CN104151794B - Four (O, O-dibutyl phosphoryl) glycoluril fire retardant combination and application process thereof - Google Patents
Four (O, O-dibutyl phosphoryl) glycoluril fire retardant combination and application process thereof Download PDFInfo
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Abstract
The present invention relates to a kind of four (O, O-dibutyl phosphoryl) glycoluril fire retardant combination. This fire retardant combination is by four (O; O-dibutyl phosphoryl) glycoluril (TBG) with in melamine cyanurate (MCA), melamine polyphosphate (MPP) and diethyl phosphinic acids aluminium (1240) any one, two or three by composite, even mixing of weight ratio makes arbitrarily; and four (O, O-dibutyl phosphoryl) glycoluril weight fraction in fire retardant combination is greater than zero. Fire retardant combination of the present invention, has multielement Synergistic, good with material compatibility, fire resistance is high, halogen-free environmental, can reduce the advantages such as application cost, can be used for the fire retardant of polyester, polyamide etc.
Description
Technical field
The present invention relates to a kind of four (O, O-dibutyl phosphoryl) glycoluril fire retardant combination and application process thereof, this fire retardant combination can be used for the fire-retardant of the engineering plastics such as polyester, polyamide.
Background technology
Polyester material is the every field to modern society through century-old development rapid permeability, and is bringing into play more and more important effect, but the inflammable characteristic of most of polyester makes material be limited by very large again in a lot of application aspect. Along with the enhancing of people's safety and environmental protection consciousness, develop the important directions that flame retarding efficiency is high, harm and the little polyester flame-retardant agent of environmental pollution are become to research. Phosphorus nitrogen is synergistic fire retardant, the feature such as have Halogen, low toxicity, decomposition temperature is high, machining property is good. Therefore, phosphorus-nitrogen containing flame retardant at home and abroad more and more comes into one's own in fire-retardant research, wherein by composite cooperative flame retardant improve fire retardant usefulness, to reduce production costs be the applied research topic of awfully hot door.
The invention discloses a kind of four (O; O-dibutyl phosphoryl) glycoluril fire retardant combination; in this fire retardant combination four (O, O-dibutyl phosphoryl) glycoluril has symmetrical P-N-C-N-P conjugation and mixes imide structure, contains many many nitrogen of phosphorus ignition-proof elements. Its composition cooperative flame retardant is effective, and stability is high, has good compatibility with macromolecular material, is adapted to high temperature process, does not reduce the mechanical strength of material. This fire retardant combination preparation method is simple simultaneously, can reduce costs, and has good application prospect.
Summary of the invention
One of object of the present invention is to propose a kind of four (O, O-dibutyl phosphoryl) glycoluril fire retardant combination. This fire retardant combination cooperative flame retardant usefulness is high, and halogen-free environmental, for polyester flame-retardant agent, polyamide fire retardant etc., can meet environmental requirement, has good application and development prospect.
Another object of the present invention is to propose a kind of four (O, O-dibutyl phosphoryl) glycoluril fire retardant combination application process in polyester PET and PBT.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of four (O; O-dibutyl phosphoryl) glycoluril fire retardant combination; it is by four (O; O-dibutyl phosphoryl) glycoluril (TBG) with in melamine cyanurate (MCA), melamine polyphosphate (MPP) and diethyl phosphinic acids aluminium (1240) any one, two or three by composite, even mixing of weight ratio makes arbitrarily; and four (O, O-dibutyl phosphoryl) glycoluril weight fraction in fire retardant combination is greater than zero. But consider reduction and the fire resistance of price, the compound proportion that recommendation tables 1 is explained. Table 1 is the percentage that each component accounts for fire retardant combination weight.
The each formulation ratio table of table 1 composite flame-retardant agent
Wherein the structure of TBG is shown below:
The structure of MCA is shown below:
The structure of MPP is shown below:
1240 structure is shown below:
The application process of fire retardant combination of the present invention, is characterized in that as mentioned above, and the method is:
In polyester PET or PBT, add formula 1, formula 2, formula 3, formula 4, formula 5, formula 6 or formula 7 fire retardant combination, mix, injection moulding or the processing such as extrude under melt temperature.
Compared with prior art, beneficial effect of the present invention is:
(1) four in fire retardant combination component of the present invention (O, O-dibutyl phosphoryl) glycoluril is compounds nitrogenous, the two ignition-proof elements of phosphorus, and its many phosphorus, many nitrogen make this fire retardant have good fire resistance; Molecule has symmetrical P-N-C-N-P conjugation and mixes imide structure, polyester structure, and itself and other composition components is easy to compatibility, and has good compatibility with macromolecular material, is easy to disperse, and does not separate out, and does not reduce the mechanical strength of material.
(2) fire retardant combination of the present invention does not conform to halogen, meets environmental requirement, has good application and development prospect.
(3) fire retardant combination of the present invention, contains phosphorus, nitrogen or aluminium element, can produce synergistic fire retardation, and polyester PET and PBT etc. are had to good flame-retarded efficiency.
(4) preparation method of fire retardant combination of the present invention is simple, and equipment investment is few, can greatly reduce expensive 1240 consumption during with 1240 composite use, can reduce production costs, and application is convenient.
(5) when fire retardant combination of the present invention has the charcoal of having of one's own effect burning, do not drip, become carbon flame-proof performance good.
Detailed description of the invention
Provide embodiment below so that the invention will be further described, in order to contrast the effect of composite flame-retardant agent, also provided the embodiment that one-component TBG applies in polyester. But be pointed out that following examples can not be interpreted as limiting the scope of the invention, some nonessential improvement that the person skilled in the art of this area foregoing according to the present invention is made the present invention and adjustment still belong to protection scope of the present invention.
Embodiment 1 adds the TBG of different proportion in polyester PET, mixes, and extrudes the batten of diameter 3mm with XJ-01 type extruder under melt temperature, surveys its limited oxygen index with HC900-2 type oxygen index measurer, the results are shown in Table 2.
The fire resistance of table 2 fire retardant TBG to PET
Embodiment 2 adds TBG and the MCA of different proportion in polyester PET, mixes, and extrudes the batten of diameter 3mm with XJ-01 type extruder under melt temperature, surveys its limited oxygen index with HC900-2 type oxygen index measurer, the results are shown in Table 3.
The composite fire resistance to PET of table 3 fire retardant TBG and MCA
Table 3 can find out, when 12 parts of TBG and 8 parts of composite uses of MCA, limited oxygen index has improved 3 during than the independent use of TBG, reaches 29, has well fire-retardant collaborative usefulness. And MCA is more cheap, can reduce costs.
Embodiment 3 adds TBG and the MPP of different proportion in polyester PET, mixes, and extrudes the batten of diameter 3mm with XJ-01 type extruder under melt temperature, surveys its limited oxygen index with HC900-2 type oxygen index measurer, the results are shown in Table 4.
The composite fire resistance to PET of table 4 fire retardant TBG and MPP
Table 4 can find out, when 12 parts of TBG and 8 parts of composite uses of MPP, limited oxygen index has improved 3 during than the independent use of TBG, reaches 29, has good cooperative flame retardant usefulness.
Embodiment 4 adds the TBG and 1240 of different proportion in polyester PET, mixes, and extrudes the batten of diameter 3mm with XJ-01 type extruder under melt temperature, surveys its limited oxygen index with HC900-2 type oxygen index measurer, the results are shown in Table 5.
Table 5 fire retardant TBG and the 1240 composite fire resistances to PET
Table 5 can find out, when 12 parts of TBG and 8 part of 1240 composite use, limited oxygen index has improved 4 during than the independent use of TBG, reaches 30, and performance has good cooperative flame retardant synergistic effect. When consumption when 1240 increases, flame retardant effect is more obvious. But 1240 price is very expensive, thereby TBG and 1240 compositely can reduce by 1240 consumption, reduce costs, and can produce good cooperative flame retardant effect.
Embodiment 5 adds TBG, MCA and the MPP of different proportion in polyester PET, mixes, and extrudes the batten of diameter 3mm with XJ-01 type extruder under melt temperature, surveys its limited oxygen index with HC900-2 type oxygen index measurer, the results are shown in Table 6.
The composite fire resistance to PET of table 6 fire retardant TBG, MCA and MPP
Table 6 can find out, 12 parts of TBG, 4 parts of MCA and 4 parts of MPP are composite, and when use, limited oxygen index has improved 4 during than the independent use of TBG, reaches 30, has good cooperative flame retardant usefulness.
Embodiment 6 adds TBG, the MCA and 1240 of different proportion in polyester PET, mixes, and extrudes the batten of diameter 3mm with XJ-01 type extruder under melt temperature, surveys its limited oxygen index with HC900-2 type oxygen index measurer, the results are shown in Table 7.
Table 7 fire retardant TBG, MCA and the 1240 composite fire resistances to PET
Table 7 can find out, when 12 parts of TBG, 4 parts of MCA and 4 part of 1240 composite use, limited oxygen index has improved 4 during than the independent use of TBG, reaches 30, has good cooperative flame retardant usefulness. In the time that the consumption of MCA and 1240 increases, flame retardant effect can be better, but due to 1240 costlinesses, consider cost, when application, should reduce by 1240 consumption as far as possible.
Embodiment 7 adds TBG, the MPP and 1240 of different proportion in polyester PET, mixes, and extrudes the batten of diameter 3mm with XJ-01 type extruder under melt temperature, surveys its limited oxygen index with HC900-2 type oxygen index measurer, the results are shown in Table 8.
Table 8 fire retardant TBG, MPP and the 1240 composite fire resistances to PET
Table 8 can find out, when 12 parts of TBG, 4 parts of MPP and 4 part 1240 and composite use, limited oxygen index has improved 4 during than the independent use of TBG, reaches 30, has good cooperative flame retardant usefulness. In the time that the consumption of MPP and 1240 increases, flame retardant effect can be better, but due to 1240 costlinesses, consider cost, when application, should reduce by 1240 consumption as far as possible.
Embodiment 8 adds TBG, MCA, the MPP and 1240 of different proportion in polyester PET, mixes, and extrudes the batten of diameter 3mm with XJ-01 type extruder under melt temperature, surveys its limited oxygen index with HC900-2 type oxygen index measurer, the results are shown in Table 9.
Table 9 fire retardant TBG, MCA, MPP and the 1240 composite fire resistances to PET
Table 9 can find out, when 10 parts of TBG, 4 parts of MCA, 4 parts of MPP and 2 part of 1240 composite use, limited oxygen index has improved 3 during than the independent use of TBG, reaches 29, has good cooperative flame retardant usefulness. When consumption when 1240 increases, flame retardant effect can be better, but due to 1240 costlinesses, consider cost, when application, should reduce by 1240 consumption as far as possible.
Embodiment 9 adds the TBG of different proportion in polyester PBT, mixes, and extrudes the batten of diameter 3mm with XJ-01 type extruder under melt temperature, surveys its limited oxygen index with HC900-2 type oxygen index measurer, the results are shown in Table 10.
The fire resistance of table 10 fire retardant TBG to PBT
Embodiment 10 adds TBG, MCA and the MPP of different proportion in polyester PBT, mixes, and extrudes the batten of diameter 3mm with XJ-01 type extruder under melt temperature, surveys its limited oxygen index with HC900-2 type oxygen index measurer, the results are shown in Table 11.
The composite fire resistance to PBT of table 11 fire retardant TBG, MCA and MPP
Table 11 can find out, when 12 parts of TBG, 4 parts of MCA and 4 parts of composite uses of MPP, limited oxygen index has improved 3 during than the independent use of TBG, reaches 29, has good cooperative flame retardant usefulness.
Embodiment 11 adds TBG, the MCA and 1240 of different proportion in polyester PBT, mixes, and extrudes the batten of diameter 3mm with XJ-01 type extruder under melt temperature, surveys its limited oxygen index with HC900-2 type oxygen index measurer, the results are shown in Table 12.
Table 12 fire retardant TBG, MCA and the 1240 composite fire resistances to PBT
Table 12 can find out, when 12 parts of TBG, 4 parts of MCA and 4 part of 1240 composite use, limited oxygen index has improved 4 during than the independent use of TBG, reaches 30, has good cooperative flame retardant usefulness. In the time that the consumption of MCA and 1240 increases, flame retardant effect can be better, but due to 1240 costlinesses, consider cost, when application, should reduce by 1240 consumption as far as possible.
Embodiment 12 adds TBG, the MPP and 1240 of different proportion in polyester PBT, mixes, and extrudes the batten of diameter 3mm with XJ-01 type extruder under melt temperature, surveys its limited oxygen index with HC900-2 type oxygen index measurer, the results are shown in Table 13.
Table 13 fire retardant TBG, MPP and the 1240 composite fire resistances to PBT
Table 13 can find out, when 12 parts of TBG, 4 parts of MPP and 4 part of 1240 composite use, limited oxygen index has improved 4 during than the independent use of TBG, reaches 30, has good cooperative flame retardant usefulness. In the time that the consumption of MPP and 1240 increases, flame retardant effect can be better, but due to 1240 costlinesses, consider cost, when application, should reduce by 1240 consumption as far as possible.
Embodiment 13 adds TBG, MCA, the MPP and 1240 of different proportion in polyester PBT, mixes, and extrudes the batten of diameter 3mm with XJ-01 type extruder under melt temperature, surveys its limited oxygen index with HC900-2 type oxygen index measurer, the results are shown in Table 14.
Table 14 fire retardant TBG, MCA, MPP and the 1240 composite fire resistances to PBT
Table 14 can find out, when 10 parts of TBG, 4 parts of MCA, 4 parts of MPP and 2 part of 1240 composite use, limited oxygen index has improved 5 during than the independent use of TBG, reaches 31, has good cooperative flame retardant usefulness. When consumption when 1240 increases, flame retardant effect can be better, but due to 1240 costlinesses, consider cost, when application, should reduce by 1240 consumption as far as possible.
Claims (2)
1. one kind four (0,0-dibutyl phosphoryl) glycoluril fire retardant combination, is characterized in that, this is fire-retardantAgent composition is that four (0,0-dibutyl phosphoryl) glycolurils and melamine cyanurate, melamine gather phosphorusIn hydrochlorate and diethyl phosphinic acids aluminium any one, two or three composite by weight ratio arbitrarily, evenly mixedCloses and make, and four (0,0-dibutyl phosphoryl) glycoluril weight fraction in fire retardant combination is greater than zero,
Wherein, the structure of four (0,0-dibutyl phosphoryl) glycoluril is shown below:
The structure of melamine cyanurate is shown below:
The structure of melamine polyphosphate is shown below:
The structure of diethyl phosphinic acids aluminium is shown below:
2. a kind of four (0,0-dibutyl phosphoryl) glycoluril fire retardant combination according to claim 1Application process is: in polyester PET or PBT, add four (0,0-dibutyl phosphoryls) of different proportion sweetUrea and melamine cyanurate or four (0,0-dibutyl phosphoryl) glycoluril and melamine polyphosphate orFour (0,0-dibutyl phosphoryl) glycolurils and diethyl phosphinic acids aluminium or four (0,0-dibutyl phosphoryl) are sweetUrea, melamine cyanurate and melamine polyphosphate or four (0,0-dibutyl phosphoryl) glycoluril,Melamine cyanurate and diethyl phosphinic acids aluminium or four (0,0-dibutyl phosphoryl) glycoluril, melamineAmine Quadrafos and diethyl phosphinic acids aluminium or four (0,0-dibutyl phosphoryl) glycoluril, melamine cyanureaHydrochlorate, melamine polyphosphate and diethyl phosphinic acids aluminium, mix, injection moulding or crowded under melt temperatureGo out processing.
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| CA2250995C (en) * | 1996-04-12 | 2006-10-31 | Clariant Gmbh | Synergistic flame retardant combination for thermoplastic polymers |
| ES2254053T3 (en) * | 1999-01-30 | 2006-06-16 | Clariant Produkte (Deutschland) Gmbh | COMBINATION OF IGNIFUGENT AGENTS FOR THERMOPLASTIC POLYMERS. |
| ATE439399T1 (en) * | 2004-05-13 | 2009-08-15 | Basf Se | FLAME RETARDANTS |
| CN103396450B (en) * | 2013-08-01 | 2015-09-16 | 苏州科技学院相城研究院 | Fire retardant four (0,0-dibutyl phosphoryl) glycoluril compounds and preparation method thereof |
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