CN104945578B - A kind of rubber graft copolymer and preparation method thereof of anti-dripping melt, thermoplastification - Google Patents
A kind of rubber graft copolymer and preparation method thereof of anti-dripping melt, thermoplastification Download PDFInfo
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Abstract
The invention belongs to anti-dripping agent technical field, more particularly to a kind of anti-dripping melt, the rubber graft copolymer of thermoplastification, copolymer have the core shell structure being made up of stratum nucleare and shell, and stratum nucleare is poly-（Tetrafluoroethene is grafted butadiene）, and stratum nucleare is in nano level two-phase inierpeneirating network structure, and shell is the polymeric layer being polymerized by least one of alkyl methacrylate, styrene and acrylonitrile monomer；The quality of shell and the mass ratio of stratum nucleare are（30~50）：（70~50）；The preparing raw material of copolymer includes：Ptfe emulsion, divinylic monomer, alkyl methacrylate monomer, styrene monomer and acrylonitrile monemer；Wherein, ptfe emulsion, the part by weight of divinylic monomer are（25~75）：（75~25）.Relative to prior art, in the present invention, polytetrafluoroethylene (PTFE) can be uniformly distributed in the plastic, and the rubber graft copolymer has the advantages that increasing tougheness is good, low-temperature flexibility is good, good weatherability, anti-dripping melt is good, compatibility is good.
Description
Technical field
The invention belongs to anti-dripping agent technical field, more particularly to a kind of anti-dripping melt, the rubber graft copolymer of thermoplastification
And preparation method thereof.
Background technology
Thermoplastic have the advantages that it is light and handy, be easy to manufacture and industrialized production, in the side of our daily production and living
There is its figure in aspect face, and it brings huge power to the development of the mankind.But due to thermoplastic easy firing, it is heated
Easy softening transform, or even drop, need addition fire retardant to make it have the bigger scope of application in process of production, at present, modeling
The verified intensity for being capable of retarded combustion and reduction burning by adding fire retardant of flame-retardant modified research and application of material products.
But plastic products are during burning, in addition to own combustion, it can also produce drippage and ignite other combustibles, cause fire
The sprawling of gesture, this often produces the consequence more serious than plastic products own combustion.Therefore, during flame retardance of polymer,
It is inadequate only to add fire retardant, often also needs to add the drippage that auxiliary agent prevents polymer in combustion process.
Currently used anti-dripping agent is polytetrafluoroethylene (PTFE), and it is the principle using polytetrafluoroethylene fibre, in plastics
During burning, fibrosis occurs for polytetrafluoroethylene (PTFE) so that the plastics around it are limited between the fibers, so as to cause plastics burning
When do not drip, so as to avoid the drippage due to the plastic grain of burning from causing spot fire.
But polytetrafluoroethylene (PTFE) is dispersed poor, causes it to be not easy to be added in the material of thermoplastification, so as to cause to add
It is not very good to enter the anti-dripping melt of the thermoplastification material of polytetrafluoroethylene (PTFE).
In view of this, rubber graft copolymer it is necessory to provide a kind of anti-dripping melt, thermoplastification and preparation method thereof, is adopted
In rubber graft copolymer with this method preparation, polytetrafluoroethylene (PTFE) can be uniformly distributed in the plastic, and the grafting rubbers
Copolymer has the advantages that increasing tougheness is good, low-temperature flexibility is good, good weatherability, anti-dripping melt is good, compatibility is good.
The content of the invention
An object of the present invention is：In view of the shortcomings of the prior art, the rubber of a kind of anti-dripping melt, thermoplastification is provided
Graft copolymer, in the rubber graft copolymer, polytetrafluoroethylene (PTFE) can be uniformly distributed in the plastic, and the grafting rubbers
Copolymer has the advantages that increasing tougheness is good, low-temperature flexibility is good, good weatherability, anti-dripping melt is good, compatibility is good.
To achieve these goals, the present invention is adopted the following technical scheme that：
The rubber graft copolymer of a kind of anti-dripping melt, thermoplastification, the copolymer have the core being made up of stratum nucleare and shell
Shell structure, the stratum nucleare are poly-（Tetrafluoroethene-grafting-butadiene）, and the stratum nucleare is in nano level two-phase interpenetrating networks
Structure, the shell are to be gathered by what at least one of alkyl methacrylate, styrene and acrylonitrile monomer was polymerized
Compound layer；
The quality of the shell and the mass ratio of the stratum nucleare are（30~50）：（70~50）；
The preparing raw material of the copolymer includes：Ptfe emulsion, divinylic monomer, alkyl methacrylate list
Body, styrene monomer and acrylonitrile monemer；
Wherein, ptfe emulsion, the part by weight of divinylic monomer are（25~75）：（75~25）.
The a kind of of rubber graft copolymer as anti-dripping melt of the present invention, thermoplastification improves, the quality of the shell and institute
The mass ratio for stating stratum nucleare is（35~45）：（65~55）；
Ptfe emulsion, the part by weight of divinylic monomer are（30~60）：（40~70）.
The a kind of of rubber graft copolymer as anti-dripping melt of the present invention, thermoplastification improves, the ptfe emulsion
To use emulsion prepared by emulsion polymerization or Aqueous phase, and the solid content of the ptfe emulsion is 30%~70%.
The a kind of of rubber graft copolymer as anti-dripping melt of the present invention, thermoplastification improves, the molecular weight of polytetrafluoroethylene (PTFE)
For 2,000,000~5,000,000.The polytetrafluoroethylene (PTFE) of small-molecular-weight can not play a part of anti-drip, and be merely able to reduce material surface
Coefficient of friction, improve material wear resistance in itself, while play a part of interior lubrication and the demoulding.
The a kind of of rubber graft copolymer as anti-dripping melt of the present invention, thermoplastification improves, the methacrylate
Ester monomer is methyl methacrylate monomer, EMA monomer, butylmethacrylate monomer and methacrylic acid
At least one of isobutyl ester monomer.
Relative to prior art, the stratum nucleare in the present invention be in nano level two-phase inierpeneirating network structure, polytetrafluoroethylene (PTFE) with
Both polymer of polybutadiene are combined closely by mutually running through for cross-linked network to be formed, distinctive between them to force mutually
Appearance effect can make both polymer form stable blend polymer, so as to realize the mutual of performance between component or function
Mend.Meanwhile morphological features such as the special cellular texture of two-phase inierpeneirating network structure, interface IPN, two-phase be continuous and thus
Caused firm interface cohesion, makes them produce special synergy on macro property again.Moreover, this two-phase IPN
The copolymer of network structure also has the characteristics of processing characteristics is good, so as to play good modifying function to rubber.
Moreover, the present invention in stratum nucleare surface grafting by coating by the good alkyl methacrylate of compatibility, styrene
The polymeric layer being polymerized with least one of acrylonitrile monomer, so as to greatly improve polytetrafluoroethylene (PTFE) in plastics material
Dispersiveness and compatibility in material, so as to improve the anti-dripping melt performance of plastics, moreover, the present invention can be added with lower dosage
Into thermoplastic, the performance of plastics anti-dripping melt is reached in flame-retardant formulations, in addition, the present invention will not separate out in the plastic,
The processing characteristics of plastics in itself is not interfered with, heat endurance is good, while enables to the surface of plastics more glossy.
In a word, the present invention has that increasing tougheness is good, low-temperature flexibility is good, good weatherability, that anti-dripping melt is good, compatibility is good etc. is many
Advantage.The present invention can be modified macromolecular toughening becomes simple and easy.
It is another object of the present invention to provide the preparation side of a kind of anti-dripping melt, the rubber graft copolymer of thermoplastification
Method, comprise the following steps：The first step, the preparation of stratum nucleare：Ptfe emulsion, initiator, emulsifying agent and water are added and reacted
In kettle, 70 DEG C~80 DEG C are warming up under atmosphere of inert gases, then adds divinylic monomer, keep polymerization temperature be 75 DEG C~
90 DEG C, polymerization pressure is 2Mpa~8Mpa, after reacting 2h~10h, pressure release blowing, stratum nucleare emulsion is made；
Second step, the preparation of copolymer：Alkyl methacrylate, benzene second are added in the stratum nucleare emulsion obtained to the first step
At least one of alkene and acrylonitrile monomer, lower addition initiator is enclosed in nitrogen protective atmosphere, controlling reaction temperature is 80 DEG C~100
DEG C, after reacting 2h~10h, blowing cohesion, washing, dry the obtained copolymer with stratum nucleare-shell structurre.
The a kind of of preparation method as anti-dripping melt of the present invention, the rubber graft copolymer of thermoplastification improves, in the first step
The quality of initiator and the mass ratio of divinylic monomer are（0.2~2）：100, the quality of emulsifying agent and butadiene list in the first step
The mass ratio of body is（1~2）：100；The mass ratio of ptfe emulsion and water is（1~5）：10.
The a kind of of preparation method as anti-dripping melt of the present invention, the rubber graft copolymer of thermoplastification improves, in the first step
Initiator is redox initiator or peroxide initiator, and redox initiator is ferrous iron-hydrogen peroxide diisopropyl
Benzene-sodium pyrosulfite system；Peroxide initiator is in hydrogen peroxide, potassium peroxydisulfate, ammonium persulfate and benzoyl peroxide
At least one；In the first step emulsifying agent be neopelex, lauryl sodium sulfate and rosin ester at least
It is a kind of.
The a kind of of preparation method as anti-dripping melt of the present invention, the rubber graft copolymer of thermoplastification improves, in second step
The quality of initiator and the mass ratio of divinylic monomer are（0.02~1）：1000.
The a kind of of preparation method as anti-dripping melt of the present invention, the rubber graft copolymer of thermoplastification improves, in second step
Initiator is redox initiator or peroxide initiator, and redox initiator is ferrous iron-hydrogen peroxide diisopropyl
Benzene-sodium pyrosulfite system；Peroxide initiator be hydrogen peroxide, potassium peroxydisulfate, ammonium persulfate, cumyl peroxide and
At least one of benzoyl peroxide.
It is simple and easy relative to prior art, present invention process, it is easy to accomplish industrialization, and can be made with two-phase
The stratum nucleare of inierpeneirating network structure and the stratum nucleare good with Compatibility in Plastics being evenly coated on stratum nucleare, so as to improve the anti-drop of plastics
Fall performance, while improve the toughness of plastics.
Embodiment
The present invention and its advantage are described in further detail with reference to embodiment, but the embodiment party of the present invention
Formula is not limited to this.
Embodiment 1
A kind of anti-dripping melt that the present embodiment provides, the rubber graft copolymer of thermoplastification, the copolymer have by stratum nucleare and
The core shell structure of shell composition, stratum nucleare is poly-（Tetrafluoroethene-grafting-butadiene）, and stratum nucleare is in nano level two-phase IPN
Network structure, shell are the polymeric layer being polymerized by methyl methacrylate monomer and styrene monomer；
The preparing raw material of copolymer includes：Ptfe emulsion, divinylic monomer, methyl methacrylate monomer and benzene
Vinyl monomer；
Wherein, ptfe emulsion, the part by weight of divinylic monomer are 10：9.
Wherein, the solid content of ptfe emulsion is 60%, and the molecular weight of polytetrafluoroethylene (PTFE) is 3,000,000.
Its preparation method is：
（1）1000 grams of ptfe emulsion for taking emulsion polymerization to prepare（Solids content 60%）, deionized water 5000
Gram, 10 grams of benzoyl peroxide, 30 grams of potassium peroxydisulfate, divinylic monomer（Liquefaction compression monomer）900 grams, DBSA
18 grams of sodium.
（2）By 1000 grams of ptfe emulsion, 5000 grams of deionized water, 10 grams of benzoyl peroxide, potassium peroxydisulfate 30
Gram, 18 grams of neopelex is added in reactor together, is warming up to 70 DEG C, is first passed through nitrogen displacement water oxygen；After
It is continuous when being warming up to 80 DEG C, add divinylic monomer；Reaction can at once start and exothermic phenomenon occurs, and pressure is in 4MPa in control kettle
Within, and between 80 DEG C -83 DEG C of temperature control.After reaction 4 hours, pressure release blowing.
（3）Take（2）1000 grams of solid weight part that step reaction is completed, then by methyl methacrylate and styrene list
600 grams of body（The weight of methyl methacrylate and styrene ratio=4：1）, 0.1 gram of di-isopropylbenzene hydroperoxide, it is passed through nitrogen guarantor
Shield adds 0.003 gram of frerrous chloride, 0.2 gram of sodium pyrosulfite after 15 minutes, and reaction temperature is controlled at 90 DEG C, after reacting 3 hours
Conversion ratio is detected more than 98%, blowing cohesion, washing, dries acquisition with poly-（Tetrafluoroethene-grafting-butadiene）For core, with first
Base acrylate-styrene copolymer is the resin of core.
Embodiment 2
A kind of anti-dripping melt that the present embodiment provides, the rubber graft copolymer of thermoplastification, the copolymer have by stratum nucleare and
The core shell structure of shell composition, stratum nucleare is poly-（Tetrafluoroethene-grafting-butadiene）, and stratum nucleare is in nano level two-phase IPN
Network structure, shell are the polymeric layer being polymerized by EMA monomer and styrene monomer；
The preparing raw material of copolymer includes：Ptfe emulsion, divinylic monomer, EMA monomer and benzene
Vinyl monomer；
Wherein, ptfe emulsion, the part by weight of divinylic monomer are 10：5.
Wherein, the solid content of ptfe emulsion is 50%, and the molecular weight of polytetrafluoroethylene (PTFE) is 3,500,000.
Its preparation method is：
（1）1000 grams of ptfe emulsion prepared by phase of fetching water method（Solids content 50%）, 5000 grams of deionized water, mistake
Aoxidize 4 grams of diisopropylbenzene (DIPB), divinylic monomer（Liquefaction compression monomer）500 grams, 10 grams of lauryl sodium sulfate.
（2）By 1000 grams of ptfe emulsion, 5000 grams of deionized water, 4 grams of cumyl peroxide, dodecyl sulphur
Sour 10 grams of sodium is added in reactor together, is warming up to 75 DEG C, is first passed through nitrogen displacement water oxygen；When continuing to be warming up to 80 DEG C,
Add divinylic monomer；Reaction can at once start and exothermic phenomenon occurs, control in kettle that pressure is within 3Mpa, and temperature control
Between 80 DEG C -83 DEG C of system.After reaction 5 hours, pressure release blowing.
（3）Take（2）1000 grams of solid weight part that step reaction is completed, then mixes EMA and styrene
Close 500 grams of monomer（The weight of EMA and styrene ratio=2.5：1）, 0.2 gram of di-isopropylbenzene hydroperoxide, it is passed through
After nitrogen is protected 15 minutes, 0.006 gram of frerrous chloride, 0.4 gram of sodium pyrosulfite are added, reaction temperature is controlled at 90 DEG C, reaction 4
Conversion ratio is detected after hour more than 98%, blowing cohesion, washing, dries acquisition with poly-（Tetrafluoroethene-grafting-butadiene）For
Core, the resin using copolymer of methyl methacrylatestyrene as core.
Embodiment 3
A kind of anti-dripping melt that the present embodiment provides, the rubber graft copolymer of thermoplastification, the copolymer have by stratum nucleare and
The core shell structure of shell composition, stratum nucleare is poly-（Tetrafluoroethene-grafting-butadiene）, and stratum nucleare is in nano level two-phase IPN
Network structure, shell are the polymeric layer being polymerized by acrylonitrile monemer and styrene monomer；
The preparing raw material of copolymer includes：Ptfe emulsion, divinylic monomer, acrylonitrile monemer and styrene list
Body；
Wherein, ptfe emulsion, the part by weight of divinylic monomer are 10：15.
Wherein, the solid content of ptfe emulsion is 55%, and the molecular weight of polytetrafluoroethylene (PTFE) is 4,500,000.
Its preparation method is：
（1）1000 grams of ptfe emulsion prepared by phase of fetching water method（Solids content 55%）, 10000 grams of deionized water, mistake
10 grams of ammonium sulfate, divinylic monomer（Liquefaction compression monomer）1500 grams, 10 grams of rosin ester.
（2）By 1000 grams of ptfe emulsion, 10000 grams of deionized water, 10 grams of ammonium persulfate, 10 gram one of rosin ester
Rise in addition reactor, be warming up to 70 DEG C, be first passed through nitrogen displacement water oxygen；When continuing to be warming up to 80 DEG C, butadiene is added
Monomer；Reaction can at once start and exothermic phenomenon occurs, control in kettle pressure within 6Mpa, and 80 DEG C -83 of temperature control
Between DEG C.After reaction 6 hours, pressure release blowing.
（3）Take（2）1000 grams of solid weight part that step reaction is completed, then by styrene-acrylonitrile mix monomer 400
Gram（Weight ratio=3 of styrene, acrylonitrile：1）, 0.15 gram of di-isopropylbenzene hydroperoxide, after being passed through nitrogen protection 15 minutes, add
Enter 0.0045 gram of frerrous chloride, 0.3 gram of sodium pyrosulfite, reaction temperature is controlled at 95 DEG C, and reaction detects conversion ratio after 6 hours and existed
More than 98%, blowing cohesion, washing, acquisition is dried with poly-（Tetrafluoroethene-grafting-butadiene）For core, with methyl methacrylate
Ester-styrol copolymer is the resin of core.
Embodiment 4
A kind of anti-dripping melt that the present embodiment provides, the rubber graft copolymer of thermoplastification, the copolymer have by stratum nucleare and
The core shell structure of shell composition, stratum nucleare is poly-（Tetrafluoroethene-grafting-butadiene）, and stratum nucleare is in nano level two-phase IPN
Network structure, shell are the polymeric layer being polymerized by Isobutyl methacrylate monomer and acrylonitrile monemer；
The preparing raw material of copolymer includes：Ptfe emulsion, divinylic monomer, Isobutyl methacrylate monomer and
Acrylonitrile monemer；
Wherein, ptfe emulsion, the part by weight of divinylic monomer are 10：7.
Wherein, the solid content of ptfe emulsion is 45%, and the molecular weight of polytetrafluoroethylene (PTFE) is 4,200,000.
Its preparation method is：
（1）1000 grams of ptfe emulsion for taking emulsion polymerization to prepare（Solids content 45%）, deionized water 5000
Gram, 10 grams of potassium peroxydisulfate, divinylic monomer（Liquefaction compression monomer）700 grams, 18 grams of neopelex.
（2）By 1000 grams of ptfe emulsion, 5000 grams of deionized water, 10 grams of potassium peroxydisulfate, DBSA
18 grams of sodium is added in reactor together, is warming up to 75 DEG C, is first passed through nitrogen displacement water oxygen；When continuing to be warming up to 85 DEG C, add
Enter divinylic monomer；Reaction can at once start and exothermic phenomenon occurs, control in kettle that pressure is within 2Mpa, and temperature control
Between 85 DEG C -90 DEG C.After reaction 5 hours, pressure release blowing.
（3）Take（2）1000 grams of the solid weight part completed is reacted, then by Isobutyl methacrylate monomer and acrylonitrile
800 grams of monomer mix monomer（The weight of Isobutyl methacrylate and acrylonitrile ratio=2：1）, di-isopropylbenzene hydroperoxide 0.1
Gram, after being passed through nitrogen protection 15 minutes, 0.003 gram of frerrous chloride, 0.2 gram of sodium pyrosulfite are added, reaction temperature is controlled 96
DEG C, conversion ratio is detected after reacting 8 hours more than 98%, blowing cohesion, washing, dries acquisition with poly-（Tetrafluoroethene-grafting-fourth
Diene）For core, the resin using copolymer of methyl methacrylatestyrene as core.
Embodiment 5
A kind of anti-dripping melt that the present embodiment provides, the rubber graft copolymer of thermoplastification, the copolymer have by stratum nucleare and
The core shell structure of shell composition, stratum nucleare is poly-（Tetrafluoroethene-grafting-butadiene）, and stratum nucleare is in nano level two-phase IPN
Network structure, shell are the polymeric layer being polymerized by butylmethacrylate monomer and acrylonitrile monemer；
The preparing raw material of copolymer includes：Ptfe emulsion, divinylic monomer, butylmethacrylate monomer and third
Alkene nitrile monomer；
Wherein, ptfe emulsion, the part by weight of divinylic monomer are 10：6.
Wherein, the solid content of ptfe emulsion is 42%, and the molecular weight of polytetrafluoroethylene (PTFE) is 4,800,000.
Its preparation method is as follows：
（1）1000 grams of ptfe emulsion prepared by phase of fetching water method（Solids content 42%）, 5000 grams of deionized water, mistake
0.1 gram of hydrogen oxide diisopropylbenzene (DIPB), 0.003 gram of frerrous chloride, 0.2 gram of sodium pyrosulfite, divinylic monomer（Liquefaction compression monomer）
600 grams, 18 grams of neopelex.
（2）By 1000 grams of ptfe emulsion, 5000 grams of deionized water, 0.1 gram of di-isopropylbenzene hydroperoxide and 12
18 grams of sodium alkyl benzene sulfonate is added in reactor together, after being passed through nitrogen protection 15 minutes, adds 0.003 gram of frerrous chloride, burnt
0.2 gram of sodium sulfite, is warming up to 70 DEG C, is first passed through nitrogen displacement water oxygen；When continuing to be warming up to 80 DEG C, butadiene list is added
Body；Reaction can at once start and exothermic phenomenon occurs, control in kettle pressure within 5Mpa, and 80 DEG C -83 DEG C of temperature control
Between.After reaction 7 hours, pressure release blowing.
（3）Take（2）1000 grams of solid weight part that step reaction is completed, then mixes butyl methacrylate and acrylonitrile
Close 400 grams of monomer（The weight of butyl methacrylate and acrylonitrile ratio=3：1）, 3 grams of benzoyl peroxide（First it is dissolved into methyl
In butyl acrylate and acrylonitrile mix monomer）Reaction temperature control at 85 DEG C, reaction 5 hours after detect conversion ratio 98% with
On, blowing cohesion, washing, acquisition is dried with poly-（Tetrafluoroethene-grafting-butadiene）For core, with methyl methacrylate-benzene second
Alkene copolymer is the resin of core.
By the product and polycarbonate blending of embodiment 1 to 5, sample strip is made, in order to as a comparison, by polytetrafluoroethylene (PTFE)
（Comparative example 1）With polycarbonate blending, sample strip is made, then detects the anti-dripping melt performance of its blend, the results are shown in Table 1.
Wherein, UL94 combustion tests examination criteria：
1）Sample strip is vertically disposed in combustion chamber；
2）Sample strip is put into 10s in flame, then removes, and detects the time t1 of the flame self-gravitation of sample strip；
3）Sample strip is put into flame again, then removed, detects second of burning time t2；
4）Can the particle of sample strip or dropping ignite article after judging burning as indicator by the use of cotton.
The product of the embodiment 1 to 5 of table 1 and comparative example 1 with it is polycarbonate-copolymerized after anti-dripping effects
As can be seen from Table 1：The present invention can significantly improve the anti-dripping melt performance of plastics.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and changed.Therefore, the invention is not limited in embodiment disclosed and described above, to the present invention's
Some modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, although used in this specification
Some specific terms, but these terms are merely for convenience of description, do not form any restrictions to the present invention.
Claims (2)
1. a kind of preparation method of the rubber graft copolymer of anti-dripping melt, thermoplastification, the copolymer has by stratum nucleare and shell group
Into core shell structure, stratum nucleare is poly- (tetrafluoroethene-grafting-butadiene), and stratum nucleare is in nano level two-phase interpenetrating networks knot
Structure, shell are the polymeric layer being polymerized by methyl methacrylate monomer and styrene monomer；
The preparing raw material of copolymer includes：Ptfe emulsion, divinylic monomer, methyl methacrylate monomer and styrene
Monomer；
Wherein, ptfe emulsion, the part by weight of divinylic monomer are 10：9；
Wherein, the solid content of ptfe emulsion is 60%, and the molecular weight of polytetrafluoroethylene (PTFE) is 3,000,000；
The preparation method is specially：
(1) 1000 grams of the ptfe emulsion of the solids content 60% of emulsion polymerization preparation, 5000 grams of deionized water, mistake are taken
10 grams of BP, 30 grams of potassium peroxydisulfate, 900 grams of the divinylic monomer for compression of liquefying, 18 grams of neopelex；
(2) by 1000 grams of ptfe emulsion, 5000 grams of deionized water, 10 grams of benzoyl peroxide, 30 grams of potassium peroxydisulfate, ten
18 grams of dialkyl benzene sulfonic acids sodium is added in reactor together, is warming up to 70 DEG C, is first passed through nitrogen displacement water oxygen；Continue to heat up
During to 80 DEG C, divinylic monomer is added；Reaction can at once start and exothermic phenomenon occur, control kettle in pressure within 4MPa,
And between 80 DEG C -83 DEG C of temperature control；After reaction 4 hours, pressure release blowing；
(3) 1000 grams of solid weight part for taking the reaction of (2) step to complete, then by 600 grams of methyl methacrylate and benzene second
Weight ratio=4 of alkene：1 methyl methacrylate and styrene monomer, 0.1 gram of di-isopropylbenzene hydroperoxide, it is passed through nitrogen guarantor
Shield adds 0.003 gram of frerrous chloride, 0.2 gram of sodium pyrosulfite after 15 minutes, and reaction temperature is controlled at 90 DEG C, after reacting 3 hours
Conversion ratio is detected more than 98%, blowing cohesion, washing, dries acquisition with poly- (tetrafluoroethene-grafting-butadiene) as core, with
Copolymer of methyl methacrylatestyrene is the resin of shell.
2. the rubber graft copolymer of a kind of anti-dripping melt that preparation method according to claim 1 is prepared, thermoplastification.
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| CN106750034A (en) * | 2017-01-25 | 2017-05-31 | 郑勇 | A kind of anti-dripping agent with good workability and dispersiveness and preparation method thereof |
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| CN115043991B (en) * | 2021-03-08 | 2023-07-25 | 中国石油天然气股份有限公司 | Method for preparing fluorine-containing thermoplastic elastomer by emulsion polymerization method and prepared thermoplastic elastomer |
| CN114230720B (en) * | 2021-12-30 | 2024-01-23 | 山东东岳高分子材料有限公司 | Additive with flame-retardant and anti-dripping functions, preparation method and composition thereof |
| WO2023142949A1 (en) * | 2022-01-30 | 2023-08-03 | 熵能创新材料(珠海)有限公司 | Anti-dripping agent, preparation method therefor and use thereof |
| CN115842130A (en) * | 2022-08-30 | 2023-03-24 | 宁德时代新能源科技股份有限公司 | Binder composition, positive electrode sheet, secondary battery, battery module, battery pack, and electric device |
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| CN101628957A (en) * | 2009-09-09 | 2010-01-20 | 常熟三爱富中昊化工新材料有限公司 | Anti-dripping agent preparation method |
| CN102933619A (en) * | 2011-05-25 | 2013-02-13 | 泰国Abs有限公司 | Compositions including polytetrafluoroethylene and processes for preparation thereof |
| CN103755862A (en) * | 2013-12-14 | 2014-04-30 | 衢州市中通化工有限公司 | Preparation method of core-shell polymer using polytetrafluoroethylene emulsion particles as seeds |
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2015
- 2015-07-22 CN CN201510431244.XA patent/CN104945578B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628957A (en) * | 2009-09-09 | 2010-01-20 | 常熟三爱富中昊化工新材料有限公司 | Anti-dripping agent preparation method |
| CN102933619A (en) * | 2011-05-25 | 2013-02-13 | 泰国Abs有限公司 | Compositions including polytetrafluoroethylene and processes for preparation thereof |
| CN103755862A (en) * | 2013-12-14 | 2014-04-30 | 衢州市中通化工有限公司 | Preparation method of core-shell polymer using polytetrafluoroethylene emulsion particles as seeds |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of Poly(tetrafluoroethylene)/Poly(butadiene) Core-Shell Particles and Their Graft Copolymerization;Motoki Okaniwa;《Journal of Applied Polymer Science》;19981231;第68卷;第185-190页 * |
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