CN104479353B - Novel halogen-free flame-retardant composition, halogen-free flame-retardant PBT engineering plastic composite material and preparation method thereof - Google Patents
Novel halogen-free flame-retardant composition, halogen-free flame-retardant PBT engineering plastic composite material and preparation method thereof Download PDFInfo
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- CN104479353B CN104479353B CN201410799557.6A CN201410799557A CN104479353B CN 104479353 B CN104479353 B CN 104479353B CN 201410799557 A CN201410799557 A CN 201410799557A CN 104479353 B CN104479353 B CN 104479353B
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- halogen
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- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 49
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- 239000000463 material Substances 0.000 abstract description 28
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 abstract description 23
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- 239000012757 flame retardant agent Substances 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910019213 POCl3 Inorganic materials 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
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Classifications
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- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
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- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention relates to the field of flame-retardant high polymer materials, and particularly relates to a novel halogen-free flame-retardant composition, a halogen-free flame-retardant PBT engineering plastic composite material and a preparation method thereof. The halogen-free flame retardant FRs is mainly obtained by mixing FR1, FR2, FR3, FR4 and FR5 according to a specific proportion, and the halogen-free flame retardant system has higher heat resistance stability and good flame retardant property by matching the substances. A kind of halogen-free inflaming retarding PBT engineering plastics composite material, this material is mainly made of PBT, alkali-free glass fibre, halogen-free flame retardant FRs, CTI synergist, anti-oxidant, lubricant, coupling agent, compatibilizer, flexibilizer, every component cooperates, the halogen-free inflaming retarding PBT engineering plastics composite material made is flame retardant, electrical property, heat resistance, mechanical property, colorability, etc. comprehensive performance superiority; the preparation method of the composite material is simple and feasible, and the prepared composite material has excellent comprehensive performance.
Description
Technical field
The present invention relates to flame retarded polymeric material field, in particular to a kind of novel halogen-free flame-retardant composition, Halogen
Flame-retardant PBT engineering plastic composite material and preparation method thereof.
Background technology
Polybutylene terephthalate (PBT) (PBT) is a kind of crystallinity line style saturated polyester, with excellent processing characteristics,
Mechanical performance, heat-resistant aging, solvent resistance, water stability and electric property etc., be widely used in automobile, plant equipment,
In household electrical appliance, electric manufacturing industry, as a member important in engineering plastics.
Addition fire retardant is needed to improve its fire resistance in PBT engineering plastics.For a long time, flame-retardant PBT engineering plastic
Expect that composite generally selects bromide fire retardant.The features such as bromide fire retardant has high flame retarding efficiency, good flame retardation effect, but bromine system
Contain in fire retardant and dysgenic hazardous substance is likely to result in environment.With issuing for RoHS Directive and REACH regulations
The fire proofing requirement nothing used in cloth, execution, the industry such as electric, information, office household electrical appliances in European Union, North America market
Halogenation, therefore many modified PBT engineering plastics manufacturers active development fire retardant PBT with no halogen product,
Fire retardant PBT with no halogen is mainly using the resistance such as inorganic matter, red phosphorus flame-retardant system, phosphorus-nitrogen containing flame retardant and organic hypophosphites
Fire agent.Wherein, inorganic matter is mainly magnesium hydroxide, aluminium hydroxide, and resistance is can be only achieved because needing largely to add two kinds of inorganic matters
Fuel efficiency fruit so that poor compatibility between inorganic matter and PBT matrix materials, causes the physical and mechanical properties decline of final products very big,
It is difficult to meet application request.Although it is big, properties of product decline partly to solve addition using red phosphorus flame-retardant system
Problem, but be due to red phosphorus combustion inhibitor color articles poor performance, particularly red phosphorus heat endurance is poor, with PBT hybrid process mistakes
Produce that substantial amounts of smell is larger and poisonous gas in journey, limit red phosphorus flame-retardant PBT many purposes.For above-mentioned situation,
Phosphorus-nitrogen containing flame retardant or organic phosphonateflame retardant are one of preferable halogen-free flame retardants of current fire retardant PBT with no halogen.However, state
Interior prior art remains certain defect compared with the high-end product of a small number of international major companies, mainly compared to leaking electricity
Trace index (CTI), heat-resistant stability are relatively low, therefore, halogen free flame-retardant reinforced PBT composite wood of the exploitation with independent intellectual property right
Material, with major application value and broad development space.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of novel halogen-free flame-retardant agent FRs, and described halogen-free flame retardants FRs is main
It is mixed to get by FR1, FR2, FR3, FR4 and FR5 according to specific ratio, wherein, FR1 is a kind of heat-resistant stability Halogen phosphorus system
Fire retardant, the high heat stability phosphate containing four quaternary carbon structures, with preferable coking performance, phosphorus content is up to more than 20%；FR2
It is a kind of melamine pyrophosphate, belongs to Halogen phosphorus-nitrogenated flame retardant；FR3 is a kind of dendritic bittern-free phosphorous-nitrogen flame retardant,
Belong to hyperbranched phosphorus-nitrogenated flame retardant, with certain increasing tougheness, three has good cooperative flame retardant efficiency；FR4 is a kind of
Improve the PEI of material combination property, FR5 is a kind of anti-molten drop and improves the additive of processing characteristics, FR4 and FR5's
Add the anti-dropping performance that can further improve halogen-free flame-retardant system FRs flame-retardant PBTs and improve the combination property of material；This is several
Material is with the use of so that halogen-free flame-retardant system has higher heat-resistant stability and good fire resistance.
The second object of the present invention is to provide a kind of fire retardant PBT with no halogen engineering plastic composite material, and the material is main
By PBT, alkali-free glass fibre, halogen-free flame retardants FRs, CTI synergist, antioxidant, lubricant, coupling agent, bulking agent, toughener
It is made.Wherein, the insulating layer structure generated when halogen-free flame retardants FRs is conducive to flame-retardant PBT engineering plastic composite material to burn is more
Hole is fine and close, completely cut off material and energy transmission, effectively raises the fire resistance of halogen-free flame-retardant system；Each composition coordinated,
Fire resistance, electric property, heat resistance, mechanical performance, the coloring of obtained fire retardant PBT with no halogen engineering plastic composite material
The combination properties such as energy are superior.
The third object of the present invention is to provide a kind of preparation side of described fire retardant PBT with no halogen engineering plastic composite material
Method, this method is simple and easy to apply, fire retardant PBT with no halogen engineering plastic composite material combination property is made superior.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of novel halogen-free flame-retardant agent FRs, mainly compares 2.6-2.8 by FR1, FR2, FR3, FR4 and FR5 according to weight:
0.8-1.2:0.4-0.6:0.9-1.1:0.05-0.15 is mixed to get；
Wherein, FR1 structures are as follows：
FR2 structures are as follows：
FR3 structures are as follows：
FR4 structures are as follows：
FR5 structures are as follows：
The heat resistance of fire retardant PBT with no halogen engineering plastic composite material presence is prepared for existing halogen-free flame retardants, resists and melts
The problems such as dripping performance, low CTI values and colour undesirable, the present invention provides a kind of novel halogen-free flame-retardant agent FRs, described FRs
Mainly it is mixed to get by FR1, FR2, FR3, FR4 and FR5 according to specific ratio, wherein, FR1 is a kind of heat-resistant stability Halogen
Phosphorus flame retardant, the high heat stability phosphate containing four quaternary carbon structures, with preferable coking performance, phosphorus content up to 20% with
On；FR2 is a kind of melamine pyrophosphate, belongs to Halogen phosphorus-nitrogenated flame retardant；FR3 is a kind of dendritic bittern-free phosphorous-nitrogen system
Fire retardant, belongs to hyperbranched phosphorus-nitrogenated flame retardant, with certain increasing tougheness, the flame-retardant system that three's composition is efficiently cooperateed with；
FR4 is a kind of PEI of improvement material combination property, and FR5 is a kind of anti-molten drop and improves the additive of processing characteristics,
FR4 and FR5 addition can further improve the anti-dropping performance of halogen-free flame-retardant system FRs flame-retardant PBTs and improve the synthesis of material
Performance；This several material is with the use of so that halogen-free flame-retardant system has higher heat-resistant stability and good fire resistance.
Wherein, FR1 is Caged bicyclic phosphate flame retardant disclosed in application number 200810147613.2；FR2's is logical
Model MPP is used, can be bought from Jiangsu Su Li groups, Su Li fine chemistry industries limited company；FR3 is according to document (Han Huan, clock
Willow, Liu Zhiguo.Hyperbranched phosphorus flame retardant is prepared and its fire retarding epoxide resin, Chinese fire-retardant Annual Conference in 2010) synthesis；
FR4 model ULTEM 1000, trade name is ULTEM HU1000, can be bought from radical innovations plastics (U.S.) manufacture
Arrive；FR5 is Teflon powder, can be bought from Dongguan City Ji Hong plastic cement Co., Ltd.
As FR1 can be prepared in the following manner：Using resorcinol, POCl3, pentaerythrite as raw material, course of reaction
For：Pentaerythrite, Isosorbide-5-Nitrae-dioxane are added into reactor, interior 80 DEG C of temperature is heated to, in adding three in 1h first quick and back slow
Chlorethoxyfos, finish continuation back flow reaction 2h, and standing is cooled to room temperature, filters to obtain white powdery solids pentaerythrite phosphonate ester
PEPA.By POCl3 and resorcinol (mol ratio 1:2) and in catalyst addition reaction vessel, 3h is reacted under heating, then
The PEPA of above-mentioned synthesis is added, fire retardant FR 1 is obtained under acid binding agent effect.
Such as FR3 is prepared according to above-mentioned document, specific as follows：Dimethylbenzene, m-phenylene diamine (MPD) and triethylamine are added in reactor,
Nitrogen protect and mechanical agitation under material is well mixed while heated to 50 DEG C, POCl3 is slowly added dropwise and controls that speed is added dropwise
Degree makes reaction temperature be no more than 80 DEG C.Completion of dropping reacts 4h in 100 DEG C, and infrared spectrum judges reaction end, and reaction is mixed
Thing is cooled to room temperature, separates solidfied material, crushes, untill being washed with distilled water to no chlorion, is overspend after vacuum drying
Change m-phenylene diamine (MPD) phosphamide product F R3.
Preferably, the halogen-free flame retardants FRs by FR1, FR2, FR3, FR4 and FR5 according to weight ratio 2.7:1:0.5:1:
0.1 is mixed to get；
Wherein, FR1 fusing point is 294-301 DEG C, and P% is 20.24；
FR3 melting temperature is 101-103 DEG C.
The weight than FR1, FR2, FR3, FR4 and FR5 mixing, with more preferable collaboration enhancing effect；And specific choosing
It it is 294-301 DEG C with FR1 fusing point, the melting temperature that P% is 20.24, FR3 is 101-103 DEG C, the halogen-free flame retardants being made
FRs combination properties are more superior.Wherein, P% is the weight/mass percentage composition of phosphorus.
Halogen-free flame retardants FRs is to be uniformly mixed so as to obtain FR1, FR2, FR3, FR4 and FR5.Such as can be by FR1, FR2, FR3, FR4
Kneading machine is put into FR5, is mixed with 60-200r/min rotating speed；After being put into due to total material, it is difficult to stir, therefore
It can then increase mixing speed from relatively low speed stirring a period of time and be stirred again, to accelerate the mixing of each composition.
Present invention also offers fire retardant PBT with no halogen engineering plastic composite material, mainly it is made up of following component, by weight
Meter,
For the defect of PBT processes plastic composite in the market, the present invention uses heat-resistant stability good and had
The halogen-free flame retardants FRs of high coking performance, halogen-free flame retardants FRs, which have, to strengthen alkali-free glass fibre and PBT is carried out
The effect that halogen-free flameproof is modified, it is heat-insulated that halogen-free flame retardants FRs is generated when being conducive to flame-retardant PBT engineering plastic composite material to burn
Porous fine and close, the isolation material of Rotating fields and energy transmission, effectively raise the fire resistance of halogen-free flame-retardant system；And compound
CTI synergist etc. prepare a kind of high thermal stability, anti-dropping, high CTI and be easy to coloring fire retardant PBT with no halogen engineering plastics be combined
Material.
In order that PBT is preferably merged with other compositions, scattered more homogeneous, the obtained halogen-free flameproof of each material composition
More preferably, further, the intrinsic viscosity of the PBT is 0.85-1.20dlg to the performance of PBT engineering plastic composite materials-1, phase
It is 1.30-1.33 to density, melting range is content of carboxyl end group≤30mol/t in 220~235 DEG C, and the PBT resin.
In order that alkali-free glass fibre is preferably merged with other compositions, the obtained fire retardant PBT with no halogen engineering plastics of enhancing
Insulating properties, heat resistance, corrosion resistance and mechanical strength height of composite etc., it is preferable that the alkali-free glass fibre diameter
For 4-17 μm；
Between CTI synergists and organophosphorous fire retardant have antagonistic effect, can reduce PBT composite mechanical property and
Fire resistance, in order that CTI synergists neither influence the mechanical property and fire resistance of PBT composite, can improve material again
CTI, the specific CTI synergists from 0.1~0.5 part of the present invention.Further, the CTI synergists are calcium oxide.CTI
Synergist is calcium oxide, with more preferable trade-off effect.
In order to suppress the progress of oxidizing process in fire retardant PBT with no halogen engineering plastic composite material, so as to prevent the old of material
Change, it is preferable that the antioxidant is four [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, β-(3,5- bis-
Tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, N, N- is double-[3- (3,5- di-tert-butyl-hydroxy phenyls) propiono]
Hexamethylene diamine, phosphorous acid three (2,4- 6- di-tert-butyl phenyl esters), triethylene glycol are double [3- (3- di-t-butyl -4- hydroxy-5-methyl bases phenyl)]
At least one of acrylonitrile.
Empirical tests, the antioxidant is preferably by four [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrites
Ester and phosphorous acid three (2,4- 6- di-tert-butyl phenyl esters) are 1 by weight:1.5-2.5 is constituted, and the antioxidant has more superior resist
Oxidation susceptibility.
In order that each composition is preferably merged, each component distributing of obtained mixture it is more homogeneous, it is preferable that the profit
Lubrication prescription is at least one of ethylene bis-fatty acid amides and pentaerythritol stearate；Further, the lubricant is served as reasons
Pentaerythritol stearate and ethylene bis-fatty acid amides are 1 by weight:1.2-1.5 composition.
In order to reduce the viscosity of mixture melt, increase the decentralization of each composition to improve processing characteristics, and then improve material
The interface performance of material, it is preferable that the coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane, the second of γ-aminopropyl three
At least one of TMOS；Further, the coupling agent is preferably γ-glycidyl ether oxygen propyl trimethoxy silicon
Alkane；In order that each composition is preferably compatible, the bulking agent is preferably ABS-g-MAH.
In order to increase the toughness of obtained fire retardant PBT with no halogen engineering plastic composite material, bearing strength is improved, it is preferable that
The toughener is ethylene methyl methacrylate-glycidyl acrylate copolymer, methyl methacrylate-acrylic acid
Butyl ester bipolymer, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer, diallyl phthalate-
At least one of vinyl chloride copolymer.
Present invention also offers the preparation method of above-mentioned fire retardant PBT with no halogen engineering plastic composite material, comprise the following steps：
(a), the composition stirring 10-20min in addition to alkali-free glass fibre is mixed, speed of agitator is 100-500r/min；
(b), the composition mixed is granulated by Bitruder melting extrusion, processing conditions is：Twin-screw extrusion
200-210 DEG C of the area's temperature of machine one, two 210-230 DEG C of area's temperature, three 210-230 DEG C of area's temperature, four 210-230 DEG C of area's temperature, five
200-220 DEG C of area's temperature, six 200-220 DEG C of area's temperature, seven 200-220 DEG C of area's temperature, eight 210-230 DEG C of area's temperature；
Wherein, alkali-free glass fibre is added in the stage casing of Bitruder, the alkali-free glass fibre is through silane coupled
Agent immersion treatment；
Screw speed is 350-500r/min.
The preparation method for the fire retardant PBT with no halogen engineering plastic composite material that the present invention is provided, will first remove alkali-free glass fibre
Outer composition is mixed, and is then granulated through Bitruder melting extrusion, meanwhile, nothing will be added in the stage casing of Bitruder
Alkali containing glass fibre, it is therefore prevented that can degrade alkali-free glass fibre during high temperature process；Further, since alkali-free glass fibre surface polarity compared with
Greatly, with the poor compatibility of other compositions, alkali-free glass fibre is coupled to glass surface through silane coupler immersion treatment, by silicon and entered
Row is modified, increase alkali-free glass fibre and high polymer material compatibility and dispersive property；Each composition is used into Bitruder
Melting extrusion is granulated, and is heated by multiple high temp, is enhanced the compatibility and homogeneity between each composition, is made a kind of fire-retardant
The preferable fire retardant PBT with no halogen engineering plastics of the combination properties such as performance, electric property, heat resistance, mechanical performance, tinctorial property are answered
Condensation material.
Compared with prior art, beneficial effects of the present invention are：
(1) halogen-free flame retardants FRs is mixed to get by FR1, FR2, FR3, FR4 and FR5 according to specific ratio, obtained nothing
Halogen fire retardant FRs has extraordinary cooperative flame retardant performance, anti-dropping performance and improves the combination property of material；And this is several
Material is planted with the use of so that halogen-free flame-retardant system has higher heat-resistant stability and with coking performance；
(2) halogen-free flame retardants FRs is used to prepare fire retardant PBT with no halogen engineering plastic composite material, is conducive to flame-retardant PBT engineering
Porous fine and close, the isolation material of insulating layer structure and energy transmission that plastic composite is generated when burning, effectively raise nothing
The fire resistance of halogen flame-retardant system；And with other each composition coordinateds, obtained fire retardant PBT with no halogen engineering plastics composite wood
The combination properties such as fire resistance, electric property, heat resistance, mechanical performance, the tinctorial property of material are superior；
(3) preparation method of fire retardant PBT with no halogen engineering plastic composite material is simple and easy to apply, and fire retardant PBT with no halogen engineering is made
Plastic composite excellent combination property.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, be
Can be by the conventional products of commercially available acquisition.
Embodiment 1
5.4kg FR1,2.0kg FR2,1.0kg FR3,2.0kg FR4 and 0.2kg FR5 are added into kneading machine, point
Do not stirred respectively with 60rpm, 100rpm, 160rpm, 200rpm 5 minutes, obtain novel halogen-free flame-retardant agent FRs；
After being soaked in the alkali-free glass fibre immersion silane coupler of 11-15 μm of selection, dry for standby is taken out；
By PBT resin in being bakeed 5.5 hours at 120-130 DEG C, by the 45kgPBT resins after baking, 10kg halogen-free flameproofs
Agent FRs, 0.1kg calcium oxide, 0.6kg antioxidant, 0.3kg lubricants, 0.4kg coupling agents, 1kg bulking agents and 5kg toughener
Sequentially add in kneading machine, then respectively stirred with 100rpm, 200rpm 5 minutes, obtain halogen-free flame retardants FRs flame-retardant PBTs and be combined
Material pre-composition；
Wherein, antioxidant is by four [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and phosphorous acid three
(2,4- 6- di-tert-butyl phenyl esters) is 1 by weight:1.5 composition；Lubricant is by pentaerythritol stearate and the double fat of ethylene
Sour acid amides is 1 by weight:1.2 composition；Coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane；Bulking agent is
ABS-g-MAH；Toughener is ethylene methyl methacrylate-glycidyl acrylate copolymer；
Pre-composition is added in double screw extruder loading hopper, respectively with 200-210 DEG C, 210-230 DEG C, 210-230
DEG C, the machine barrel and machine of 210-230 DEG C, 200-220 DEG C, 200-220 DEG C, 200-220 DEG C, 210-230 DEG C temperature control extruder
Head temperature, while 20kg alkali-free glass fibres are added in the loading hopper of twin-screw centre position, and using screw speed as 350r/
The extruded machine extrusion of PBT composite, pelletizing, drying are obtained fire retardant PBT with no halogen engineering plastic composite material by min.
Embodiment 2
7.8kg FR1,3.6kg FR2,1.2kg FR3,3.3kg FR4 and 0.15kg FR5 are added into kneading machine,
Respectively stirred with 80rpm, 120rpm, 140rpm, 180rpm 5 minutes respectively, obtain novel halogen-free flame-retardant agent FRs；
After being soaked in the alkali-free glass fibre immersion silane coupler of 4-8 μm of selection, dry for standby is taken out；
By 60kg PBT resins, 16kg halogen-free flame retardants FRs, 0.3kg calcium oxide, 0.3kg antioxidant, 0.5kg lubricants,
0.2kg coupling agents, 3kg bulking agents and 1kg toughener are sequentially added in kneading machine, then respectively with 100rpm, 140rpm,
180rpm, 220rpm are respectively stirred 5 minutes, obtain halogen-free flame retardants FRs anti-flaming PBT composite pre-compositions；
Wherein, antioxidant is by four [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and phosphorous acid three
(2,4- 6- di-tert-butyl phenyl esters) is 1 by weight:2.5；Lubricant is by pentaerythritol stearate and ethylene bis-fatty acid acyl
Amine is 1 by weight:1.5 composition；Coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane and the second of γ-aminopropyl three
The mixture of TMOS, wherein, γ-glycidyl ether oxygen propyl trimethoxy silicane 0.1kg, gamma-aminopropyl-triethoxy
Silane 0.1kg；Bulking agent is ABS-g-MAH；Toughener is methyl methacrylate-butyl acrylate bipolymer and second
The mixture of alkene-butyl acrylate-glycidyl methacrylate copolymer, wherein, methyl methacrylate-acrylic acid fourth
Ester bipolymer 0.3kg, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer 0.7kg；
Pre-composition is added in double screw extruder loading hopper, respectively with 200-210 DEG C, 210-230 DEG C, 210-230
DEG C, the machine barrel and machine of 210-230 DEG C, 200-220 DEG C, 200-220 DEG C, 200-220 DEG C, 210-230 DEG C temperature control extruder
Head temperature, while 25kg alkali-free glass fibres are added in the loading hopper of twin-screw centre position, and using screw speed as 450r/
The extruded machine extrusion of PBT composite, pelletizing, drying are obtained fire retardant PBT with no halogen engineering plastic composite material by min.
Embodiment 3
14kg FR1,4kg FR2,3kg FR3,4.5kg FR4 and 0.25kg FR5 are added into kneading machine, respectively with
80rpm, 140rpm, 200rpm are respectively stirred 5 minutes, obtain novel halogen-free flame-retardant agent FRs；
After being soaked in the alkali-free glass fibre immersion silane coupler of 10-13 μm of selection, dry for standby is taken out；
By 70kg PBT resins, 23kg halogen-free flame retardants FRs, 0.5kg calcium oxide, 0.4kg antioxidant, 0.8kg lubricants,
0.6kg coupling agents, 6kg bulking agents and 12kg toughener are sequentially added in kneading machine, then respectively with 100rpm, 160rpm,
200rpm, each stirring 5 minutes, obtain halogen-free flame retardants FRs anti-flaming PBT composite pre-compositions；
Wherein, antioxidant is β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid；Lubricant is season penta
Tetrol stearate；Coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane；Bulking agent is ABS-g-MAH；Toughener
It is total to for ethylene methyl methacrylate-glycidyl acrylate copolymer, methyl methacrylate-butyl acrylate binary
Polymers, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer and diallyl phthalate-vinyl chloride are common
The mixture of polymers, wherein, methyl methacrylate-butyl acrylate bipolymer 2kg, Ethylene-butyl acrylate-methyl
Glycidyl acrylate copolymer 3kg, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer 5kg, adjacent benzene
Diformazan diallyl phthalate-vinyl chloride copolymer 2kg；
Pre-composition is added in double screw extruder loading hopper, respectively with 200-210 DEG C, 210-230 DEG C, 210-230
DEG C, the machine barrel and machine of 210-230 DEG C, 200-220 DEG C, 200-220 DEG C, 200-220 DEG C, 210-230 DEG C temperature control extruder
Head temperature, while 32kg alkali-free glass fibres are added in the loading hopper of twin-screw centre position, and using screw speed as 500r/
The extruded machine extrusion of PBT composite, pelletizing, drying are obtained fire retardant PBT with no halogen engineering plastic composite material by min.
Embodiment 4
8.0kg FR1,3.0kg FR2,1.5kg FR3,3.0kg FR4 and 0.3kg FR5 are added into kneading machine, point
Do not stirred respectively with 80rpm, 150rpm 10 minutes, obtain novel halogen-free flame-retardant agent FRs；
After being soaked in the alkali-free glass fibre immersion silane coupler of 15-17 μm of selection, dry for standby is taken out；
By 50kg PBT resins, 14kg halogen-free flame retardants FRs, 0.3kg calcium oxide, 0.5kg antioxidant, 0.6kg lubricants,
0.4kg coupling agents, 2kg bulking agents and 8kg toughener are sequentially added in kneading machine, then respectively with 120rpm, 160rpm,
200rpm is respectively stirred 5 minutes, obtains halogen-free flame retardants FRs anti-flaming PBT composite pre-compositions；
Wherein, antioxidant be four [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.1kg, β-(3,
5- di-tert-butyl-hydroxy phenyls) positive octadecanol ester 0.1kg, N, N- pairs-[3- (3,5- di-t-butyl -4- hydroxy benzenes of propionic acid
Base) propiono] double [3- (3- di-t-butyl -4- hydroxyls of hexamethylene diamine, (2,4- 6- di-tert-butyl phenyl esters) 0.1kg of phosphorous acid three and triethylene glycol
Base -5- aminomethyl phenyls)] acrylonitrile 0.2kg mixture；Lubricant is ethylene bis-fatty acid amides；Coupling agent is that γ-shrink is sweet
Oily ether oxygen propyl trimethoxy silicane；Bulking agent is ABS-g-MAH；Toughener is that diallyl phthalate-vinyl chloride is common
Polymers；
Pre-composition is added in double screw extruder loading hopper, while being added in the loading hopper of twin-screw centre position
12.00Kg alkali-free glass fibres, respectively with 200-210 DEG C, 210-230 DEG C, 210-230 DEG C, 210-230 DEG C, 200-220 DEG C,
The machine barrel and head temperature of 200-220 DEG C, 200-220 DEG C, 210-230 DEG C temperature control extruder, and using screw speed as
The extruded machine extrusion of PBT composite, pelletizing, drying are obtained fire retardant PBT with no halogen engineering plastic composite material by 400r/min.
Chemical reagent used purchase or self-control, specific as follows in embodiment 1-4：
Prepared by FR1 modes according to disclosed in application number 200810147613.2, specific as follows：With resorcinol, trichlorine oxygen
Phosphorus, pentaerythrite are raw material, and course of reaction is：Pentaerythrite, Isosorbide-5-Nitrae-dioxane are added into reactor, interior temperature is heated to
80 DEG C, in adding POCl3 in 1h first quick and back slow, continuation back flow reaction 2h is finished, standing is cooled to room temperature, filters white
Pulverulent solids pentaerythrite phosphonate ester PEPA.By POCl3 and resorcinol (mol ratio 1:2) and catalyst add reaction
In container, 3h is reacted under heating, the PEPA of above-mentioned synthesis is added, and fire retardant FR 1 is obtained under acid binding agent effect；It is obtained
FR1 fusing points are 294-301 DEG C, and P% is 20.24.
According to document, (hyperbranched phosphorus flame retardant is prepared and its fire retarding epoxide resin FR3, China's fire-retardant academic year in 2010
Meeting) prepared, it is specific as follows：Dimethylbenzene, m-phenylene diamine (MPD) and triethylamine are added in reactor, nitrogen protection and mechanical agitation
It is lower that material is well mixed while heated to 50 DEG C, POCl3 is slowly added dropwise and controls rate of addition to be no more than reaction temperature
80℃.Completion of dropping reacts 4h in 100 DEG C, and infrared spectrum judges reaction end, reactant mixture is cooled into room temperature, separates solid
Compound, crushes after vacuum drying, untill being washed with distilled water to no chlorion, obtains hyperbranched m-phenylene diamine (MPD) phosphinylidyne amine product
FR3.FR3 melting temperature is 101-103 DEG C.
FR2 is bought from Su Li fine chemistry industries limited company；FR4 model ULTEM1000, trade name is
ULTEM HU1000, are commercially available from radical innovations plastics (U.S.) manufacture；FR5 is Teflon powder, from the lucky letter modeling of Dongguan City
Glue Co., Ltd buys.
In addition, PBT intrinsic viscosity is 0.85-1.20dlg-1, relative density is 1.30-1.33, melting range is 220~
Content of carboxyl end group≤30mol/t in 235 DEG C, and the PBT resin.
By fire retardant PBT with no halogen engineering plastic composite material made from embodiment 1-4 according to national standard measure tensile strength,
The non-notch impact strength of fracture strength, bending strength, bending modulus, Izod notched impact strength, cantilever beam, thermal change temperature,
Fire resistance, molding shrinkage, CTI values etc., specific standards are as shown in table 1.What is measured the results are shown in Table 2.
The testing standard of each performance parameter of table 1
The numerical value of each performance of the fire retardant PBT with no halogen engineering plastic composite material of table 2
From table 2 it can be seen that the fire retardant PBT with no halogen engineering plastic composite material that the present invention is provided has good resultant force
Performance, thermal property and fire resistance are learned, particularly with excellent CTI values.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that without departing substantially from the present invention's
Many other changes and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (15)
1. a kind of fire retardant FR s, it is characterised in that mainly compare 2.6-2.8 according to weight by FR1, FR2, FR3, FR4 and FR5:
0.8-1.2:0.4-0.6:0.9-1.1:0.05-0.15 is mixed to get；
Wherein, FR1 structures are as follows：
FR2 structures are as follows：
FR3 structures are as follows：
FR4 structures are as follows：
FR5 structures are as follows：
2. fire retardant FR s according to claim 1, it is characterised in that the fire retardant FR s is by FR1, FR2, FR3, FR4
With FR5 according to weight ratio 2.7:1:0.5:1:0.1 is mixed to get；
Wherein, FR1 fusing point is 294-301 DEG C, and P% is 20.24；
FR3 melting temperature is 101-103 DEG C.
3. include any one of claim 1-2 FRs flame-retardant PBT engineering plastic composite material, it is characterised in that it is main by
Following component is made, by weight,
4. flame-retardant PBT engineering plastic composite material according to claim 3, it is characterised in that the intrinsic viscosity of the PBT
For 0.85-1.20dlg-1, relative density is 1.30-1.33, and melting range is end carboxyl in 220~235 DEG C, and the PBT resin
Content≤30mol/t.
5. flame-retardant PBT engineering plastic composite material according to claim 3, it is characterised in that the alkali-free glass fibre
A diameter of 4-17 μm.
6. flame-retardant PBT engineering plastic composite material according to claim 3, it is characterised in that the CTI synergists are oxygen
Change calcium.
7. flame-retardant PBT engineering plastic composite material according to claim 3, it is characterised in that the antioxidant is four [3-
(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid positive ten
Eight carbon alcohol esters, N, N- pairs-[3- (3,5- di-tert-butyl-hydroxy phenyls) propiono] hexamethylene diamine, (the tertiary fourths of 2,4- bis- of phosphorous acid three
Base phenyl ester), at least one of double [3- (3- di-t-butyl -4- hydroxy-5-methyl bases phenyl)] acrylonitrile of triethylene glycol.
8. flame-retardant PBT engineering plastic composite material according to claim 7, it is characterised in that the antioxidant is by four
[3- (3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester and phosphorous acid three (2,4- 6- di-tert-butyl phenyl esters) are by weight
Than for 1:1.5-2.5 composition.
9. flame-retardant PBT engineering plastic composite material according to claim 3, it is characterised in that the lubricant is ethylene
At least one of bis-fatty acid amides and pentaerythritol stearate.
10. flame-retardant PBT engineering plastic composite material according to claim 9, it is characterised in that the lubricant is by season
Penta tetrol stearate and ethylene bis-fatty acid amides are 1 by weight:1.2-1.5 composition.
11. flame-retardant PBT engineering plastic composite material according to claim 3, it is characterised in that the coupling agent be γ-
At least one of glycidyl ether oxygen propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane.
12. flame-retardant PBT engineering plastic composite material according to claim 11, it is characterised in that the coupling agent be γ-
Glycidyl ether oxygen propyl trimethoxy silicane.
13. flame-retardant PBT engineering plastic composite material according to claim 11, it is characterised in that the bulking agent is
ABS-g-MAH。
14. flame-retardant PBT engineering plastic composite material according to claim 3, it is characterised in that the toughener is second
Alkene-methyl methacrylate-glycidyl acrylate copolymer, methyl methacrylate-butyl acrylate bipolymer,
In Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer, diallyl phthalate-vinyl chloride copolymer
At least one.
15. the preparation method of the flame-retardant PBT engineering plastic composite material described in claim any one of 3-14, it is characterised in that
Comprise the following steps：
(a), the composition stirring 10-20min in addition to alkali-free glass fibre is mixed, speed of agitator is 100-500r/min；
(b), the composition mixed is granulated by Bitruder melting extrusion, processing conditions is：Double screw extruder one
200-210 DEG C of area's temperature, two 210-230 DEG C of area's temperature, three 210-230 DEG C of area's temperature, four 210-230 DEG C of area's temperature, five area's temperature
200-220 DEG C of degree, six 200-220 DEG C of area's temperature, seven 200-220 DEG C of area's temperature, eight 210-230 DEG C of area's temperature；
Wherein, alkali-free glass fibre is added in the stage casing of Bitruder, the alkali-free glass fibre soaks through silane coupler
Bubble processing；
Screw speed is 350-500r/min.
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| CN106243638B (en) * | 2015-06-08 | 2018-04-13 | 江苏理工学院 | Halogen-free flame-retardant PBT (polybutylene terephthalate) material |
| TWI598482B (en) * | 2015-10-27 | 2017-09-11 | 財團法人紡織產業綜合研究所 | Fiber, fiber-masterbatch, and method of fabricating the same |
| US10982088B2 (en) * | 2016-09-30 | 2021-04-20 | Sabic Global Technologies B.V. | Polymer composition comprising poly(butylene terephthalate) |
| CN108102359A (en) * | 2017-12-27 | 2018-06-01 | 重庆普利特新材料有限公司 | A kind of environmentally protective, high-performance, high CTI flame-retardant reinforced nylon materials and preparation method thereof |
| CN109337305A (en) * | 2018-10-12 | 2019-02-15 | 浙江富丽新材料有限公司 | A kind of high CTI fire retardant PBT with no halogen resin and preparation method thereof |
| CN112144204B (en) * | 2020-10-09 | 2021-06-25 | 东莞澳思制衣有限公司 | Flame-retardant functional garment material preparation equipment |
| CN113683730A (en) * | 2021-08-27 | 2021-11-23 | 西华大学 | Corn straw cellulose-based water-absorbent resin composite material and preparation method thereof |
| CN115449207B (en) * | 2022-09-21 | 2024-02-23 | 中车青岛四方机车车辆股份有限公司 | Halogen-free flame-retardant reinforced PC composite material and preparation method and application thereof |
| CN118126384A (en) * | 2024-05-10 | 2024-06-04 | 江苏恒力化纤股份有限公司 | Preparation method of flame-retardant smoke-suppressing polyester film |
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