CN101302305B - Use of diantimony trioxide as nylon main flame retardant, and product and preparation thereof - Google Patents
Use of diantimony trioxide as nylon main flame retardant, and product and preparation thereof Download PDFInfo
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Abstract
The invention discloses an application of a main fire retardant which takes nano diantimony trioxide prepared by the high-frequency plasma method as fire retarding nylon. According to the weight portions, the fire retarding nylon is prepared by 90 to 98 portions of nylon and 2 to 10 portions of fire retardant; the fire retardant is the nano diantimony trioxide prepared by the high-frequency plasma method; compared with prior art, the invention takes the nano diantimony trioxide prepared by the high-frequency plasma method as a main fire retardant to be used to the production of the fire retarding nylon, which provides a new halogen-free fire retardant for nylon; moreover, the method for preparing the fire retarding is simple and suitable for the mass production, and the prepared nylon has good fire retarding effect, and the nano diantimony trioxide undergoing modification treatment can also make the fire retarding nylon possess of better mechanical property; because the nano diantimony trioxide prepared by the high-frequency plasma method is used as the main fire retardant, the addition quantity is less than 10 percent; the preparation method is simple, and the production cost is effectively lowered.
Description
Technical field
The present invention relates to second purposes and products thereof and the preparation method of antimonous oxide, particularly relate to of the application of the nanmeter antimong trioxide of high frequency plasma method preparation as nylon main flame retardant, and fire-retardant nylon and preparation method thereof.
Background technology
The fire retardant that is applied in the fire-retardant nylon (PA6) mainly contains halogenated flame retardant, phosphorus flame retardant, nitrogen flame retardant, metallic compound fire retardant and their compound flame retardant etc.With regard to global fire retardant consumption, halogenated flame retardant is still one of organic fire-retardant of current production rate maximum, in halogenated flame retardant based on bromide fire retardant (account for halogenated flame retardant total amount 80%).Most of halogenated flame retardant can generate toxic flue dust, corrosive gases etc. when burning, because dioxin (Dioxin) problem in recent years, the part bromide fire retardant is banned use of by the RoSH of European Union instruction.The characteristics of various flame-proof PA 6s see the following form:
| Fire retardant material | Halogen flame retardant PA6 | Red phosphorus flame-retardant PA6 | Mg(OH) 2Flame-proof PA 6 | Melamine class flame-proof PA 6 |
| Flame retarding efficiency to PA6 | High | Higher | Lower | Higher |
| Glass is strengthened the flame retarding efficiency of PA6 | High | In | Low | Low |
| The toxic substance release rate | High | Less | Do not have | Do not have |
| Density | In | Little | Greatly | Little |
| Rigidity | In | Good | Good | In |
| Toughness | Relatively poor | In | Relatively poor | Good |
| Arc resistance | Relatively poor | Good | Good | In |
| The amount of being fuming | Greatly | In | Little | Little |
| Tint permanence | In | Difference | Difference | Good |
Along with the raising of domestic environmental consciousness and the variation of world's fire retardant market structure, domestic halogen-free flameproof PA6 industry has had significant progress in recent years, but there be big gap with comparing still abroad, be mainly reflected in following several respects: the kind of fire retardant that is applicable to PA6 is few, of low quality, output is little, can not form scale effect; The tradition halogenated flame retardant is used more, the halogen-free flame retardants underexploitation, and the currently available products flame retarding efficiency is low, cost an arm and a leg, lack the market competitiveness; The flame-proof PA 6 product of high-performance and multifunction lacks; Therefore further accelerate the development of novel halogen-free flame-retardant agent, develop the flame-proof PA 6 product of high comprehensive performance energetically, shorten scientific payoffs to the transformation period of industrialization, the breaks through foreign environmental regulation is severe challenge and urgent tasks that domestic PA6 industrial community faces to China's formed technology barriers of electronic product outlet industry as early as possible.
At present, antimonous oxide is applied in the flame-retardant polymer mainly as the synergist of main flame retardant, the flame retardant properties that singly adds antimonous oxide in polymkeric substance does not have obvious change, has only with main flame retardant the effect that just main flame retardant is played synergy when shared by a certain percentage.
Summary of the invention
Technical problem to be solved by this invention provides the application of the nanmeter antimong trioxide of high frequency plasma method preparation as main flame retardant in the fire-retardant nylon, it is fire-retardant nylon of main flame retardant and preparation method thereof that a kind of nanmeter antimong trioxide with the preparation of high frequency plasma method is provided simultaneously, to improve the flame retardant properties of nylon, improve the mechanical property of nylon simultaneously, reduce production costs.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme:
The nanmeter antimong trioxide of high frequency plasma method preparation is as the application of the main flame retardant of fire-retardant nylon.
The nanmeter antimong trioxide of high frequency plasma method preparation is as the application of the main flame retardant of fire-retardant Nylon 6.
A kind of fire-retardant nylon: according to listed as parts by weight, according to listed as parts by weight, it mainly is to be prepared from for 2～10 parts by 90～98 parts of nylon and fire retardant, and fire retardant is the nanmeter antimong trioxide of high frequency plasma method preparation.
Fire retardant in the above-mentioned fire-retardant nylon can carry out modification with silane coupling agent to be handled.Can improve the mechanical property of fire-retardant nylon like this.
In the above-mentioned fire-retardant nylon, can also add melamine cyanurate.The composite use of nanmeter antimong trioxide of melamine cyanurate and high frequency plasma method preparation can synergy, strengthens its flame retardant effect.
After adding melamine cyanurate, fire-retardant nylon mainly is to be prepared from for 5～9 parts by 1～5 part of nanmeter antimong trioxide and melamine cyanurate that 0～98 part of nylon 9, high frequency plasma method prepare.
In above-mentioned fire-retardant nylon, can also add 1～5 part of maleic anhydride graft POE (Polyolefin elastomer, polyolefin elastomer) mechanical property of fire-retardant nylon is improved.
Used nylon raw material is a nylon 6 in the aforementioned fire-retardant nylon.
The nanmeter antimong trioxide of the high frequency plasma method preparation described in the technical solution of the present invention is that method described in the patent No. ZL2005102000098 is produced, and is mainly used in the electronic ceramics at present.The nanmeter antimong trioxide of high frequency plasma method preparation is applied in the nylon as main flame retardant, and the contriver has carried out a large amount of experiments, has drawn above-mentioned technical scheme.
The contriver has carried out contrast verification to the performance of fire-retardant nylon, and is specific as follows:
1, specimen preparation
1.1, unmodified fire-retardant nylon
Raw material: the nanmeter antimong trioxide (singly adding) of 900-980g nylon 6, the preparation of 20-100g high frequency plasma method
The preparation method: the nanmeter antimong trioxide of nylon 6 and the preparation of high frequency plasma method was dried 8-10 hour under 90 ℃ of conditions respectively, mix, extrude with forcing machine, pelletizing is dried pellet 8-10 hour under 90 ℃ of conditions, promptly.
1.2, modified flame-retardant nylon
Raw material: nanmeter antimong trioxide (singly adding), the 1g silane coupling agent of 900-980g nylon 6, the preparation of 20-100g high frequency plasma method
Preparation method: the nanmeter antimong trioxide of getting the preparation of high frequency plasma method, oven dry is 8-10 hour under 90 ℃ of conditions, add the high-speed mixer that is warming up to 80～100 ℃ in advance, pre-assigned silane coupler modified liquid is sprayed on the nanmeter antimong trioxide powder in proportion, capping was stirred 15-30 minute, derive powder, oven dry more than 120 ℃ 2 hours, mix with 8-10 hour nylon 6 of oven dry under 90 ℃ of conditions, extrude with forcing machine, pelletizing is dried pellet 8 hours under 100 ℃ of conditions, promptly.
1.3, unmodified compositional flame-retardant nylon
Raw material: nanmeter antimong trioxide, the 50-90g melamine cyanurate of 900-980g nylon 6, the preparation of 10-50g high frequency plasma method
Preparation method: the nanmeter antimong trioxide of nylon 6, melamine cyanurate and the preparation of high frequency plasma method was dried 8-10 hour under 90 ℃ of conditions respectively, mix, extrude, pelletizing with forcing machine, pellet was dried 8-10 hour under 90 ℃ of conditions, promptly.
1.4, modification compositional flame-retardant nylon
Raw material: nanmeter antimong trioxide, 50-90g melamine cyanurate, the 10-50g maleic anhydride graft POE of 850-890g nylon 6, the preparation of 10-50g high frequency plasma method
Preparation method: the nanmeter antimong trioxide of nylon 6, melamine cyanurate and the preparation of high frequency plasma method was dried 8-10 hour under 90 ℃ of conditions respectively, nanmeter antimong trioxide, melamine cyanurate, the maleic anhydride graft POE of nylon 6, the preparation of high frequency plasma method are mixed, extrude with forcing machine, pelletizing, pellet was dried 8-10 hour under 90 ℃ of conditions, promptly.
2, method for testing performance
2.1. limiting oxygen index(LOI) (LOI) test
Carry out according to ASTM D 2863-2006a standard, specimen size is 100mm * 10mm * 4mm; Used instrument is the oxygen index instrument (model HC-2C) in Sichuan University's degraded and flame retarded polymeric material research centre.
2.2. vertical combustion UL94 rank test
Carry out according to the GB/T2408-1996 standard, specimen size is 125mm * 12.7mm * 3.2mm; Used instrument is UL94 horizontal/vertical burning tester (model SH5300, a China).
2.3. the taper calorimeter detects:
Carry out according to ASTM E1354-04a standard, specimen size is 50mm * 50mm * 10mm; Used instrument is the taper calorimeter in Engineering Research Center degraded of the environmental friendliness macromolecular material the Ministry of Education of Sichuan University and flame retarded polymeric material research centre.
2.4.TG analyze: carry out on TGA (model Q50, the U.S.) thermal analyzer, (1 20ml/min, temperature rise rate are 30 ℃/min (0-300 ℃) to air atmosphere, 10 ℃/min (300-650 ℃).
2.5. mechanical property detects: the tensile strength of plastics, flexural strength and modulus in flexure are pressed ASTM D 638-99, ASTM D 790-99 test respectively on WDW-10C type microcomputer control electronics universal testing machine; The shock strength of plastics (socle girder) is pressed ASTM D 256-97 test on ZBC-48 type liquid crystal type plastics-pendulum impact experiment machine.
3, Performance Detection data
3.1, flame retardant properties
3.1.1 limiting oxygen index(LOI):
| Composition | Limiting oxygen index(LOI) (%) |
| Pure PA6 | 25.9 |
| Unmodified fire-retardant nylon | 26.0-30.0 |
| Modified flame-retardant nylon | 26.0-29.8 |
| Unmodified compositional flame-retardant nylon | 28.3-32.5 |
| Modification compositional flame-retardant nylon | 28.3-32.5 |
3.1.2 vertical combustion:
| Composition | Vertical combustion |
| Pure PA6 | FV-2 |
| Unmodified fire-retardant nylon | FV-0* |
| Modified flame-retardant nylon | FV-0* |
| Unmodified compositional flame-retardant nylon | FV-0* |
| Modification compositional flame-retardant nylon | FV-0* |
3.1.3, the taper calorimeter
As shown in Figure 1, A is pure nylon 6 among the figure, and D2 is that the nanmeter antimong trioxide (unmodified) for preparing with the high frequency plasma method is the fire-retardant nylon of main flame retardant, and the heat release rate peak value of A is about 800KW/m
2, the peak value of D2 is about 740KW/m
2, and the time that D2 arrives the heat release peak value significantly postpone than A, significantly reduced the fire odds.
3.2, mechanical property
Being compared as follows of the best mechanical property of fire-retardant nylon that proportioning of the present invention is made:
3.2.1, tensile property:
3.2.2, impact property:
| Composition | Shock strength KJ/m 2 |
| Pure PA6 | 5.76 |
| Unmodified fire-retardant nylon | 4.65 |
| Modified flame-retardant nylon | 5.34 |
3.2.3, bending property:
| Composition | Bending load N | Flexural strength Mpa | Modulus in flexure Gpa |
| Pure PA6 | ?146 | ?82.1 | ?2.076 |
| Unmodified fire-retardant nylon | ?168 | ?94.5 | ?2.386 |
| Modified flame-retardant nylon | ?224.5 | ?129.3 | ?3.331 |
3.3, thermal degradation performance:
3.3.1, the comparison of pure nylon and unmodified fire-retardant nylon
As shown in Figure 2, the thermal destruction of pure nylon 6 extrapolation temperature is 403.14 ℃, and decomposing end temp is 467.65 ℃, and total thermal weight loss ratio is 95.11%; The thermal destruction extrapolation temperature of unmodified nanmeter antimong trioxide/nylon 6 is 423.33 ℃, and decomposing end temp is 473.02 ℃, and total thermal weight loss ratio is 95.96%.Unmodified antimonous oxide makes the thermal destruction extrapolation temperature of nylon 6 improve about 20 ℃, and total thermal weight loss ratio changes little.
3.3.2, the comparison of pure nylon and modified flame-retardant nylon
As shown in Figure 3, the thermal destruction of pure nylon 6 extrapolation temperature is 403.14 ℃, and decomposing end temp is 467.65 ℃, and total thermal weight loss ratio is 95.11%; The thermal destruction extrapolation temperature of silane coupler modified nanmeter antimong trioxide/nylon 6 is 417.80 ℃, and decomposing end temp is 476.73 ℃, and total thermal weight loss ratio is 98.03%.Unmodified antimonous oxide makes the thermal destruction extrapolation temperature of nylon 6 improve about 15 ℃, and total thermal weight loss ratio changes little.
4, conclusion
4.1. the adding of the nanmeter antimong trioxide main flame retardant of high frequency plasma method preparation obviously improves the flame retardant properties of nylon material;
4.2. singly add the nanmeter antimong trioxide of unmodified high frequency plasma method preparation, Flame Retardancy reaches requirement, but material mechanical performance worsens; Available silane coupling agent improves the mechanical property of material.
4.3. the nanmeter antimong trioxide of unmodified high frequency plasma method preparation is added in the nylon with melamine cyanurate is composite, Flame Retardancy reaches requirement, but the material mechanical performance deterioration; Available maleic anhydride graft POE improves the mechanical property of material.
Compared with prior art, the present invention is applied to the nanmeter antimong trioxide of high frequency plasma method preparation the production of fire-retardant nylon as main flame retardant, a kind of new halogen-free flame retardants that is applicable to nylon is provided, and the preparation method is simple for this fire retardant, be fit to scale production, prepared nylon has the good flame effect, nanmeter antimong trioxide is carried out also can making fire-retardant nylon have good mechanical property after modification is handled, heavy metal content is in strict conformity with the requirement of the RoSH of European Union instruction, and, nanmeter antimong trioxide with the preparation of high frequency plasma method is a main flame retardant, its addition is less than 10%, and the preparation method is simple, has effectively reduced production cost.
Description of drawings
Fig. 1 is the heat release rate and the time relation comparison diagram of pure nylon 6 and unmodified fire-retardant Nylon 6; A curve: pure nylon 6, D2 curve: unmodified fire-retardant Nylon 6.
Fig. 2 is the comparison of pure nylon 6 and unmodified fire-retardant Nylon 6 thermal destruction curve; A curve: pure nylon 6, D2 curve: unmodified fire-retardant Nylon 6.
Fig. 3 is the comparison of unmodified fire-retardant Nylon 6 and modified flame-retardant nylon 6 thermal destruction curves; Article two, curve almost overlaps.
Embodiment
Embodiment 1:
Raw material: the nanmeter antimong trioxide (singly adding) of 900g nylon 6, the preparation of 100g high frequency plasma method
The preparation method: the nanmeter antimong trioxide of nylon 6 and the preparation of high frequency plasma method was dried 8～10 hours under 90 ℃ of conditions respectively, mix, extrude at 220～250 ℃ with forcing machine, pelletizing is dried pellet 8-10 hour under 90 ℃ of conditions, promptly.
Embodiment 2: modified flame-retardant nylon
Raw material: nanmeter antimong trioxide (singly adding), the 1g silane coupling agent of 980g nylon 6, the preparation of 20g high frequency plasma method
Preparation method: the nanmeter antimong trioxide of getting the preparation of high frequency plasma method, oven dry is 10 hours under 80 ℃ of conditions, add the high-speed mixer that is warming up to 80～100 ℃ in advance, pre-assigned silane coupler modified liquid is sprayed on the nanmeter antimong trioxide powder, capping was stirred 25 minutes, derive powder, oven dry more than 120 ℃ 2 hours, mix with 8-10 hour nylon 6 of oven dry under 90 ℃ of conditions, extrude at 220～250 ℃ with forcing machine, pelletizing is dried pellet 8 hours under 100 ℃ of conditions, promptly.
The preparation of silane coupler modified solution: get silane coupling agent and add water and dehydrated alcohol, be mixed with the modified solution that contains silane coupling agent 20%, water 8%, dehydrated alcohol 72%.
Embodiment 3: unmodified compositional flame-retardant nylon
Raw material: nanmeter antimong trioxide, the 80g melamine cyanurate of 950g nylon 6, the preparation of 30g high frequency plasma method
Preparation method: the nanmeter antimong trioxide of nylon 6, melamine cyanurate and the preparation of high frequency plasma method was dried 8 hours under 100 ℃ of conditions respectively, mix, extrude pelletizing at 220～250 ℃ with forcing machine, pellet was dried 8-10 hour under 90 ℃ of conditions, promptly.
Embodiment 4: modification compositional flame-retardant nylon
Raw material: nanmeter antimong trioxide, 50g melamine cyanurate, the 10g maleic anhydride graft POE of 930g nylon 6, the preparation of 50g high frequency plasma method
Preparation method: the nanmeter antimong trioxide of nylon 6, melamine cyanurate and the preparation of high frequency plasma method was dried 8 hours under 90 ℃ of conditions respectively, nanmeter antimong trioxide, melamine cyanurate, the maleic anhydride graft POE of nylon 6, the preparation of high frequency plasma method are mixed, extrude at 220～250 ℃ with forcing machine, pelletizing, pellet was dried 8-10 hour under 90 ℃ of conditions, promptly.
Claims (1)
1. modification compositional flame-retardant nylon, it is characterized in that: the raw material of described fire-retardant nylon is: nanmeter antimong trioxide, 50-90g melamine cyanurate, the 10-50g maleic anhydride graft POE of 850-890g nylon 6, the preparation of 10-50g high frequency plasma method, and wherein POE is a polyolefin elastomer; Adopt following method preparation:
The nanmeter antimong trioxide of nylon 6, melamine cyanurate and the preparation of high frequency plasma method was dried 8-10 hour under 90 ℃ of conditions respectively, nanmeter antimong trioxide, melamine cyanurate, the maleic anhydride graft POE of nylon 6, the preparation of high frequency plasma method are mixed, extrude with forcing machine, pelletizing, pellet was dried 8-10 hour under 90 ℃ of conditions, promptly.
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| CN109354714B (en) * | 2018-11-15 | 2020-09-04 | 江西盛达隆科技有限公司 | Antimony trioxide reinforcing agent and application thereof in high-strength acrylic sheet |
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