CN106633187A - Safe and environment-friendly inorganic aluminum hypophosphite flame retardant and application thereof in PBT (polybutylene terephthalate) - Google Patents
Safe and environment-friendly inorganic aluminum hypophosphite flame retardant and application thereof in PBT (polybutylene terephthalate) Download PDFInfo
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Abstract
The invention belongs to the field of materials and discloses an environment-friendly inorganic aluminum hypophosphite flame retardant and an application thereof in a PBT (polybutylene terephthalate) composite. The flame retardant is obtained by adding a hydrogen phosphide absorbent during surface modification of inorganic aluminum hypophosphite. At the last stage of synthesis of aluminum hypophosphite, the hydrogen phosphide absorbent is added, so that the contact area between aluminum hypophosphite and the hydrogen phosphide absorbent reaches the maximum; besides, different surface modifiers are selected for surface treatment on aluminum hydroxide and the hydrogen phosphide absorbent, so that the heat stability of inorganic aluminum hypophosphite is improved, meanwhile, the compatibility of inorganic aluminum hypophosphite with resin is also improved, the shearing force during extrusion pelletizing processing is reduced, release of hydrogen phosphide from inorganic aluminum hypophosphite in the extrusion pelletizing process is further reduced, release of hydrogen phosphide of the inorganic aluminum hypophosphite flame retardant PBT composite reaches the minimum, and release limit (0.08 ppm) of hydrogen phosphide in VOC substance objects and management standard is met.
Description
Technical field
The invention belongs to Material Field, more particularly to a kind of environment friendly inorganic hypo-aluminum orthophosphate combustion inhibitor and its in poly- terephthaldehyde
Application in sour butanediol ester composite.
Background technology
At present, diethyl phosphinates are by German Clariant Corporation industrialized production.Phosphinates has good
Fire retardation, but its industrial production is relatively complex and costly, limits its using in a large number as fire retardant.Therefore, with secondary phosphine
The hypophosphites that hydrochlorate has analog structure is attracted wide attention.Hypophosphites as fire retardant be mainly hypo-aluminum orthophosphate,
Hypophosphorous acid lanthanum, cerous hypophosphate.
Hypo-aluminum orthophosphate, its molecular formula is Al (H2PO2)3, its phosphorus content height (41.89%), heat endurance and hydrolytic stability
Get well, plus man-hour does not cause the decomposition of polymer, can be used for the fire-retardant of Glass-fiber-reinforcpolybutylene polybutylene terephthalate material；
Halogenated flame retardant can be replaced to carry out polyurethane material flame-retardant modified；Can also cooperate with other fire retardants and use, advantage is mutual
Mend, effectively improve the fire resistance of material.But hypo-aluminum orthophosphate is in further practical application process, when temperature is higher
Micro phosphatization hydrogen release can be produced and put (10ppm), its course of reaction is as follows：Al(H2PO2)3==AlPO4+2PH3.And at home and abroad
VOC material objects and management standard in define product component hydrogen phosphide release limit amount：0.08ppm, so as to limit
Inorganic hypo-aluminum orthophosphate using in a large number as fire retardant.
The content of the invention
In order to overcome the shortcoming and deficiency of above-mentioned prior art, the primary and foremost purpose of the present invention is to provide a kind of safety and environmental protection
Inorganic hypo-aluminum orthophosphate combustion inhibitor.
Another object of the present invention is to provide the inorganic hypo-aluminum orthophosphate combustion inhibitor of above-mentioned safety and environmental protection in poly terephthalic acid fourth
Application in terephthalate composite.
The purpose of the present invention is realized by following proposal：
A kind of environment friendly inorganic hypo-aluminum orthophosphate combustion inhibitor, is that inorganic hypo-aluminum orthophosphate is being carried out to add phosphorus while surface is modified
Change what hydrogen absorbent was obtained, specifically prepared by following methods：
The aluminum sulfate solution of the one waterside sodium radio-phosphate,P-32 solution of 200mL, 8mol/L and 500mL, 5.5mol/L is mixed, then
70～100 DEG C of isothermal reaction 3h are heated to, the hydrogen phosphide absorbent of 20～30g is added, continuing will after constant temperature 0.5～1h of stirring
Temperature is down to 60～90 DEG C, adds 1～5g surfactants, stirs 0.1～0.5h, and cooling is precipitated, filters, by institute
Obtain washing of precipitate to be dried, gained powder is environment friendly inorganic hypo-aluminum orthophosphate combustion inhibitor.
Described hydrogen phosphide absorbent can be activated carbon, molecular sieve, activated carbon fiber, activated alumina, cupric oxide, oxidation
Zinc, nickel chloride, nickel nitrate, nickel sulfate, nickel acetate, postassium hypochlorite, calcium hypochlorite, calcium chloride, active aluminium hydroxide, zinc carbonate,
One or more mixtures in talcum powder.
Described surface modifier can be stearic acid, odium stearate, silane coupler, titanate coupling agent, Aluminate idol
At least one in connection agent.
Described silane coupler is silane coupler commonly used in the art, preferably methacryloxy front three
At least one in TMOS, 3- glycidyl ether oxygen propyl trimethoxy silicanes, Y- aminopropyl triethoxysilanes；It is described
Aluminate coupling agent be aluminate coupling agent commonly used in the art, preferably distearyl acyl-oxygen isopropyl Aluminate；Institute
The titanate coupling agent stated is titanate coupling agent commonly used in the art, preferably monoalkoxytitanates, pyrophosphate
At least one in titanate esters, monoalkoxy unrighted acid titanate esters.
Application of the above-mentioned environment friendly inorganic hypo-aluminum orthophosphate combustion inhibitor in polybutylene terephthalate (PBT) composite.
A kind of fire retardant polybutylene terephthalate prepared by above-mentioned environment friendly inorganic hypo-aluminum orthophosphate combustion inhibitor
Composite, specifically includes the component of following mass fraction：
Described polybutylene terephthalate (PBT) is Jiangsu Changchun 1100-211M；The glass is megalith EDR14-
2000-988A；The lubricant is Tissuemat E；The antioxidant is 1 for 1010,168 in mass ratio:1 mixture.
A kind of preparation method of above-mentioned fire retardant polybutylene terephthalate composite, specifically includes following step
Suddenly：
(1) at room temperature, by the inorganic hypo-aluminum orthophosphate combustion inhibitor of safety and environmental protection, lubricant and antioxidant in high-speed mixer
In mix 1～10min in 1000r/min～2000r/min, then add described polybutylene terephthalate (PBT) and exist
1000r/min～2000r/min mixes 5～15min, and then discharging is obtained mixed material；
(2) mixed material in step (1) is added in double screw extruder, while side feeding adds glass, 200
DEG C～230 DEG C of extruding pelletizations, then obtained fire retardant polybutylene terephthalate and be combined in 230 DEG C of injections with injection machine
Material.
The present invention has the following advantages and beneficial effect relative to prior art：
(1) in the final stage of synthesis hypo-aluminum orthophosphate, hydrogen phosphide absorbent, hydrogen phosphide absorbent is added in the liquid phase, to make
Its more preferable absorption is deposited on the hypo-aluminum orthophosphate particulate that reaction is generated, so that both contacts area reach maximization, is had
The hydrogen phosphide of hypo-aluminum orthophosphate release is more effectively absorbed in the very first time beneficial to hydrogen phosphide absorbent；
(2) from different stearic acid, odium stearate, silane coupler, aluminate coupling agent, titanate coupling agent to hydrogen
Aluminum oxide and hydrogen phosphide absorbent are surface-treated, and improve the heat endurance of inorganic hypo-aluminum orthophosphate, while improving it with tree
The compatibility of fat, reduces shearing force in extruding pelletization process, so as to further reduce inorganic time during extruding pelletization
Aluminum phosphate discharges hydrogen phosphide, so that the hydrogen phosphide release of inorganic hypo-aluminum orthophosphate fire retardant polybutylene terephthalate compound
Minimum is reached, meets hydrogen phosphide release limit amount (0.08ppm) in VOC material objects and management standard.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Agents useful for same can routinely be buied if no special instructions from market in embodiment.It is used in embodiment to gather to benzene two
Formic acid butanediol ester is Jiangsu Changchun 1100-211M；Glass used is megalith EDR14-2000-988A.
Each performance parameter is measured in accordance with the following methods in embodiment：
Flame retardant rating：Vertical burn test is carried out according to UL-94；
Tensile strength：According to GB/T 1040-2006；
The method of testing of phosphine release amount is：Sample to be tested 300g is taken, is placed in the hermetic bag of 19*13cm, addition 5～
10ml water, hermetic bag is sealed, and then hermetic bag is put in 80 DEG C of insulating boxs, is placed and take out after 2hr cooling more than 15min,
Detected with hydrogen phosphide detection pipe, the red point of GASTEC manual gas sampling pumps be directed at into 100, extracted 5 times repeatedly, every time between
Every 15s.
Embodiment 1
The waterside phosphorus of 200ml mono- is added in the four-neck flask (1L) equipped with reflux condensing tube, electric mixer and thermometer
Acid sodium solution (8mol/L).500ml aluminum sulfate solutions (5.5mol/L) are added in sodium hypophosphite solution again.90 DEG C are heated to,
After isothermal reaction 3h, 10g molecular sieves, 10g cupric oxide are added, continue constant temperature stirring 1h, cool the temperature to 60 DEG C, add 5g bis-
Stearoyl keto isopropoxy Aluminate, cooling, obtains white precipitate, filter, washing, be dried after obtain powder for safety and environmental protection
Inorganic hypo-aluminum orthophosphate combustion inhibitor.
Then by the inorganic hypo-aluminum orthophosphate combustion inhibitor 200g of safety and environmental protection manufactured in the present embodiment and 10gH108PE waxes,
1g1010,1g168 are added in high mixer, and under room temperature, speed is 2000r/min mixing 3min, then by the poly- terephthaldehydes of 488g
Sour butanediol ester is added in high mixer, and speed is 2000r/min mixed at high speed 10min, and discharging is obtained compound.
By material mixed above double screw extruder extruding pelletization, temperature adjusts extruder main frame at 200 DEG C～230 DEG C
Frequency is 300r/min, and feeding frequency is 10Hz, and side feeding adds roving glass fiber 300g.Then obtained in 230 DEG C of injections with injection machine
To fire retardant polybutylene terephthalate compound A.
Embodiment 2
The waterside phosphorus of 200ml mono- is added in the four-neck flask (1L) equipped with reflux condensing tube, electric mixer and thermometer
Acid sodium solution (8mol/L).500ml aluminum sulfate solutions (5.5mol/L) are added in sodium hypophosphite solution again.90 DEG C are heated to,
After isothermal reaction 3h, 10g activated carbons, 10g cupric oxide are added, continue constant temperature stirring 1h, cool the temperature to 70 DEG C, add 4g bis-
Stearoyl keto isopropoxy Aluminate, cooling, obtains white precipitate, filter, washing, be dried after obtain powder for safety and environmental protection
Inorganic hypo-aluminum orthophosphate combustion inhibitor.
Then by the inorganic hypo-aluminum orthophosphate combustion inhibitor 200g of safety and environmental protection manufactured in the present embodiment and 10gH108PE waxes,
1g1010,1g168 are added in high mixer, and under room temperature, speed is 2000r/min mixing 3min, then by the poly- terephthaldehydes of 488g
Sour butanediol ester is added in high mixer, and speed is 2000r/min mixed at high speed 10min, and discharging is obtained compound.
By material mixed above double screw extruder extruding pelletization, temperature adjusts extruder main frame at 200 DEG C～230 DEG C
Frequency is 300r/min, and feeding frequency is 10Hz, and side feeding adds roving glass fiber 300g.Then obtained in 230 DEG C of injections with injection machine
To fire retardant polybutylene terephthalate compound B.
Embodiment 3
The waterside phosphorus of 200ml mono- is added in the four-neck flask (1L) equipped with reflux condensing tube, electric mixer and thermometer
Acid sodium solution (8mol/L).500ml aluminum sulfate solutions (5.5mol/L) are added in sodium hypophosphite solution again.90 DEG C are heated to,
After isothermal reaction 3h, 20g activated carbon fibers are added, continue constant temperature stirring 0.5h, cool the temperature to 80 DEG C, add 2gY- ammonia third
Ethyl triethoxy silicane alkane, cooling, obtains white precipitate, filter, washing, be dried after obtain the inorganic phosphorus that powder is safety and environmental protection
Sour aluminium fire retardant.
Then by the inorganic hypo-aluminum orthophosphate combustion inhibitor 200g of safety and environmental protection manufactured in the present embodiment and 10gH108PE waxes,
1g1010,1g168 are added in high mixer, and under room temperature, speed is 2000r/min mixing 3min, then by the poly- terephthaldehydes of 488g
Sour butanediol ester is added in high mixer, and speed is 2000r/min mixed at high speed 10min, and discharging is obtained compound.
By material mixed above double screw extruder extruding pelletization, temperature adjusts extruder main frame at 200 DEG C～230 DEG C
Frequency is 300r/min, and feeding frequency is 10Hz, and side feeding adds roving glass fiber 300g.Then obtained in 230 DEG C of injections with injection machine
To fire retardant polybutylene terephthalate compound C.
Embodiment 4
The waterside phosphorus of 200ml mono- is added in the four-neck flask (1L) equipped with reflux condensing tube, electric mixer and thermometer
Acid sodium solution (8mol/L).500ml aluminum sulfate solutions (5.5mol/L) are added in sodium hypophosphite solution again.90 DEG C are heated to,
After isothermal reaction 3h, 10g activated carbon fibers, 20g cupric oxide are added, continue constant temperature stirring 0.5h, cool the temperature to 80 DEG C, then added
Enter 1gY- aminopropyl triethoxysilanes, cool down, obtain white precipitate, filter, washing, be dried after obtain powder for safety and environmental protection
Inorganic hypo-aluminum orthophosphate combustion inhibitor.
Then by the inorganic hypo-aluminum orthophosphate combustion inhibitor 200g of safety and environmental protection manufactured in the present embodiment and 10gH108PE waxes,
1g1010,1g168 are added in high mixer, and under room temperature, speed is 2000r/min mixing 3min, then by the poly- terephthaldehydes of 488g
Sour butanediol ester is added in high mixer, and speed is 2000r/min mixed at high speed 10min, and discharging is obtained compound.
By material mixed above double screw extruder extruding pelletization, temperature adjusts extruder main frame at 200 DEG C～230 DEG C
Frequency is 300r/min, and feeding frequency is 10Hz, and side feeding adds roving glass fiber 300g.Then obtained in 230 DEG C of injections with injection machine
To fire retardant polybutylene terephthalate compound D.
Embodiment 5
The waterside phosphorus of 200ml mono- is added in the four-neck flask (1L) equipped with reflux condensing tube, electric mixer and thermometer
Acid sodium solution (8mol/L).500ml aluminum sulfate solutions (5.5mol/L) are added in sodium hypophosphite solution again.90 DEG C are heated to,
After isothermal reaction 3h, 10g molecular sieves, 20g cupric oxide are added, continue constant temperature stirring 0.5h, cool the temperature to 80 DEG C, added
2gY- aminopropyl triethoxysilanes, cooling, obtain white precipitate, filter, washing, be dried after obtain powder for safety and environmental protection
Inorganic hypo-aluminum orthophosphate combustion inhibitor.
Then by the inorganic hypo-aluminum orthophosphate combustion inhibitor 200g of safety and environmental protection manufactured in the present embodiment and 10gH108PE waxes,
1g1010,1g168 are added in high mixer, and under room temperature, speed is 2000r/min mixing 3min, then by the poly- terephthaldehydes of 488g
Sour butanediol ester is added in high mixer, and speed is 2000r/min mixed at high speed 10min, and discharging is obtained compound.
By material mixed above double screw extruder extruding pelletization, temperature adjusts extruder main frame at 200 DEG C～230 DEG C
Frequency is 300r/min, and feeding frequency is 10Hz, and side feeding adds roving glass fiber 300g.Then obtained in 230 DEG C of injections with injection machine
To fire retardant polybutylene terephthalate compound E.
Embodiment 6
The waterside phosphorus of 200ml mono- is added in the four-neck flask (1L) equipped with reflux condensing tube, electric mixer and thermometer
Acid sodium solution (8mol/L).500ml aluminum sulfate solutions (5.5mol/L) are added in sodium hypophosphite solution again.90 DEG C are heated to,
After isothermal reaction 3h, 15g molecular sieves, 15g cupric oxide are added, continue constant temperature stirring 0.5h, cool the temperature to 80 DEG C, added
2gY- aminopropyl triethoxysilanes, cooling, obtain white precipitate, filter, washing, be dried after obtain powder for safety and environmental protection
Inorganic hypo-aluminum orthophosphate combustion inhibitor.
Then by the inorganic hypo-aluminum orthophosphate combustion inhibitor 200g of safety and environmental protection manufactured in the present embodiment and 10gH108PE waxes,
1g1010,1g168 are added in high mixer, and under room temperature, speed is 2000r/min mixing 3min, then by the poly- terephthaldehydes of 488g
Sour butanediol ester is added in high mixer, and speed is 2000r/min mixed at high speed 10min, and discharging is obtained compound.
By material mixed above double screw extruder extruding pelletization, temperature adjusts extruder main frame at 200 DEG C～230 DEG C
Frequency is 300r/min, and feeding frequency is 10Hz, and side feeding adds roving glass fiber 300g.Then obtained in 230 DEG C of injections with injection machine
To fire retardant polybutylene terephthalate compound F.
Comparative example 1
Inorganic hypo-aluminum orthophosphate combustion inhibitor 200g and 10gH108PE waxes, 1g1010,1g168 are added in high mixer, room temperature
Under, speed is 2000r/min mixing 3min, then 488g polybutylene terephthalate (PBT)s is added in high mixer, speed
For 2000r/min mixed at high speed 10min, discharging, compound is obtained.
By material mixed above double screw extruder extruding pelletization, at 200 DEG C -230 DEG C, adjustment extruder main frame is frequently for temperature
Rate is 300r/min, and feeding frequency is 10Hz, and side feeding adds roving glass fiber 300g.Then obtained in 230 DEG C of injections with injection machine
Fire retardant polybutylene terephthalate compound G.
Fire retardant polybutylene terephthalate compound to obtaining in embodiment 1～6 and comparative example 1 hinders
Combustion grade, tensile strength and phosphine release amount test, acquired results are as shown in table 1：
Fire retardant polybutylene terephthalate compound (A～G) in the embodiment 1～6 of table 1 and comparative example 1
Performance test data
From table 1 it follows that when the mass fraction of the fire retardant of addition is 20%, 1～6h of embodiment and contrast are real
Applying the fire resistance of the fire retardant polybutylene terephthalate compound obtained in example 1 can reach V-0 ranks, and stretch strong
Degree makes moderate progress, but because the fire retardant in comparative example 1 is pure hypo-aluminum orthophosphate, does not add hydrogen phosphide absorbent,
Also do not carry out surface to hypo-aluminum orthophosphate to be modified, therefore the fire-retardant polybutylene terephthalate prepared in embodiment 1～6
The phosphine release amount of ester complexes reduces more than 98%, and respectively less than 0.08ppm compared to comparative example 1, meets VOC
The requirement of hydrogen phosphide release limit amount (0.08ppm) in material object and management standard.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any Spirit Essences without departing from the present invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. the inorganic hypo-aluminum orthophosphate combustion inhibitor of a kind of safety and environmental protection, it is characterised in that：It is to carry out surface to inorganic hypo-aluminum orthophosphate
Add what hydrogen phosphide absorbent was obtained while modified.
2. the inorganic hypo-aluminum orthophosphate combustion inhibitor of safety and environmental protection according to claim 1, it is characterised in that specifically by following methods
Prepare：
The aluminum sulfate solution of the one waterside sodium radio-phosphate,P-32 solution of 200mL, 8mol/L and 500mL, 5.5mol/L is mixed, is then heated
To 70～100 DEG C of isothermal reaction 3h, the hydrogen phosphide absorbent of 20～30g is added, continue constant temperature and stir temperature after 0.5～1h
60～90 DEG C are down to, 1～5g surfactants are added, 0.1～0.5h is stirred, cooling is precipitated, filters, gained is sunk
Form sediment and wash drying, gained powder is environment friendly inorganic hypo-aluminum orthophosphate combustion inhibitor.
3. the inorganic hypo-aluminum orthophosphate combustion inhibitor of safety and environmental protection according to claim 1 and 2, it is characterised in that：
Described hydrogen phosphide absorbent is activated carbon, molecular sieve, activated carbon fiber, activated alumina, cupric oxide, zinc oxide, chlorine
Change nickel, nickel nitrate, nickel sulfate, nickel acetate, postassium hypochlorite, calcium hypochlorite, calcium chloride, active aluminium hydroxide, zinc carbonate, talcum powder
In one or more mixtures.
4. the inorganic hypo-aluminum orthophosphate combustion inhibitor of safety and environmental protection according to claim 1 and 2, it is characterised in that：
Described surface modifier is in stearic acid, odium stearate, silane coupler, titanate coupling agent, aluminate coupling agent
At least one.
5. the inorganic hypo-aluminum orthophosphate combustion inhibitor of safety and environmental protection described in any one of Claims 1 to 4 is in polybutylene terephthalate
Application in ester composite.
6. what a kind of inorganic hypo-aluminum orthophosphate combustion inhibitor of safety and environmental protection by described in any one of Claims 1 to 4 was prepared is fire-retardant
Polybutylene terephthalate (PBT) composite, it is characterised in that specifically include the component of following mass fraction：
7. fire retardant polybutylene terephthalate composite according to claim 6, it is characterised in that：
Described polybutylene terephthalate (PBT) is Jiangsu Changchun 1100-211M；The glass is megalith EDR14-2000-
988A；The lubricant is Tissuemat E；The antioxidant is 1010,168 by 1:1 mixture.
8. a kind of preparation method of the fire retardant polybutylene terephthalate composite according to claim 6 or 7, its
It is characterised by comprising the following steps：
(1) at room temperature, by the inorganic hypo-aluminum orthophosphate combustion inhibitor of safety and environmental protection, lubricant and antioxidant in high-speed mixer
1000r/min～2000r/min mixes 1～10min, then adds described polybutylene terephthalate (PBT) in 1000r/
Min～2000r/min mixes 5～15min, and then discharging is obtained mixed material；
(2) mixed material in step (1) is added in double screw extruder, at the same side feeding add glass, 200 DEG C～
230 DEG C of extruding pelletizations, then obtain fire retardant polybutylene terephthalate composite with injection machine in 230 DEG C of injections.
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| CN201611242876.2A CN106633187A (en) | 2016-12-29 | 2016-12-29 | Safe and environment-friendly inorganic aluminum hypophosphite flame retardant and application thereof in PBT (polybutylene terephthalate) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265979A (en) * | 2018-09-17 | 2019-01-25 | 佛山市森昂生物科技有限公司 | A kind of preparation method of the compound imitated wood material of polyurethane plant fiber |
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| CN115073819A (en) * | 2022-06-15 | 2022-09-20 | 兰州瑞朴科技有限公司 | Aluminum phosphate salt flame retardant based on growth nucleus and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109265979A (en) * | 2018-09-17 | 2019-01-25 | 佛山市森昂生物科技有限公司 | A kind of preparation method of the compound imitated wood material of polyurethane plant fiber |
| CN113980353A (en) * | 2021-11-24 | 2022-01-28 | 湖北航云科技有限公司 | Environment-friendly aluminum hypophosphite flame retardant |
| CN115073819A (en) * | 2022-06-15 | 2022-09-20 | 兰州瑞朴科技有限公司 | Aluminum phosphate salt flame retardant based on growth nucleus and preparation method and application thereof |
| CN115073819B (en) * | 2022-06-15 | 2024-05-03 | 兰州瑞朴科技有限公司 | Growth-nucleus-based aluminum phosphate flame retardant, and preparation method and application thereof |
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