains the phenyl ring polymkeric substance, polyolefin polymers or their blends; Wherein the consumption of halogen-free flame retardants is 5 ~ 25%wt of polymer weight.
The polymer materials that contains described halogen-free flame retardants can also comprise one or more in toughner, compatilizer, oxidation inhibitor, lubricant, stablizer, static inhibitor, pigment, filler or the strongthener.
Styrenic polymer is selected from Acrylonitrile-butadiene-styrene Copolymer (ABS), polystyrene (PS), high-impact polystyrene (HIPS), vinylbenzene-acrylonitrile copolymer, vinyl cyanide-vinylbenzene-terpolymer EP rubber multipolymer (AES), vinyl cyanide-vinylbenzene-acrylic copolymer (ASA), methyl methacrylate-divinyl-styrol copolymer (MBS), methyl methacrylate-acrylate-styrol copolymer (MAS), vinylbenzene-divinyl-styrene block copolymer (SBS) or vinylbenzene-isoprene-styrene block copolymer (SIS).
Contain the phenyl ring polymkeric substance and be selected from ethylene glycol terephthalate (PET), mutual-phenenyl two acid bromide two alcohol ester (PBT) or polycarbonate (PC).
Several application of fire retardant the best of the present invention:
ABS, HIPS, PC/ABS polymer materials and goods with BPOZ or BOZ and red phosphorus composite flame-proof.
SBS, SIS elastomer material and goods with BPOZ or BOZ and red phosphorus composite flame-proof.
With polymer materials and goods such as PET, the PBT of BPOZ or BOZ and red phosphorus composite flame-proof, nylon.
To contain C
4~ C
18The PP that the benzoxazine colophony of long carbon-chain structure is fire-retardant, polyolefine material and goods such as PE.
Described benzoxazine colophony can be single phenol or amine synthetic, also can be their resin that reacts to each other or resin compound, with the consistency of coupling with matrix resin.
Bisphenol A-type benzoxazine (BPOZ) can prepare according to the preparation method among the ZL 200710032522.X.Press 1:2:4 mol ratio synthetic by dihydroxyphenyl propane, aniline, Paraformaldehyde 96.
Phenol type benzoxazine (BOZ) can be pressed 1:1:2 mol ratio synthetic by phenol, aniline, Paraformaldehyde 96
Described benzoxazine colophony (is example with benzene phenol type oxazine resin) partly solidified reaching in the course of processing forms phenolic hydroxyl group when meeting fire burns.Reaction formula is as follows:
The phosphorus oxide that described red phosphorus generates when burning, phosphoric acid, metaphosphoric acid, polyphosphoric acid etc. generate the inorganic-organic hybridization thing with the reaction of part phenolic hydroxyl group:
React in the combustion processes of being heated by benzoxazine and red phosphorus and to generate the inorganic-organic hybridization thing, because of good with the organic matrix consistency, can intact wetting covering matrix surface, barriering effect is good.In addition, can also adsorb and catch the flue dust that burning forms, make its part that becomes barrier layer, make the flame retarding efficiency multiplication.
Described halogen-free flame retardants at styrenic polymer, contain the application in phenyl ring polymkeric substance or polyolefin polymers and their blends fire-retardant.
The present invention is with respect to advantage and beneficial effect that prior art had.
(1) halogen-free flame-retardant system based on benzoxazine and red phosphorus of technical solution of the present invention proposition has been given full play to the synergy between benzoxazine and the red phosphorus, and the flame retardant resistance of adding red phosphorus more separately has significantly raising.
(2) can select the specific benzoxazine colophony good with the matrix consistency for use at fire-retardant matrix simultaneously, it is wide to have usability, the characteristics of good flame resistance.
(3) react in the combustion processes of being heated by benzoxazine and red phosphorus and generate the inorganic-organic hybridization thing, because of good with the organic matrix consistency, can intact wetting covering matrix surface, barriering effect is good.In addition, can also adsorb and catch the flue dust that burning forms, make its part that becomes barrier layer, make the flame retarding efficiency multiplication.
Embodiment
Following embodiment is a detailed description of the present invention, but the present invention not only is confined to these embodiment.
Embodiment 1-8:
The preparation technology of reference examples 1-2 and embodiment 1-8: with a certain amount of ABS or HIPS after plasticizing in two roller mills of 170 ~ 180 ℃, successively add raw materials such as oxidation inhibitor (mass ratio is the antioxidant 1076 and 168 of 1:1), benzoxazine colophony, microcapsule red phosphorus by prescription (seeing Table 1), mixing evenly after, be positioned in the mould after the discharging, hot pressing is 10 minutes on 180 ℃ vulcanizing press, room temperature was colded pressing 10 minutes then, and depanning makes sheet material then, is used for performance test.Testing standard sees Table 6.
Every physicals based on the halogen-free flame retardant ABS of benzoxazine among reference examples and the embodiment is as shown in table 2, and testing standard sees Table 6.Tensile strength of material, shock strength, fire-retardant combustion performance that 9 parts of bisphenol A-type benzoxazines of embodiment 1 usefulness substitute 9 parts of micro encapsulation red phosphorus preparations all are improved.Embodiment 2 and 3 further increases the amounts of benzoxazines and micro encapsulation red phosphorus, and the flame retardant resistance of material further gets a promotion, add paracril simultaneously after, the shock strength of gained material improves.
Table 1 flame-proof ABS and HIPS blend prescription/(weight part)
| ? | Reference examples 1 | Reference examples 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| ABS | 100 | 85 | 84.7 | 78 | 69 | 76 | 76 | 76 | — |
| HIPS | — | — | — | — | — | — | — | — | 74 |
| The bisphenol A-type benzoxazine | — | — | 9 | 11 | 15 | 10 | 8 | — | 12 |
| Phenol type benzoxazine | — | — | — | — | — | — | — | 10 | — |
| Micro encapsulation red phosphorus | — | 15 | 6 | 7 | 10 | 10 | 12 | 10 | 8 |
| Aluminium hydroxide | — | — | 0.6 | — | — | — | — | — | — |
| Paracril | — | — | — | 4 | 6 | 4 | 4 | 4 | 6 |
| Oxidation inhibitor | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
Table 2 flame-proof ABS and HIPS physicals
Embodiment 9 ~ 10
After each component (seen Table 3) in proportion and mix, add in the twin screw extruder and melt extrude 200 ~ 250 ℃ of extrusion temperatures.To the material granulation and the aftertreatment of extruding, injection moulding gets test bars then.It is antioxidant 1076 and 168 composite antioxidants of 1:1 that antioxidant is selected mass ratio for use.Table 3 fire retardation PC/ABS alloy formula/(weight part)
Every physicals based on the halogen-free flame retardant PC/ABS alloy of benzoxazine among reference examples and the embodiment is shown in Table 4, and testing standard sees Table 6.
Table 4 fire retardation PC/ABS alloy physics performance
| Project | Reference examples | Embodiment 9 | Embodiment 10 |
| Tensile strength (MPa) | 52 | 46 | 42 |
| Notched Izod impact strength (KJm -2） | 42 | 38 | 32 |
| Flame retardant resistance (1.6mm) | Burning | V-1 | V-0 |
Embodiment 11
Join temperature after 10 parts of BPOZ and 10 parts of red phosphorus powder and 0.2 part of magnesium hydroxide mixed and be set at extruding pelletization in 120 ℃ the twin screw extruder, obtain containing the halogen-free flame retardants A of benzoxazine and red phosphorus.
10 parts of ABS are mixed back extruding pelletization on 200 ℃ of twin screw extruders with 1.8 parts of above-mentioned benzoxazines that contain with the halogen-free flame retardants A of red phosphorus, then with the flame-proof ABS of gained on injection moulding machine in 220 ℃ of injection moulding sample preparations.The gained properties of sample sees Table 5
Table 5 embodiment 11 properties of sample
| Project | Embodiment 11 |
| Tensile strength (MPa) | 35 |
| Notched Izod impact strength (KJm -2） | 6.3 |
| Flame retardant resistance (1.6mm) | V-0 |
Embodiment 12
With 30 parts of BPOZ, 0.6 part of mixing of 30 parts in particulate state red phosphorus and aluminium hydroxide is positioned in the high speed disintegrator, and inflated with nitrogen protection grinds down and mixes to such an extent that contain the halogen-free flame retardants B of benzoxazine and red phosphorus.
It is in 50% the tackiness agent with the allotment of SBS/ terpine resin that 10 parts of the halogen-free flame retardants B that will contain benzoxazine and red phosphorus join 80 parts of solid contents, be coated on the acetate fibre cloth after stirring, about 200 microns of gluing thickness, preparation halogen-free flameproof Pressuresensitive Tape.The flame retardant properties of this adhesive tape reaches UL 94 V-0 levels.
Embodiment 13
With 7.9 parts of ABS plastic, 1.0 parts of phenol type benzoxazine colophonies, 1.0 parts of microcapsule red phosphorus, 0.6 part of acrylonitrile-butadiene rubber powder, 0.2 part in oxidation inhibitor, the black Masterbatch mixes in high-speed mixer for 0.1 part, then this mixture is joined temperature and be controlled at extruding pelletization in 210 ~ 230 ℃ the twin screw extruder, obtain black flame-retardant ABS pellet C.
ABS pellet C in 80 ℃ of oven dry, is joined temperature and is in 230 ℃ the injection moulding machine, be injected in the remote control switch of electrical appliance box mould, obtain the remote control switch of electrical appliance box D of halogen-free flameproof.
This switch capsule is hung in the vertical-horizontal burning tester, the ignition test, these goods from putting out, reach UL 94 V-0 levels from fire.
Table 6 testing standard
| Project | Testing standard |
| Tensile strength | GB/T1040-2006 |
| Notched Izod impact strength | GB/T1843-1996 |
| Flame retardant resistance | UL-94 |
Claims (10)
1. contain the halogen-free flame retardants of benzoxazine, it is characterized in that, form by benzoxazine colophony, red phosphorus and metal oxide or metal hydroxides;
Wherein the weight ratio of benzoxazine colophony and red phosphorus is 0.25 ~ 4;
Metal oxide or metal hydroxides account for 0 ~ 10% weight percentage of benzoxazine colophony and red phosphorus gross weight.
2. halogen-free flame retardants according to claim 1 is characterized in that, described benzoxazine colophony Shi mono-oxazines ring benzoxazine colophony, and its structural formula is:
R wherein
1Be H, alkyl or aryl; R
2Be alkyl or aryl.
3. halogen-free flame retardants according to claim 2 is characterized in that, described mono-oxazines ring benzoxazine colophony is a phenol type benzoxazine, and its structural formula is as follows:
4. halogen-free flame retardants according to claim 1 is characterized in that, described benzoxazine colophony is bisphenol type bisoxazines ring benzoxazine colophony or diamines Xing bisoxazines ring benzoxazine colophony; The bisphenol type structural formula is as follows:
R wherein
1Be alkyl or aryl; R
2Be alkyl or aryl;
Diamines type structural formula is as follows:
R wherein
1Be alkyl or aryl; R
2Be H, alkyl or aryl.
5. halogen-free flame retardants according to claim 4 is characterized in that, described bisphenol type bisoxazines ring benzoxazine colophony is the bisphenol A-type benzoxazine colophony, and its structural formula is as follows:
6. according to the described halogen-free flame retardants of one of claim 1-5, it is characterized in that described red phosphorus is pure red phosphorus or micro encapsulation red phosphorus.
7. halogen-free flame retardants according to claim 6 is characterized in that, described metal hydroxides is aluminium hydroxide or magnesium hydroxide; Metal oxide is magnesium oxide or zinc oxide.
8. contain the polymer materials and the goods of the described halogen-free flame retardants of claim 1, it is characterized in that, comprise described halogen-free flame retardants of claim 1 and polymkeric substance; Described polymkeric substance is selected from styrenic polymer, contains the phenyl ring polymkeric substance, polyolefin polymers or their blends; Wherein the consumption of halogen-free flame retardants is 5 ~ 25%wt of polymer weight.
9. polymer materials according to claim 8 is characterized in that, also comprises in toughner, compatilizer, oxidation inhibitor, lubricant, stablizer, static inhibitor, pigment, filler or the strongthener one or more.
The described halogen-free flame retardants of claim 1 at styrenic polymer, contain the application in phenyl ring polymkeric substance or polyolefin polymers and their blends fire-retardant.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110176175 CN102250383B (en) | 2011-06-28 | 2011-06-28 | Halogen-free fire retardant containing benzoxazine and polymer material comprising same |
| PCT/CN2011/078955 WO2013000198A1 (en) | 2011-06-28 | 2011-08-25 | Halogen-free flame retardant containing benzoxazine, and polymer material containing halogen-free flame retardant |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110176175 CN102250383B (en) | 2011-06-28 | 2011-06-28 | Halogen-free fire retardant containing benzoxazine and polymer material comprising same |
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|---|---|
| CN102250383A true CN102250383A (en) | 2011-11-23 |
| CN102250383B CN102250383B (en) | 2013-02-13 |
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|---|---|---|---|
| CN 201110176175 Expired - Fee Related CN102250383B (en) | 2011-06-28 | 2011-06-28 | Halogen-free fire retardant containing benzoxazine and polymer material comprising same |
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| WO (1) | WO2013000198A1 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504475A (en) * | 2011-11-30 | 2012-06-20 | 华南理工大学 | Halogen-free flame retardant containing linear phenolic aldehyde and polymer material containing halogen-free flame retardant |
| CN103834169A (en) * | 2014-03-21 | 2014-06-04 | 厦门大学 | Flame-retardant benzoxazine resin and preparation method thereof |
| CN105001452A (en) * | 2015-07-13 | 2015-10-28 | 中科院广州化学有限公司南雄材料生产基地 | Phosphorus-nitrogen halogen-free flame retardant and preparation method and application thereof |
| CN105504639A (en) * | 2013-07-30 | 2016-04-20 | 江苏理工学院 | Preparation method for halogen-free flame-retardant high-impact polystyrene |
| CN109942894A (en) * | 2019-02-23 | 2019-06-28 | 河南大学 | A kind of the halogen-free expanded flame-retardant system and its fire-retardant thermoplastic resin of the carbon forming agent containing benzoxazine |
| CN111531983A (en) * | 2020-05-20 | 2020-08-14 | 山东金宝电子股份有限公司 | High-heat-resistance low-dielectric copper-clad plate and preparation method thereof |
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| CN115160664A (en) * | 2022-07-05 | 2022-10-11 | 沈阳化工大学 | Method for preparing reinforced nitrile rubber from low-viscosity benzoxazine |
| CN115613358A (en) * | 2022-10-31 | 2023-01-17 | 中国科学院宁波材料技术与工程研究所 | Compound plant fiber flame-retardant modifier and application thereof |
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| CN102504475A (en) * | 2011-11-30 | 2012-06-20 | 华南理工大学 | Halogen-free flame retardant containing linear phenolic aldehyde and polymer material containing halogen-free flame retardant |
| CN105504639A (en) * | 2013-07-30 | 2016-04-20 | 江苏理工学院 | Preparation method for halogen-free flame-retardant high-impact polystyrene |
| CN103834169A (en) * | 2014-03-21 | 2014-06-04 | 厦门大学 | Flame-retardant benzoxazine resin and preparation method thereof |
| CN105001452A (en) * | 2015-07-13 | 2015-10-28 | 中科院广州化学有限公司南雄材料生产基地 | Phosphorus-nitrogen halogen-free flame retardant and preparation method and application thereof |
| CN105001452B (en) * | 2015-07-13 | 2017-12-26 | 中科院广州化学有限公司南雄材料生产基地 | A kind of phosphorus nitrogen halogen-free flame retardants and preparation method and application |
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| CN111531983B (en) * | 2020-05-20 | 2022-03-04 | 山东金宝电子股份有限公司 | High-heat-resistance low-dielectric copper-clad plate and preparation method thereof |
| CN112876820A (en) * | 2021-01-19 | 2021-06-01 | 浙江理工大学 | Polyethylene terephthalate composite material |
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| CN115160664B (en) * | 2022-07-05 | 2023-06-02 | 沈阳化工大学 | Method for preparing reinforced nitrile rubber from low-viscosity benzoxazine |
| CN115613358A (en) * | 2022-10-31 | 2023-01-17 | 中国科学院宁波材料技术与工程研究所 | Compound plant fiber flame-retardant modifier and application thereof |
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| CN102250383B (en) | 2013-02-13 |
| WO2013000198A1 (en) | 2013-01-03 |
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