CN105085990B - Nano load halogen-free flameproof composite assistant and its preparation method and application - Google Patents
Nano load halogen-free flameproof composite assistant and its preparation method and application Download PDFInfo
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- CN105085990B CN105085990B CN201510489590.3A CN201510489590A CN105085990B CN 105085990 B CN105085990 B CN 105085990B CN 201510489590 A CN201510489590 A CN 201510489590A CN 105085990 B CN105085990 B CN 105085990B
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Abstract
The present invention provides a kind of nano load halogen-free flameproof composite assistant, belongs to fire retardant and fire proofing technical field.The composite assistant is according to mass fraction meter, including 10 40 part, nanometer Mg (OH) of fire retardant240 70 parts, 13 parts of titanate coupling agent, 6 15 parts of toughener, 0.5 2 parts of anti-aging agent, 1.5 5 parts of antioxidant；The fire retardant is cyclic annular polyphosphonates oligomer.The present invention also provides a kind of preparation methods of nano load halogen-free flameproof composite assistant.The present invention also provides application of the nano load halogen-free flameproof composite assistant in ABS/PC alloys.For the composite assistant of the present invention as a result of cyclic annular polyphosphonates oligomer as fire retardant, the product being prepared has excellent flame retardant property and mechanical property.
Description
Technical field
The invention belongs to fire retardant and fire proofing technical fields, and in particular to a kind of nano load halogen-free flameproof is compound to be helped
Agent and its preparation method and application.
Background technology
With attention of the people to environmental protection and safety, social every field to the flame-retardancy requirements of high molecular material increasingly
Height, then the modified polymer material of flame retarding function come into being.Earliest fire retardant type is halogenated flame retardant and inorganic gold
Belong to class.Although halogenated flame retardant has good flame retardant effect, a large amount of poisonous and harmful gas can be generated in combustion
Body, therefore requirement of the people to environmental protection cannot be met.And inorganic metal based flame retardant is in use, additive amount is larger, generally
40%~60%, easily cause the physical mechanical property of material is greatly lowered.
Occurred aggretion type organic halogen-free agent in recent years, the development of flame retarded polymeric material is made to make rapid progress.Such as
Due to the presence of P-C keys in aggretion type polymeric phosphinic acid ester, enhance its chemical stability, there is high temperature resistant, water resistance and resistance to
Therefore the advantages that solvent borne and good material compatibility, has been widely used as the fire retardant of high molecular material.
But any fire retardant can not all ensure to take into account the comprehensive performance of material, strongly limit opening up for its application field
Exhibition.Process Technology of Polymer is all that a variety of auxiliary agents are used in combination at present, although improving the comprehensive performance of material, process is made to become non-
Often complicated, the stability of production process and the reliability of product can not all ensure, the concept for the composite assistant that has then been born.
Patent application No. is 20110398865.4 discloses a kind of copolymer polypropylene tubing special assistant SYNOXM4228
And its application, the special assistant component include：It is prepared by the compositions such as antioxidant, light stabilizer, acid absorbent, lubricant, nucleating agent
In copolymer polypropylene tubing PP Pipe Compound, need to only add in this small amount of auxiliary agent can improve the processing performance and mechanics of copolymer polypropylene
Performance is more convenient for carrying out industrialized production.
But the patent about nano load halogen-free flameproof composite assistant also belongs to blank at present, and especially ABS/PC alloys are special
The preparation method and applications of nano load halogen-free flameproof composite assistant are even more to have not been reported.
Invention content
The purpose of the invention is to provide a kind of nano load halogen-free flameproof composite assistant and its preparation method and application,
The composite assistant has excellent flame retardant property and mechanical property.
Present invention firstly provides a kind of nano load halogen-free flameproof composite assistant, according to mass fraction meter, including such as the following group
Point：
The fire retardant is cyclic annular polyphosphonates oligomer.
Preferably, the structural formula of the cyclic annular polyphosphonates oligomer is as shown in formula I：
In formula I, n=2-6, R1For phenyl, R2ForOr
Preferably, the titanate coupling agent is titanate coupling agent TMC-102.
Preferably, the toughener is toughener ACR.
Preferably, the anti-aging agent is anti-aging agent TMQ.
Preferably, the antioxidant is selected from one or both of antioxidant 1010 or irgasfos 168.
The present invention also provides a kind of preparation method of nano load halogen-free flameproof composite assistant, including：
By nanometer Mg (OH)2It is added in ultra-high-speed mixing device with titanate coupling agent, is pre-mixed 30-60S, Ran Houjia
Enter cyclic annular polyphosphonates oligomer fire retardant, mix 30-60S, be eventually adding toughener, anti-aging agent and antioxidant, continue to mix
30-60S obtains nano load halogen-free flameproof composite assistant.
The present invention also provides application of the above-mentioned nano load halogen-free flameproof composite assistant in ABS/PC alloys.
Beneficial effects of the present invention
The present invention provides a kind of nano load halogen-free flameproof composite assistant, according to mass fraction meter, including fire retardant 10-40
Part, nanometer Mg (OH)240-70 parts, 1-3 parts of titanate coupling agent, 6-15 parts of toughener, 0.5-2 parts of anti-aging agent, antioxidant 1.5-
5 parts；The fire retardant is cyclic annular polyphosphonates oligomer, and composite assistant of the invention is neat as a result of cyclic annular polyphosphonates
The heat decomposition temperature that polymers is effectively improved as fire retardant, cricoid molecular structure, expansion have been sent out processing temperature range, have been improved
Flame retardant effect；Meanwhile phthalate ester coupling agent assists to complete chemical load function as surfactant；Toughener selects propylene
The core-shell copolymerized object ACR of acid esters family macromolecule enhances the polarity of surface of material, makes its dispersibility and compatibility more preferable, further
Improve the comprehensive performance of system.
The present invention also provides a kind of preparation method of nano load halogen-free flameproof composite assistant, this method is by nanometer Mg
(OH)2It is added in ultra-high-speed mixing device with titanate coupling agent, is pre-mixed 30-60S, it is neat then to add in cyclic annular polyphosphonates
Polymers fire retardant mixes 30-60S, is eventually adding toughener, anti-aging agent and antioxidant, continues to mix 30-60S, obtains nanometer and bear
Carry halogen-free flameproof composite assistant.The preparation method of the present invention is simple, raw material is easy to get.
The present invention also provides application of the nano load halogen-free flameproof composite assistant in ABS/PC alloys, with ABS/PC alloys
For matrix resin, nano load halogen-free flameproof composite assistant is added, prepares halogen-free flame retardant ABS/PC alloys, the product being prepared
With excellent flame retardant property and mechanical property.
Specific embodiment
Present invention firstly provides a kind of nano load halogen-free flameproof composite assistant, according to mass fraction meter, including fire retardant
10-40 parts, nanometer Mg (OH)240-70 parts, 1-3 parts of titanate coupling agent, 6-15 parts of toughener, 0.5-2 parts of anti-aging agent, antioxygen
1.5-5 parts of agent；Preferably 25 part, nanometer Mg (OH) of fire retardant255 parts, 2 parts of titanate coupling agent, 12 parts of toughener, anti-aging agent 1
Part, 5 parts of antioxidant；The fire retardant is cyclic annular polyphosphonates oligomer.
According to the present invention, the structural formula of the cyclic annular polyphosphonates oligomer is preferably as shown in formula I：
In formula I, n=2-6, R1For phenyl, R2ForOrShown in concrete structure such as formula II (CPBA), formula III (CPPA) or formula IV (CPFP)：
According to the present invention, the preparation method of the cyclic annular polyphosphonates oligomer includes the following steps：
Compound with formula (V) structure is mixed with the compound with formula (VI) structure, in catalyst or acid binding agent
Polymerisation is carried out under the conditions of existing, obtains the cyclic polyphosphoric acid ester oligomer with formula (I) structure,
The present invention using the compound with formula (V) structure and the compound with formula (VI) structure as raw material prepare with
During the cyclic polyphosphoric acid ester oligomer of formula (I) structure, prepared by the method that polymerisation in solution may be used, and can also use interface
It is prepared by the method for polymerization.
Wherein, the specific method of the polymerisation in solution is：By the compound with formula (V) structure with being tied with formula (VI)
The compound mixing of structure, polymerisation is carried out under the conditions of existing for acid binding agent, obtains the cyclic polyphosphoric acid with formula (I) structure
Ester oligomer.
Compound with formula (V) structure and the compound with formula (VI) structure are configured to solution by the present invention first,
Specifically, the compound with formula (V) structure is dissolved in the first solvent, the compound with formula (V) structure is obtained
Solution, first solvent are organic solvent, preferably dichloromethane or chloroform, the compound with formula (V) structure
The concentration of solution is preferably 0.1mmol/mL~0.2mol/mL；The compound for having formula (VI) structure is dissolved in the second solvent
In, the solution with the compound of formula (VI) structure is obtained, second solvent is organic solvent, preferably dichloromethane or chlorine
Imitative, the concentration of the solution of the compound with formula (VI) structure is preferably 0.1mmol/mL~0.2mol/mL.In the present invention
In, the molar ratio of the compound with formula (V) structure and the compound with formula (VI) structure is 1:(0.5~2), more preferably
It is 1:1.
It is dripped after the solution of compound with formula (V) structure is mixed with the solution of the compound with formula (VI) structure
It adds in reaction vessel, in N2Protection under, while be added dropwise while be stirred.The present invention is to the chemical combination with formula (V) structure
The hybrid mode of object and the compound with formula (VI) structure above-mentioned will preferably have formula (V) structure there is no specifically limited
The solution of compound and the solution of the compound with formula (VI) structure are added dropwise in reaction vessel simultaneously respectively by peristaltic pump.
That is, the present invention prepares cyclic polyphosphoric acid ester oligomer by pseudo-high dilution technique.Specifically, by control with formula (V) structure
The reaction solution concentration of compound and the compound with formula (VI) structure builds high dilute reaction condition.In the present invention, respectively
The rate of addition for controlling the solution of solution and the compound with formula (VI) structure of the compound with formula (V) structure is 5~
10ml/h.The temperature of the dropwise addition is -20 DEG C~20 DEG C, preferably -10 DEG C~10 DEG C.
There is no specifically limited for mode of the present invention to the stirring, it is preferred to use mechanical agitation.In the reaction vessel
It is contained with acid binding agent solution.In the present invention, the acid binding agent solution is configured as follows：Acid binding agent is dissolved in
In third solvent, acid binding agent solution is obtained.Wherein, the acid binding agent be organic amine compound, preferably triethylamine, pyridine or
N,N-diisopropylethylamine, more preferably triethylamine.The third solvent is organic solvent, preferably dichloromethane or chloroform.
In the acid binding agent solution, the volumetric concentration of acid binding agent is 0.1~10%, preferably 1~5%.
After the solution of compound with formula (V) structure and the solution of the compound with formula (VI) structure are added dropwise,
Under conditions of above-mentioned dropping temperature, i.e., -20 DEG C~20 DEG C, preferably -10 DEG C~10 DEG C, mixed solution in reaction vessel after
Continuous reaction, time of the reaction for 1~for 24 hours, preferably 2~5h.From dropwise reaction solution is started to the time for reacting end
For the time of polymerisation, the time of the polymerisation is preferably 5~30h, more preferably 12~20h.
After reaction, the solvent is evaporated, obtains crude product.There is no special limits to the mode being evaporated by the present invention
System, well known to a person skilled in the art method is evaporated, in the present invention, it is preferred to be evaporated the solvent using rotary evaporation.
Obtained crude product is cleaned using deionized water, cyclic polyphosphoric acid ester oligomer is obtained after drying.
According to the present invention, the titanate coupling agent, toughener, anti-aging agent and antioxidant are not particularly limited, metatitanic acid
Ester coupling agent is preferably titanate coupling agent TMC-102, and toughener is preferably toughener ACR, and anti-aging agent is preferably anti-aging agent
TMQ, antioxidant are preferably selected from one or both of antioxidant 1010 or irgasfos 168.
The present invention also provides a kind of preparation method of nano load halogen-free flameproof composite assistant, this method is by nanometer Mg
(OH)2It is added in ultra-high-speed mixing device with titanate coupling agent, is pre-mixed 30-60S, it is neat then to add in cyclic annular polyphosphonates
Polymers fire retardant mixes 30-60S, is eventually adding toughener, anti-aging agent and antioxidant, continues to mix 30-60S, obtains nanometer and bear
Halogen resistance is carried, preferably at 50-80 DEG C, rotating speed is preferably 4000-6000r/min for temperature control in the mixed process.
The present invention also provides application of the above-mentioned nano load halogen-free flameproof composite assistant in ABS/PC alloys, with ABS/PC
Alloy is matrix resin, and ABS and PC quality proportionings are preferably 30:70, the processing technology squeezed out using double-screw melt blending, system
Standby halogen-free flame retardant ABS/PC alloys, wherein, the additive amount of nano load halogen-free flameproof composite assistant is the 10-40% of ABS/PC.
Further detailed description is done to the present invention with reference to specific embodiment.
Embodiment 1
First by 40 parts of nanometer Mg (OH)2It is added in ultra-high-speed mixing device with 2 parts of titanate coupling agent TMC-102,
Under conditions of temperature 60 C, rotating speed 8000r/min, 45S is pre-mixed, it is cyclic annular neat then to add in 40 parts of phenylphosphonyl dichloride bisphenol-As
Polymers (CPBA), continues mixed at high speed 45S, temperature 60 C, and rotating speed 8000r/min completes loading process, is finally introducing 12 parts of increasings
Tough dose of ACR, 1 part of anti-aging agent TMQ, 3 parts of antioxidant 1010s, 2 parts of irgasfos 168s continue to mix 45S, temperature 70 C, rotating speed
8000r/min obtains ABS/PC alloys special-purpose nanometer load halogen-free flameproof composite assistant MF-01.
Embodiment 2
First by 55 parts of nanometer Mg (OH)2It is added in ultra-high-speed mixing device with 2 parts of titanate coupling agent TMC-102,
Under conditions of temperature 60 C, rotating speed 8000r/min, 45S is pre-mixed, it is cyclic annular neat then to add in 25 parts of phenylphosphonyl dichloride bisphenol-As
Polymers (CPBA), continues mixed at high speed 45S, temperature 60 C, and rotating speed 8000r/min completes loading process, is finally introducing 12 parts of increasings
Tough dose of ACR, 1 part of anti-aging agent TMQ, 3 parts of antioxidant 1010s, 2 parts of irgasfos 168s continue to mix 45S, temperature 70 C, rotating speed
8000r/min obtains ABS/PC alloys special-purpose nanometer load halogen-free flameproof composite assistant MF-02.
Embodiment 3
First by 70 parts of nanometer Mg (OH)2It is added in ultra-high-speed mixing device with 2 parts of titanate coupling agent TMC-102,
Under conditions of temperature 60 C, rotating speed 8000r/min, 45S is pre-mixed, it is cyclic annular neat then to add in 10 parts of phenylphosphonyl dichloride bisphenol-As
Polymers (CPBA), continues mixed at high speed 45S, temperature 60 C, and rotating speed 8000r/min completes loading process, is finally introducing 12 parts of increasings
Tough dose of ACR, 1 part of anti-aging agent TMQ, 3 parts of antioxidant 1010s, 2 parts of irgasfos 168s continue to mix 45S, temperature 70 C, rotating speed
8000r/min obtains ABS/PC alloys special-purpose nanometer load halogen-free flameproof composite assistant MF-03.
Embodiment 4
First by 40 parts of nanometer Mg (OH)2It is added in ultra-high-speed mixing device with 2 parts of titanate coupling agent TMC-102,
Under conditions of temperature 60 C, rotating speed 8000r/min, 45S is pre-mixed, then adds in 40 parts of phenylphosphonyl dichloride phenolphthalein ring-type oligomerisations
Object (CPPA), continues mixed at high speed 45S, temperature 60 C, and rotating speed 8000r/min completes loading process, is finally introducing 12 parts of toughenings
Agent ACR, 1 part of anti-aging agent TMQ, 3 parts of antioxidant 1010s, 2 parts of irgasfos 168s continue to mix 45S, temperature 70 C, rotating speed 8000r/
Min obtains ABS/PC alloys special-purpose nanometer load halogen-free flameproof composite assistant MF-04.
Embodiment 5
First by 55 parts of nanometer Mg (OH)2It is added in ultra-high-speed mixing device with 2 parts of titanate coupling agent TMC-102,
Under conditions of temperature 60 C, rotating speed 8000r/min, 45S is pre-mixed, then adds in 25 parts of phenylphosphonyl dichloride phenolphthalein ring-type oligomerisations
Object (CPPA), continues mixed at high speed 45S, temperature 60 C, and rotating speed 8000r/min completes loading process, is finally introducing 12 parts of toughenings
Agent ACR, 1 part of anti-aging agent TMQ, 3 parts of antioxidant 1010s, 2 parts of irgasfos 168s continue to mix 45S, temperature 70 C, rotating speed 8000r/
Min obtains ABS/PC alloys special-purpose nanometer load halogen-free flameproof composite assistant MF-05.
Embodiment 6
First by 70 parts of nanometer Mg (OH)2It is added in ultra-high-speed mixing device with 2 parts of titanate coupling agent TMC-102,
Under conditions of temperature 60 C, rotating speed 8000r/min, 45S is pre-mixed, then adds in 10 parts of phenylphosphonyl dichloride phenolphthalein ring-type oligomerisations
Object (CPPA), continues mixed at high speed 45S, temperature 60 C, and rotating speed 8000r/min completes loading process, is finally introducing 12 parts of toughenings
Agent ACR, 1 part of anti-aging agent TMQ, 3 parts of antioxidant 1010s, 2 parts of irgasfos 168s continue to mix 45S, temperature 70 C, rotating speed 8000r/
Min obtains ABS/PC alloys special-purpose nanometer load halogen-free flameproof composite assistant MF-06.
Embodiment 7
First by 40 parts of nanometer Mg (OH)2It is added in ultra-high-speed mixing device with 2 parts of titanate coupling agent TMC-102,
Under conditions of temperature 60 C, rotating speed 8000r/min, 45S is pre-mixed, it is cyclic annular neat then to add in 40 parts of phenylphosphonyl dichloride bisphenol fluorenes
Polymers (CPFP), continues mixed at high speed 45S, temperature 60 C, and rotating speed 8000r/min completes loading process, is finally introducing 12 parts of increasings
Tough dose of ACR, 1 part of anti-aging agent TMQ, 3 parts of antioxidant 1010s, 2 parts of irgasfos 168s continue to mix 45S, temperature 70 C, rotating speed
8000r/min obtains ABS/PC alloys special-purpose nanometer load halogen-free flameproof composite assistant MF-07.
Embodiment 8
First by 55 parts of nanometer Mg (OH)2It is added in ultra-high-speed mixing device with 2 parts of titanate coupling agent TMC-102,
Under conditions of temperature 60 C, rotating speed 8000r/min, 45S is pre-mixed, it is cyclic annular neat then to add in 25 parts of phenylphosphonyl dichloride bisphenol fluorenes
Polymers (CPFP), continues mixed at high speed 45S, temperature 60 C, and rotating speed 8000r/min completes loading process, is finally introducing 12 parts of increasings
Tough dose of ACR, 1 part of anti-aging agent TMQ, 3 parts of antioxidant 1010s, 2 parts of irgasfos 168s continue to mix 45S, temperature 70 C, rotating speed
8000r/min obtains ABS/PC alloys special-purpose nanometer load halogen-free flameproof composite assistant MF-08.
Embodiment 9
First by 70 parts of nanometer Mg (OH)2It is added in ultra-high-speed mixing device with 2 parts of titanate coupling agent TMC-102,
Under conditions of temperature 60 C, rotating speed 8000r/min, 45S is pre-mixed, it is cyclic annular neat then to add in 10 parts of phenylphosphonyl dichloride bisphenol fluorenes
Polymers (CPFP), continues mixed at high speed 45S, temperature 60 C, and rotating speed 8000r/min completes loading process, is finally introducing 12 parts of increasings
Tough dose of ACR, 1 part of anti-aging agent TMQ, 3 parts of antioxidant 1010s, 2 parts of irgasfos 168s continue to mix 45S, temperature 70 C, rotating speed
8000r/min obtains ABS/PC alloys special-purpose nanometer load halogen-free flameproof composite assistant MF-09.
Embodiment 10-27
The halogen-free flameproof composite assistant MF-01 to MF-09 that will be prepared in embodiment 1-9, is answered in ABS/PC systems
With verification, the wherein proportioning of two kinds of matrix resins of ABS/PC is 30:The introduction volume of 70, halogen-free flameproof composite assistant MF are respectively to match
10%, 25%, the 40% of square gross mass number, is formulated after premixing to be added in double screw extruder and melt altogether
Mixed, processing temperature is 190-210-230-240-240-235-230 DEG C, screw speed 150r/min.The sample trade mark and proportioning are shown in
Table 1.
Table 1
Embodiment 28
It is FRAP01- by the trade mark in above-described embodiment 10-27 according to the method for GB/T2048 and GB/T2406-83
FRAP27 samples be made standard batten carry out respectively vertical burn test and limit oxygen index test, and with pure ABS/PC samples into
Row comparison, test result are shown in Table 2.
Table 2
| The sample trade mark | LOI (%) | UL-94 |
| Pure ABS/PC | 20.1 | - |
| FRAP01 | 22.4 | V-2 |
| FRAP02 | 27.9 | V-0 |
| FRAP03 | 31.8 | V-0 |
| FRAP04 | 21.5 | - |
| FRAP05 | 26.8 | V-0 |
| FRAP06 | 30.4 | V-0 |
| FRAP07 | 21.9 | - |
| FRAP08 | 26.3 | V-1 |
| FRAP09 | 30.1 | V-0 |
| FRAP10 | 22.6 | V-2 |
| FRAP11 | 25.9 | V-1 |
| FRAP12 | 30.0 | V-0 |
| FRAP13 | 21.0 | - |
| FRAP14 | 25.8 | V-1 |
| FRAP15 | 29.8 | V-0 |
| FRAP16 | 20.7 | - |
| FRAP17 | 26.0 | V-1 |
| FRAP18 | 29.7 | V-0 |
| FRAP19 | 20.4 | - |
| FRAP20 | 25.4 | V-1 |
| FRAP21 | 30.1 | V-0 |
| FRAP22 | 21.0 | - |
| FRAP23 | 24.9 | V-2 |
| FRAP24 | 29.2 | V-0 |
| FRAP25 | 20.9 | - |
| FRAP26 | 25.0 | V-2 |
| FRAP27 | 29.1 | V-0 |
Embodiment 29
It is FRAP01-FRAP27 samples to the trade mark in pure ABS/PC alloys and embodiment 10-27 according to national standard
Carry out the sample preparation and test of mechanical property.Reference standard is：Tensile strength presses GB/T1040-2006, bending strength GB/T9341-
2000, cantilever beam impact strength (notch) GB/T1843-2008, heat distortion temperature GB/T1634-2004.Test result is shown in Table 3.
Table 3
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of nano load halogen-free flameproof composite assistant, which is characterized in that according to mass fraction meter, including following component：
The fire retardant is cyclic annular polyphosphonates oligomer
The structural formula of the cyclic annular polyphosphonates oligomer is as shown in formula I：
In formula I, n=2-6, R1For phenyl, R2For
A kind of 2. nano load halogen-free flameproof composite assistant according to claim 1, which is characterized in that the titanate esters
Coupling agent is titanate coupling agent TMC-102.
A kind of 3. nano load halogen-free flameproof composite assistant according to claim 1, which is characterized in that the toughener
For toughener ACR.
A kind of 4. nano load halogen-free flameproof composite assistant according to claim 1, which is characterized in that the anti-aging agent
For anti-aging agent TMQ.
A kind of 5. nano load halogen-free flameproof composite assistant according to claim 1, which is characterized in that the antioxidant
Selected from one or both of antioxidant 1010 or irgasfos 168.
6. a kind of preparation method of nano load halogen-free flameproof composite assistant according to claim 1-5 any one,
It is characterized in that, including：
By nanometer Mg (OH)2It is added in ultra-high-speed mixing device with titanate coupling agent, is pre-mixed 30-60S, then adds in ring
Shape polyphosphonates oligomer fire retardant mixes 30-60S, is eventually adding toughener, anti-aging agent and antioxidant, continues to mix 30-
60S obtains nano load halogen-free flameproof composite assistant.
7. application of the nano load halogen-free flameproof composite assistant described in claim 1-5 any one in ABS/PC alloys.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1234413A (en) * | 1998-04-28 | 1999-11-10 | 协和化学工业株式会社 | Fire-retardant resin composition and use thereof |
| CN101423666A (en) * | 2008-10-31 | 2009-05-06 | 广东新会美达锦纶股分有限公司 | Halogen-free flame retardant polyamide 6 composition |
| CN102492226A (en) * | 2011-12-05 | 2012-06-13 | 大连兴辉化工有限公司 | Special additive SYNOXM4228 for copolymerized polypropylene tube material and application thereof |
| CN104629087A (en) * | 2015-03-11 | 2015-05-20 | 中国科学院长春应用化学研究所 | Cyclic polyphosphoester oligmer, and preparation method and application thereof |
-
2015
- 2015-08-11 CN CN201510489590.3A patent/CN105085990B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1234413A (en) * | 1998-04-28 | 1999-11-10 | 协和化学工业株式会社 | Fire-retardant resin composition and use thereof |
| CN101423666A (en) * | 2008-10-31 | 2009-05-06 | 广东新会美达锦纶股分有限公司 | Halogen-free flame retardant polyamide 6 composition |
| CN102492226A (en) * | 2011-12-05 | 2012-06-13 | 大连兴辉化工有限公司 | Special additive SYNOXM4228 for copolymerized polypropylene tube material and application thereof |
| CN104629087A (en) * | 2015-03-11 | 2015-05-20 | 中国科学院长春应用化学研究所 | Cyclic polyphosphoester oligmer, and preparation method and application thereof |
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