CN105440565B - A kind of hud typed halogen-free flameproof polyformaldehyde composite material and preparation method thereof - Google Patents
A kind of hud typed halogen-free flameproof polyformaldehyde composite material and preparation method thereof Download PDFInfo
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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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
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
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- 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
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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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
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Abstract
The invention discloses a kind of hud typed halogen-free flameproof polyformaldehyde composite material and preparation method thereof, wherein the raw material of hud typed halogen-free flameproof polyformaldehyde composite material is as follows by mass fraction composition：50~80 parts of polyformaldehyde, 10~30 parts of ammonium polyphosphate microcapsules, 5~20 parts of fire retarding synergist, 2~15 parts of carbon forming agent, 0.1~1 part of antioxidant, 0.1~1 part of stabilizer.The polyformaldehyde flame retardant composite material of gained of the invention has high flame resistance, and the fire retardant additive amount of more traditional fire-retardant polyformaldehyde composite material is less, has the characteristics that physical and mechanical property is good, simple process.
Description
First, technical field
The present invention relates to Halogen highly effective flame-retardant polyformaldehyde materials and preparation method thereof, specifically a kind of hud typed Halogen
Fire-retardant polyformaldehyde composite material and preparation method thereof.
2nd, background technology
Polyformaldehyde (POM) also known as " taking steel by force ", " match steel ", including two kinds of acefal homopolymer and copolymerized methanal, with high intensity, height
The characteristics of modulus, is listed in one of five large-engineering plastics.POM main chains for simple C-O singly-bounds and without side group, have crystallinity it is high,
The features such as product size is stable, self-lubricating is good.However, POM molecular backbones oxygen content is high, limit oxygen index is low, is generally only
15%, when burning, releases formaldehyde gas, and with serious melting drip phenomenon.Easily crystallization, the characteristics of crystallinity is big, cause
Polyformaldehyde is extremely sensitive to notch, and the notch impact strength of polyformaldehyde is low, this is extremely asymmetric with formaldehyde others excellent properties.It is right
The features such as notch sensitive and easy firing, has seriously constrained application and expansion of the polyformaldehyde in more areas, therefore studies polyformaldehyde resistance
It is to have important practical significance to fire toughening performance.
The research workers both domestic and external research flame-retardant modified to POM has achieved certain progress, however hinders
The contradiction that combustion performance cannot get both with mechanical property is still the very crux.Such as：The patent of Application No. 201310703049.9 is public
One kind is opened with the fire-retardant POM of red phosphorus microcapsule, when packing quality ratio is 35%, oxygen index (OI) can reach 34%, and tensile strength reaches
46.4MPa.Have foreign literature report (J.Polym.Res., 2011,18:293-303), with resistances such as ammonium polyphosphate, melamines
Fire modified polyacetal, when amount of filler is 40%, flame retardant property up to UL94V-0 ranks, but material mechanical property it is notable under
Drop, notch impact strength is down to 2.6kJ/m2.Recent studies in China report (Chinese Plastics, 2014,28 (2):50-54), with red
Phosphorus coats POM for main flame retardant, and with the composite modified POM of other fire retardants, when fire-retardant filler is 35%, composite material
Can slow self-extinguishment, tensile strength is for 40MPa or so, but its notch impact strength is only 2.0kJ/m2.From expansion polyformaldehyde work
The angle of industry application, while polyformaldehyde material flame retardant property is improved, it is also necessary to consider amount of filler and its to mechanical property
Influence.
The polyformaldehyde flame retardant composite material of gained of the invention has high flame resistance, and more traditional fire-retardant polyformaldehyde composite wood
The fire retardant additive amount of material is less, while has the characteristics that physical and mechanical property is good, simple process.
3rd, the content of the invention
The present invention proposes a kind of hud typed for the characteristics of fire-retardant POM systems fire-retardant filler ratio is high, flame retarding efficiency is low
Halogen-free flameproof polyformaldehyde composite material and preparation method thereof.The hud typed halogen-free flameproof polyformaldehyde composite material of the present invention is realizing height
It imitates fire-retardant while has both excellent mechanical property.
The raw material of the hud typed halogen-free flameproof polyformaldehyde composite material of the present invention is formed as follows by mass fraction：
The fire retarding synergist is melamine cyanurate, the one or several kinds in melamine.
The carbon forming agent is one or more of pentaerythrite, bipentaerythrite or polyurethane.
The antioxidant is antioxidant 1010, antioxidant AT-10, antioxidant 164, one kind in antioxidant 1076 or several
Kind.
The stabilizer is one or more of calcium stearate, zinc stearate or barium stearate.
The ammonium polyphosphate microcapsules are synthesized by the component of following mass parts：
1~10 mass parts of isocyanates, 70~95 mass parts of ammonium polyphosphate, 5~15 mass parts of polyethers or polyester polyol,
0.1~1 mass parts of catalyst, 0~5 mass parts of chain extender.
The isocyanates is PAPI (polyphenyl polymethylene polyisocyanates), MDI (diphenylmethane diisocyanates
Ester), TDI (toluene di-isocyanate(TDI)), PPDI (phenylene diisocyanate), the one or several kinds in NDI (naphthalene diisocyanate).
The polyethers or polyester polyol are one kind in polyethers N220, polyethers N210, polyethers N204, polyethers N303, PEG
It is or several.
The catalyst is dibutyl tin laurate or stannous octoate.
The chain extender is pentaerythrite or bipentaerythrite.
The preparation method of the hud typed halogen-free flameproof POM composite materials of the present invention, includes the following steps：
1st, the preparation of ammonium polyphosphate microcapsules
Ammonium polyphosphate, isocyanates are added in organic solvent, in 40 DEG C of 20~30min of ultrasonic disperse, then added in poly-
Ether or polyester polyol stirring 20min, then temperature is risen to 70-80 DEG C, add in catalyst and chain extender carry out cross-linking reaction 1~
4h, filtered, washing, dry, grinding successively after reaction, it is poly- phosphorus of the capsule material ammonium polyphosphate as core to be made using polyurethane
Sour ammonium microcapsules.
The organic solvent is acetone, one kind in toluene, dimethylbenzene, methanol, ethyl alcohol, chloroform.
The mass ratio of capsule material and core is 1 in ammonium polyphosphate microcapsules:20~1:5.
2nd, the preparation of POM flame retardant composite materials
POM, ammonium polyphosphate microcapsules, fire retarding synergist, carbon forming agent, antioxidant and stabilizer are added in into twin-screw extrusion
In machine, through cooling, pelletizing, hud typed Halogen resistance is made in the melting extrusion under 165~185 DEG C of temperature, 20~60r/min of rotating speed
Fire POM composite materials.
POM and ammonium polyphosphate microcapsules in raw material dry 4~6h first at 80 DEG C and put into again in double screw extruder.
The present invention carries out POM by ammonium polyphosphate microcapsule flame retardant fire-retardant.Because the capsule material of ammonium polyphosphate microcapsules is gathered
Urethane can be used as carbon forming agent, help to improve charring rate；Burning when ammonium polyphosphate microcapsule flame retardant surface polyurethane also
Contacting directly for ammonium polyphosphate and POM can be obstructed, prevents propagation of flame；In terms of mechanical property, the polyurethane on surface can be with
With certain elasticity, and the interface compatibility of ammonium polyphosphate microcapsules and POM are preferable, ensure that having for composite material is preferable
Physical and mechanical property.
4th, illustrate
Fig. 1 is the flow chart of core-shell type flame retardant synthesis of the present invention.
Fig. 2 is the transmission electron microscope photo of ammonium polyphosphate raw material, in irregular shape, and particle is larger.
Fig. 3 is the transmission electron microscope photo of PAPI raw materials coated ammonium polyphosphate (embodiment 1), it is evident that white cladding
Layer, capsule-core and capsule material are high-visible, and surface is smooth.
Fig. 4 is the transmission electron microscope photo of MDI raw materials coated ammonium polyphosphate (embodiment 2), it is seen that apparent white clad, capsule
Core and capsule material interface are clear, and clad shape is regular.Transmission electron microscope results show：Two kinds of polyurethane coat polyphosphoric acid completely
Ammonium.
5th, specific embodiment
The POM trades mark used in the present invention are M90 (Yunnan Yuntianhua Co., Ltd).
Embodiment 1：
The preparation method of hud typed halogen-free flameproof POM composite materials, includes the following steps in the present embodiment：
1st, the preparation of ammonium polyphosphate microcapsules
1000g ammonium polyphosphate is taken to dry 10~12h in an oven, is positioned in 5000ml three-necked flasks, adds in the more benzene of 30g
Quito methylene polyisocyanates (PAPI) and 2000ml dimethylbenzene, mechanical agitation is carried out at the same time ultrasonic disperse 20min at 40 DEG C,
Then to the mixed solution that 30g polyether polyol N204 and 100ml dimethylbenzene is added dropwise in three-necked flask, 20min is dripped off, Ran Housheng
Temperature adds in 2g dibutyl tin laurates and carries out cross-linking reaction 2h to 75 DEG C, after reaction successively filtered, washing, it is dry,
Grinding, it is ammonium polyphosphate microcapsules of the capsule material ammonium polyphosphate as core to be made using polyurethane.
2nd, the preparation of POM flame retardant composite materials
Ammonium polyphosphate microcapsules 360g, melamine cyanurate prepared by POM 1400g dried through 4~6h, step 1
Salt 60g, melamine 60g, pentaerythrite 100g, AT-10 antioxidant 10g and KF-1 stabilizer 10g are pre-mixed, with after
Melt blending, rotating speed 30rad/min, cooling and dicing, dry obtained hud typed Halogen are carried out at 175 DEG C in double screw extruder
Fire-retardant POM composite materials.
Embodiment 2：
The preparation method of hud typed halogen-free flameproof POM composite materials, includes the following steps in the present embodiment：
1st, the preparation of ammonium polyphosphate microcapsules
1000g ammonium polyphosphate is taken to dry 10~12h in an oven, is positioned in 5000ml three-necked flasks, adds in 30g
MDI-50 and 2000ml dimethylbenzene, mechanical agitation is carried out at the same time ultrasonic disperse 20min at 40 DEG C, then to being added dropwise in three-necked flask
The mixed solution of 70g polyether polyol N220 and 100ml dimethylbenzene, 20min are dripped off, and then heat to 75 DEG C, add in 8g seasons penta
Tetrol and 2g dibutyl tin laurates carry out cross-linking reaction 2h, after reaction filtered, washing, dry, grinding successively, system
It is the ammonium polyphosphate microcapsules that capsule material ammonium polyphosphate is core to be able to polyurethane.
2nd, the preparation of POM flame retardant composite materials
Ammonium polyphosphate microcapsules 360g, melamine cyanurea prepared by the polyformaldehyde 1400g dried through 4~6h, step 1
Hydrochlorate 60g, melamine 60g, pentaerythrite 100g, AT-10 antioxidant 10g and KF-1 stabilizer 10g are pre-mixed, then
Melt blending, rotating speed 30r/min, cooling and dicing, dry obtained hud typed Halogen are carried out in double screw extruder at 175 DEG C
Fire-retardant POM composite materials.
Comparative example 1：
Pure POM is added in 175 DEG C in conical double screw extruder and carries out melting extrusion, rotating speed 30r/min.Cooling, cuts
Grain carries out pressing plate in vulcanizing press at 180 DEG C after drying process, preheat 5min, carries out pressurize 3min, is cold-pressed 10min.
The plate of 2mm thickness is obtained, carries out being cut into batten test.Another part carries out injection molding in miniature injection machine, injection
Pressure is 700MPa, and injection temperature is 185 DEG C, injection time 15s, dwell time 30s.
Comparative example 2：
By POM 1400g dried through 4~6h, ammonium polyphosphate 360g, melamine cyanurate 60g, melamine
60g, pentaerythrite 100g, AT-10 antioxidant 10g and KF-1 stabilizer 10g are pre-mixed, with after at 175 DEG C in double spiral shells
Melt blending, rotating speed 30r/min, cooling and dicing, dry obtained hud typed halogen-free flameproof POM composite woods are carried out in bar extruder
Material.
Composite material prepared by embodiment carries out fire-retardant and mechanical property test, and test result is as follows：
1 composite material of table is fire-retardant and mechanical property
| Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | |
| LOI (%) | 42 | 43 | 16 | 34 |
| Notch impact strength (kJ/m2) | 4.1 | 4.2 | 6.5 | 4.0 |
| Tensile strength (MPa) | 46.5 | 47.3 | 57.0 | 38.9 |
Remarks：Limit oxygen index is measured according to GB/T2406.2-2009 standard testings.
From table 1 it follows that the oxygen index (OI) of pure POM (comparative example 1) is only 16%, using APP as main fire retardant POM
Gained composite material (comparative example 2) oxygen index (OI) has been increased to 34%, and composite material is (real after coating modification is carried out to main flame retardant
Apply example 1, oxygen index (OI) 2) has been respectively 42% and 43%.In addition, the notch impact strength of embodiment 1,2 and 2 phase of comparative example
When, but tensile strength increases, and is respectively 46.5kJ/m2And 47.3kJ/m2。
2 composite material dechforination in combustion of table
| Combustion parameter | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 |
| Total heat discharges (MJ/m2) | 20.9 | 25.2 | 34.2 | 28.2 |
| Total oxygen consumption (g) | 12.8 | 15.3 | 16.1 | 17.1 |
| Heat release rate peak value (kW/m2) | 190.3 | 151.1 | 239.5 | 217.4 |
| Heat release rate average (kW/m2) | 40.2 | 58.0 | 195.5 | 71.6 |
| Unit mass heat production rate peak value (MJ/kg) | 71.0 | 38.7 | 45.5 | 64.2 |
| The time (s) of mass loss 10% | 64 | 38 | 52 | 50 |
| Charring rate (%) | 34.4 | 21.6 | 5.7 | 25.7 |
| The yield peak value (%) of CO | 0.18 | 0.02 | 0 | 0.39 |
| CO2Yield peak value (%) | 1.02 | 2.73 | 2.52 | 2.73 |
Remarks：Cone calorimetry test Main Basiss ASTM E1354, ISO 5560 standard perform.
From Table 2, it can be seen that pure POM (comparative example 1) total heat release is up to 34.2MJ/m2, hindered based on ammonium polyphosphate
Total heat release is reduced to 28.2MJ/m by combustion agent composite material (comparative example 2)2, ammonium polyphosphate is carried out made from after coating modification
The release of composite material (embodiment 1,2) total heat is further reduced to 25.2 and 20.9.In addition, total oxygen consumption, heat release speed
Rate etc. significantly reduces, and charring rate is greatly improved, and the charring rate of pure POM is only 5.7%, and flame retardant composite material (is implemented
Example 1) charring rate be up to 34.4%, in summary as can be seen that the flame retardant property of POM is made to be improved significantly.
Claims (2)
1. a kind of hud typed halogen-free flameproof polyformaldehyde composite material, it is characterised in that its raw material is formed as follows by mass fraction：
The fire retarding synergist is melamine cyanurate, the one or several kinds in melamine；
The carbon forming agent is one or more of pentaerythrite, bipentaerythrite or polyurethane；
The antioxidant is one or more of antioxidant 1010, antioxidant AT-10, antioxidant 164, antioxidant 1076；
The stabilizer is one or more of calcium stearate, zinc stearate or barium stearate；
The ammonium polyphosphate microcapsules are to synthesize to obtain by the component of following mass parts：
1~10 mass parts of isocyanates, 70~95 mass parts of ammonium polyphosphate, 5~15 mass parts of polyethers or polyester polyol, catalysis
0.1~1 mass parts of agent, 0~5 mass parts of chain extender；
The isocyanates is the one or several kinds in PAPI, MDI, TDI, PPDI, NDI；
The polyethers or polyester polyol are polyethers N220, polyethers N210, polyethers N204, one kind in polyethers N303, PEG or several
Kind；
The catalyst is dibutyl tin laurate or stannous octoate；
The chain extender is pentaerythrite or bipentaerythrite；
The preparation of the ammonium polyphosphate microcapsules includes the following steps：
Ammonium polyphosphate, isocyanates are added in organic solvent, in 40 DEG C of 20~30min of ultrasonic disperse, then add in polyethers or
Polyester polyol stirs 20min, then temperature is risen to 70-80 DEG C, adds in catalyst and chain extender carries out 1~4h of cross-linking reaction,
Filtered, washing, dry, grinding successively after reaction, it is polyphosphoric acid of the capsule material ammonium polyphosphate as core to be made using polyurethane
Ammonium microcapsules；
The mass ratio of capsule material and core is 1 in ammonium polyphosphate microcapsules:20~1:5；
The organic solvent is acetone, one kind in toluene, dimethylbenzene, methanol, ethyl alcohol, chloroform；
The hud typed halogen-free flameproof polyformaldehyde composite material is to be prepared via a method which to obtain：
POM, ammonium polyphosphate microcapsules, fire retarding synergist, carbon forming agent, antioxidant and stabilizer are added in into double screw extruder
In, through cooling, pelletizing, hud typed halogen-free flameproof is made in the melting extrusion under 165~185 DEG C of temperature, 20~60r/min of rotating speed
POM composite materials.
2. hud typed halogen-free flameproof polyformaldehyde composite material according to claim 1, it is characterised in that：
POM and ammonium polyphosphate microcapsules in raw material dry 4~6h first at 80 DEG C and put into again in double screw extruder.
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| CN107286631A (en) * | 2017-07-19 | 2017-10-24 | 成都新柯力化工科技有限公司 | Double-coating microcapsules efficient flame-retarding agent for polyurethane and preparation method thereof |
| CN112500679B (en) * | 2020-11-05 | 2022-05-10 | 金发科技股份有限公司 | High-performance high glow wire polyformaldehyde composition as well as preparation method and application thereof |
| CN112921426B (en) * | 2021-01-29 | 2023-04-25 | 江苏厚生新能源科技有限公司 | Flame-retardant polyethylene composite fabric based on metal framework and preparation process thereof |
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