CN102250383B - 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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- CN102250383B CN102250383B CN 201110176175 CN201110176175A CN102250383B CN 102250383 B CN102250383 B CN 102250383B CN 201110176175 CN201110176175 CN 201110176175 CN 201110176175 A CN201110176175 A CN 201110176175A CN 102250383 B CN102250383 B CN 102250383B
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- Prior art keywords
- halogen
- benzoxazine colophony
- ring
- flame retardants
- free flame
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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
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 fire-retardant halogen-free flame retardants for polymkeric substance and contain the polymer materials of this halogen-free flame retardants.
Background technology
A large amount of polymer materials great majority that use very easily burn in our daily life.Be 18.3-20 such as the ABS limiting oxygen index(LOI), 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, all need to add fire retardant fire-retardant to it.
The traditional halogenated flame retardant of main employing on the domestic market, wherein the flame retardant effect of brominated organic compound is best.Although 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 effective to specific flame retardance of polymer, its representative is ammonium polyphosphate, tetramethylolmethane and Melamine.This system is bigger than normal because of addition, and the poor and applicable few difficult large-scale popularization of polymkeric substance of water tolerance problem is used.Although the modified phosphate based on this is good with the matrix polymer consistency, flame retardant resistance is better, and cost is high, and addition is large.Wherein the halogen-free flameproof goods with PC and the preparation of ABS blend interpolation phosphoric acid ester fire retardant have good commercial applications.Publication number is a kind of halogen-free phosphorus-free inflaming retarding PC/ABS alloy material of CN101089045A and publication number is CN101418118B that a kind of halogen-free flame retardant PC/the ABS Alloy And Preparation Method all is the representative of this respect.
Red phosphorus combustion inhibitor is because phosphorus content is high, 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 to flame retardance of polymer with red phosphorus combustion inhibitor and inorganic combustion inhibitor, and the inorganic combustion inhibitor addition is large, are unfavorable for processing.
The efficient flame-retarding agent that uses at electronic product at present is phosphinates.The composition of a kind of halogen-free and flame-retardant polycarbonate of United States Patent (USP) 7608654 reports is take phosphinates as main; United States Patent (USP) 7,803,856 disclose a kind of Flameproof polyamide, and it is comprised of phosphonate, nitrogenous compound and untreated nanoclay.Phosphinates has extensive, efficient flame retardant effect owing to having simultaneously organic and inorganic part in a molecule.Yet its production cost is high.
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 object of the invention is to overcome the prior art defective, a kind of applied widely, low-cost, efficient halogen-free flame retardants and contain the polymer materials of this halogen-free flame retardants 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 comprised 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 phenyl or the tertiary butyl.
Preferred R again
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 the goods such as PE.
Described benzoxazine colophony can be that single phenol or amine synthesizes, and 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 the 1:2:4 mol ratio by dihydroxyphenyl propane, aniline, Paraformaldehyde 96 synthetic.
It is synthetic that phenol type benzoxazine (BOZ) can be pressed the 1:1:2 mol ratio by phenol, aniline, Paraformaldehyde 96
Described benzoxazine colophony (take benzene phenol type oxazine resin as example) partly solidified reaching in the course of processing forms phenolic hydroxyl group when meeting the fire burning.Reaction formula is as follows:
The phosphorus oxide that described red phosphorus generates when burning, phosphoric acid, metaphosphoric acid, polyphosphoric acid etc. generate Inorganic-organic hybrid with the reaction of part phenolic hydroxyl group:
Reacted in the combustion processes of being heated by benzoxazine and red phosphorus and to generate Inorganic-organic hybrid, 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.
Advantage and beneficial effect that the present invention has with respect to prior art.
(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 more separately red phosphorus has significantly raising.
(2) can select the specific benzoxazine colophony good with the matrix phase capacitive for fire-retardant matrix simultaneously, have usability wide, the characteristics of good flame resistance.
(3) reacted in the combustion processes of being heated by benzoxazine and red phosphorus and generate Inorganic-organic hybrid, 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 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 the 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, then room temperature was colded pressing 10 minutes, and then depanning makes sheet material, was used for performance test.Testing standard sees Table 6.
Physical properties 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 resulting materials 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 material granulation and the aftertreatment of extruding, then injection moulding gets test bars.It is antioxidant 1076 and 168 composite antioxidants of 1:1 that antioxidant is selected mass ratio.Table 3 fire retardation PC/ABS alloy formula/(weight part)
Physical properties based on the halogen-free flame retardant PC of benzoxazine/ABS alloy 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 Setting after 10 parts of BPOZ and 10 parts of red phosphorus powder and 0.2 part of magnesium hydroxide mixed and be extruding pelletization in 120 ℃ the twin screw extruder, obtain containing the halogen-free flame retardants A of benzoxazine and red phosphorus.
With 10 parts of ABS with 1.8 parts above-mentioned contain benzoxazines and mix with the halogen-free flame retardants A of red phosphorus after on 200 ℃ of twin screw extruders extruding pelletization, 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 lower the grinding of inflated with nitrogen protection is mixed to get the halogen-free flame retardants B that contains 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, 0.1 part of black Masterbatch mixes in high-speed mixer, then this mixture is joined extruding pelletization in the twin screw extruder that temperature is controlled at 210 ~ 230 ℃, 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 (8)
1. contain the halogen-free flame retardants of benzoxazine, it is characterized in that, formed You mono-oxazines ring benzoxazine colophony, bisphenol type bisoxazines ring benzoxazine colophony or diamines Xing bisoxazines ring benzoxazine colophony, red phosphorus and metal oxide or metal hydroxides;
Wherein the weight ratio of mono-oxazines ring benzoxazine colophony, bisphenol type bisoxazines ring benzoxazine colophony or diamines Xing bisoxazines ring benzoxazine colophony and red phosphorus is 0.25～4;
0～10% weight percentage of metal oxide or metal hydroxides Zhan mono-oxazines ring benzoxazine colophony, bisphenol type bisoxazines ring benzoxazine colophony or diamines Xing bisoxazines ring benzoxazine colophony and red phosphorus gross weight;
Wherein, the structural formula of described mono-oxazines ring benzoxazine colophony is:
R wherein
1Be H, alkyl or aryl; R
2Be alkyl or aryl;
Described bisphenol type bisoxazines ring benzoxazine colophony structural formula is as follows:
R wherein
1Be alkyl or aryl; R
2Be alkyl or aryl;
Described diamines Xing bisoxazines ring benzoxazine colophony structural formula is as follows:
R wherein
1Be alkyl or aryl; R
2Be H, alkyl or aryl.
2. halogen-free flame retardants according to claim 1 is characterized in that, described mono-oxazines ring benzoxazine colophony is phenol type benzoxazine, and its structural formula is as follows:
3. halogen-free flame retardants according to claim 1 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:
4. one of according to claim 1-3 described halogen-free flame retardants is characterized in that, described red phosphorus is pure red phosphorus or micro encapsulation red phosphorus.
5. halogen-free flame retardants according to claim 4 is characterized in that, described metal hydroxides is aluminium hydroxide or magnesium hydroxide; Metal oxide is magnesium oxide or zinc oxide.
6. contain polymer materials and the goods of halogen-free flame retardants claimed in claim 1, it is characterized in that, comprise halogen-free flame retardants claimed in claim 1 and polymkeric substance; Described polymkeric substance is selected from and contains phenyl ring polymkeric substance, polyolefin polymers or their blends; Wherein the consumption of halogen-free flame retardants is 5～25%wt of polymer weight.
7. the polymer materials of halogen-free flame retardants according to claim 6 and goods is characterized in that, also comprise in toughner, compatilizer, oxidation inhibitor, lubricant, stablizer, static inhibitor, pigment, filler or the strongthener one or more.
8. the application of halogen-free flame retardants claimed in claim 1 in containing 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 |
Applications Claiming Priority (1)
| 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 CN102250383A (en) | 2011-11-23 |
| CN102250383B true 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) |
Families Citing this family (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 |
| CN103421266B (en) * | 2013-07-30 | 2016-02-03 | 江苏理工学院 | The preparation method of halogen-free flame-proof highly anti-flush polyphenylacetylene |
| CN103834169A (en) * | 2014-03-21 | 2014-06-04 | 厦门大学 | Flame-retardant benzoxazine resin and preparation method 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 |
| CN109942894B (en) * | 2019-02-23 | 2021-05-14 | 河南大学 | Halogen-free intumescent flame retardant system containing benzoxazine char former and flame retardant thermoplastic resin thereof |
| 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 |
| CN112876820B (en) * | 2021-01-19 | 2022-06-21 | 浙江理工大学 | Polyethylene terephthalate composite material |
| CN112876821B (en) * | 2021-01-19 | 2022-06-21 | 浙江理工大学 | Preparation method of polyethylene terephthalate composite material |
| CN115160664B (en) * | 2022-07-05 | 2023-06-02 | 沈阳化工大学 | Method for preparing reinforced nitrile rubber from low-viscosity benzoxazine |
| CN115613358B (en) * | 2022-10-31 | 2023-05-09 | 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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| US6645631B2 (en) * | 1999-12-13 | 2003-11-11 | Dow Global Technologies Inc. | Flame retardant phosphorus element-containing epoxy resin compositions |
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- 2011-08-25 WO PCT/CN2011/078955 patent/WO2013000198A1/en active Application Filing
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| Publication number | Publication date |
|---|---|
| CN102250383A (en) | 2011-11-23 |
| WO2013000198A1 (en) | 2013-01-03 |
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