CN104945578A - Anti-drippage heat plasticization rubber grafted copolymer and preparation method thereof - Google Patents
Anti-drippage heat plasticization rubber grafted copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of anti-drippage agents and particularly relates to an anti-drippage heat plasticization rubber grafted copolymer. The copolymer is of a core-shell structure including a core layer and a shell layer, the core layer is poly-(tetrafluoroethylene-grafted-butadiene), the core layer is of a nanosized two-phase interpenetrating network structure, and the shell layer is a polymer layer polymerized by at least one monomer of alkyl (meth) acrylate, styrene and acrylonitrile; the ratio of the mass of the shell layer to the mass of the core layer is (30-50):(70-50); the preparation raw materials of the copolymer comprise polytetrafluoroethylene emulsion, a butadiene monomer, an alkyl (meth) acrylate monomer, a styrene monomer and an acrylonitrile monomer; the weight ratio of the polytetrafluoroethylene emulsion to the butadiene monomer is (25-75):(75-25). Relative to the prior art, in the anti-drippage heat plasticization rubber grafted copolymer and the preparation method thereof, the polytetrafluoroethylene can be uniformly distributed in plastic, and the rubber grafted copolymer has the advantages that the toughness effect is good, the low-temperature toughness is good, the weather resistance is good, the anti-drippage performance is good, and the compatibility is good.
Description
Technical field
The invention belongs to anti-dripping agent technical field, particularly the rubber graft copolymer and preparation method thereof of a kind of anti-dripping melt, thermoplastification.
Background technology
Thermoplastic material has lightly, be convenient to the advantages such as manufacture and suitability for industrialized production, has its figure in the every aspect of our daily productive life, and it brings huge power to the development of the mankind.But due to thermoplastic material easy firing, be heated easy softening transform, even drop, need to add fire retardant in process of production and make it have the larger scope of application, at present, the flame-retardant modified Study and appliance of plastics is verified can retarded combustion and the intensity reducing burning by adding fire retardant.But plastics are in the process of burning, and except own combustion, also can produce drippage and to ignite other combustiblematerialss, cause spreading of the intensity of a fire, this often produces the consequence more serious than plastics own combustion.Therefore, in flame retardance of polymer process, it is inadequate for only adding fire retardant, needs toward contact the drippage adding polymkeric substance in auxiliary agent prevention combustion processes.
Anti-dripping agent conventional is at present tetrafluoroethylene, it is the principle utilizing polytetrafluoroethylene fiber, when Plastics Combustion, tetrafluoroethylene generation fibrosis, plastics around it are limited between the fibers, thus cause plastics not drip when burning, thus the drippage of the plastic grain due to burning is avoided to cause spot fire.
But the dispersiveness of tetrafluoroethylene is poor, cause it not easily to add in the material of thermoplastification, thus the anti-dripping melt causing the thermoplastification material adding tetrafluoroethylene is not very good.
In view of this, necessaryly provide rubber graft copolymer of a kind of anti-dripping melt, thermoplastification and preparation method thereof, in the rubber graft copolymer adopting the method to prepare, tetrafluoroethylene can be uniformly distributed in the plastic, and this rubber graft copolymer has advantages such as increasing tougheness is good, low-temperature flexibility is good, good weatherability, anti-dripping melt are good, consistency is good.
Summary of the invention
An object of the present invention is: for the deficiencies in the prior art, and the rubber graft copolymer of a kind of anti-dripping melt, thermoplastification is provided, in this rubber graft copolymer, tetrafluoroethylene can be uniformly distributed in the plastic, and this rubber graft copolymer has advantages such as increasing tougheness is good, low-temperature flexibility is good, good weatherability, anti-dripping melt are good, consistency is good.
To achieve these goals, the present invention adopts following technical scheme:
The rubber graft copolymer of a kind of anti-dripping melt, thermoplastification, described multipolymer has the nucleocapsid structure be made up of stratum nucleare and shell, described stratum nucleare is poly-(tetrafluoroethylene-grafting-divinyl), and described stratum nucleare is nano level two-phase inierpeneirating network structure, described shell is by the polymer layer of at least one monomer polymerization in alkyl methacrylate, vinylbenzene and vinyl cyanide;
The quality of described shell and the mass ratio of described stratum nucleare are (30 ~ 50): (70 ~ 50);
The raw materials of described multipolymer comprises: ptfe emulsion, divinylic monomer, alkyl methacrylate monomer, styrene monomer and acrylonitrile monemer;
Wherein, the part by weight of ptfe emulsion, divinylic monomer is (25 ~ 75): (75 ~ 25).
One as the rubber graft copolymer of anti-dripping melt of the present invention, thermoplastification is improved, and the quality of described shell and the mass ratio of described stratum nucleare are (35 ~ 45): (65 ~ 55);
The part by weight of ptfe emulsion, divinylic monomer is (30 ~ 60): (40 ~ 70).
One as the rubber graft copolymer of anti-dripping melt of the present invention, thermoplastification is improved, and described ptfe emulsion is the emulsion adopting emulsion polymerization or Aqueous phase to prepare, and the solid content of described ptfe emulsion is 30% ~ 70%.
One as the rubber graft copolymer of anti-dripping melt of the present invention, thermoplastification is improved, and the molecular weight of tetrafluoroethylene is 2,000,000 ~ 5,000,000.The tetrafluoroethylene of small-molecular-weight cannot play the effect of anti-drippage, and is merely able to the frictional coefficient reducing material surface, improves the wear resistance of material itself, plays the effect of interior lubrication and the demoulding simultaneously.
One as the rubber graft copolymer of anti-dripping melt of the present invention, thermoplastification is improved, and described alkyl methacrylate monomer is at least one in methyl methacrylate monomer, β-dimethyl-aminoethylmethacrylate monomer, butylmethacrylate monomer and Propenoic acid, 2-methyl, isobutyl ester monomer.
Relative to prior art, stratum nucleare in the present invention is nano level two-phase inierpeneirating network structure, tetrafluoroethylene and these two kinds of polymkeric substance of polyhutadiene were formed by mutually running through of cross-linked network combines closely, the distinctive blend polymer forcing mutual tolerance interaction energy to make this two kinds of polymer formation stable between them, thus realize the complementation of performance or function between component.Meanwhile, morphological specificity and the consequent firmly interface cohesion such as the special cellular texture of two-phase inierpeneirating network structure, interface IPN, two-phase are continuous, makes again them on macro property, produce special synergy.And the multipolymer of this two-phase inierpeneirating network structure also has the feature of good processability, thus plays good modifying function to rubber.
And, the present invention passes through at the coated alkyl methacrylate good by consistency of stratum nucleare surface grafting, the polymer layer of at least one monomer polymerization in vinylbenzene and vinyl cyanide, thus greatly can improve tetrafluoroethylene dispersiveness in a plastic material and consistency, thus improve the anti-dripping melt performance of plastics, and, the present invention can add in thermoplastics with lower consumption, the performance of plastics anti-dripping melt is reached in flame-retardant formulations, in addition, the present invention can not separate out in the plastic, the processing characteristics of plastics itself can not be affected, Heat stability is good, the surface of plastics can be made more glossy simultaneously.
In a word, the present invention has the plurality of advantages such as increasing tougheness is good, low-temperature flexibility is good, good weatherability, anti-dripping melt are good, consistency is good.The present invention can make macromolecular toughening modification become simple.
Another object of the present invention is the preparation method of the rubber graft copolymer providing a kind of anti-dripping melt, thermoplastification, comprise the following steps: the first step, the preparation of stratum nucleare: ptfe emulsion, initiator, emulsifying agent and water are added in reactor, under atmosphere of inert gases, be warming up to 70 DEG C ~ 80 DEG C, then add divinylic monomer, keep polymerization temperature to be 75 DEG C ~ 90 DEG C, polymerization pressure is 2Mpa ~ 8Mpa, after reaction 2h ~ 10h, pressure release blowing, obtained stratum nucleare emulsion;
Second step; the preparation of multipolymer: add at least one monomer in alkyl methacrylate, vinylbenzene and vinyl cyanide in the stratum nucleare emulsion that the first step obtains; initiator is added under nitrogen protection atmosphere; controlling temperature of reaction is 80 DEG C ~ 100 DEG C; after reaction 2h ~ 10h, blowing cohesion, washing, the dry obtained multipolymer with stratum nucleare-shell structure.
One as the preparation method of the rubber graft copolymer of anti-dripping melt of the present invention, thermoplastification is improved, in the first step, the quality of initiator and the mass ratio of divinylic monomer are (0.2 ~ 2): 100, and in the first step, the quality of emulsifying agent and the mass ratio of divinylic monomer are (1 ~ 2): 100; The mass ratio of ptfe emulsion and water is (1 ~ 5): 10.
One as the preparation method of the rubber graft copolymer of anti-dripping melt of the present invention, thermoplastification is improved, in the first step, initiator is redox initiator or peroxide initiator, and redox initiator is ferrous iron-di-isopropylbenzene hydroperoxide-Sodium Pyrosulfite system; Peroxide initiator is at least one in hydrogen peroxide, Potassium Persulphate, ammonium persulphate and benzoyl peroxide; In the first step, emulsifying agent is at least one in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate and rosin ester.
One as the preparation method of the rubber graft copolymer of anti-dripping melt of the present invention, thermoplastification is improved, and in second step, the quality of initiator and the mass ratio of divinylic monomer are (0.02 ~ 1): 1000.
One as the preparation method of the rubber graft copolymer of anti-dripping melt of the present invention, thermoplastification is improved, in second step, initiator is redox initiator or peroxide initiator, and redox initiator is ferrous iron-di-isopropylbenzene hydroperoxide-Sodium Pyrosulfite system; Peroxide initiator is at least one in hydrogen peroxide, Potassium Persulphate, ammonium persulphate, dicumyl peroxide and benzoyl peroxide.
Relative to prior art, present invention process is simple, is easy to realize industrialization, and can obtain the stratum nucleare with two-phase inierpeneirating network structure and the stratum nucleare good with Compatibility in Plastics be evenly coated on stratum nucleare, thus improve the anti-dripping melt performance of plastics, improve the toughness of plastics simultaneously.
Embodiment
Below in conjunction with embodiment, the present invention and beneficial effect thereof are described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of anti-dripping melt that the present embodiment provides, the rubber graft copolymer of thermoplastification, this multipolymer has the nucleocapsid structure be made up of stratum nucleare and shell, stratum nucleare is poly-(tetrafluoroethylene-grafting-divinyl), and stratum nucleare is nano level two-phase inierpeneirating network structure, and shell is the polymer layer be polymerized by methyl methacrylate monomer and styrene monomer;
The raw materials of multipolymer comprises: ptfe emulsion, divinylic monomer, methyl methacrylate monomer and styrene monomer;
Wherein, the part by weight of ptfe emulsion, divinylic monomer is 10:9.
Wherein, the solid content of ptfe emulsion is 60%, and the molecular weight of tetrafluoroethylene is 3,000,000.
Its preparation method is:
(1) ptfe emulsion 1000 grams (solids content 60%) prepared by emulsion polymerization is got, deionized water 5000 grams, benzoyl peroxide 10 grams, Potassium Persulphate 30 grams, divinylic monomer (liquefaction compression monomer) 900 grams, Sodium dodecylbenzene sulfonate 18 grams.
(2) by ptfe emulsion 1000 grams, deionized water 5000 grams, benzoyl peroxide 10 grams, Potassium Persulphate 30 grams, Sodium dodecylbenzene sulfonate 18 grams adds in reactor together, is warmed up to 70 DEG C, first passes into nitrogen replacement water oxygen gas; When continuing to be warmed up to 80 DEG C, add divinylic monomer; Reaction can will begin in a minute and occur exothermic phenomenon, controls still internal pressure within 4MPa, and temperature is controlled between 80 DEG C-83 DEG C.React after 4 hours, pressure release blowing.
(3) solid weight part 1000 grams that (2) step has been reacted is got, then by methyl methacrylate and styrene monomer 600 grams (methyl methacrylate and cinnamic weight ratio=4:1), di-isopropylbenzene hydroperoxide 0.1 gram, pass into nitrogen protection after 15 minutes, add iron protochloride 0.003 gram, Sodium Pyrosulfite 0.2 gram, temperature of reaction controls at 90 DEG C, react and detect transformation efficiency more than 98% after 3 hours, blowing condenses, washing, dry acquisition is to gather (tetrafluoroethylene-grafting-divinyl) for core, take copolymer of methyl methacrylatestyrene as the resin of core.
Embodiment 2
A kind of anti-dripping melt that the present embodiment provides, the rubber graft copolymer of thermoplastification, this multipolymer has the nucleocapsid structure be made up of stratum nucleare and shell, stratum nucleare is poly-(tetrafluoroethylene-grafting-divinyl), and stratum nucleare is nano level two-phase inierpeneirating network structure, and shell is the polymer layer be polymerized by β-dimethyl-aminoethylmethacrylate monomer and styrene monomer;
The raw materials of multipolymer comprises: ptfe emulsion, divinylic monomer, β-dimethyl-aminoethylmethacrylate monomer and styrene monomer;
Wherein, the part by weight of ptfe emulsion, divinylic monomer is 10:5.
Wherein, the solid content of ptfe emulsion is 50%, and the molecular weight of tetrafluoroethylene is 3,500,000.
Its preparation method is:
(1) ptfe emulsion 1000 grams (solids content 50%) that phase legal system of fetching water is standby, deionized water 5000 grams, dicumyl peroxide 4 grams, divinylic monomer (liquefaction compression monomer) 500 grams, sodium lauryl sulphate 10 grams.
(2) by ptfe emulsion 1000 grams, deionized water 5000 grams, dicumyl peroxide 4 grams, sodium lauryl sulphate 10 grams adds in reactor together, is warmed up to 75 DEG C, first passes into nitrogen replacement water oxygen gas; When continuing to be warmed up to 80 DEG C, add divinylic monomer; Reaction can will begin in a minute and occur exothermic phenomenon, controls still internal pressure within 3Mpa, and temperature is controlled between 80 DEG C-83 DEG C.React after 5 hours, pressure release blowing.
(3) solid weight part 1000 grams that (2) step has been reacted is got, then by β-dimethyl-aminoethylmethacrylate and vinylbenzene mix monomer 500 grams (β-dimethyl-aminoethylmethacrylate and cinnamic weight ratio=2.5:1), di-isopropylbenzene hydroperoxide 0.2 gram, pass into nitrogen protection after 15 minutes, add iron protochloride 0.006 gram, Sodium Pyrosulfite 0.4 gram, temperature of reaction controls at 90 DEG C, react and detect transformation efficiency more than 98% after 4 hours, blowing condenses, washing, dry acquisition is to gather (tetrafluoroethylene-grafting-divinyl) for core, take copolymer of methyl methacrylatestyrene as the resin of core.
Embodiment 3
A kind of anti-dripping melt that the present embodiment provides, the rubber graft copolymer of thermoplastification, this multipolymer has the nucleocapsid structure be made up of stratum nucleare and shell, stratum nucleare is poly-(tetrafluoroethylene-grafting-divinyl), and stratum nucleare is nano level two-phase inierpeneirating network structure, and shell is the polymer layer be polymerized by acrylonitrile monemer and styrene monomer;
The raw materials of multipolymer comprises: ptfe emulsion, divinylic monomer, acrylonitrile monemer and styrene monomer;
Wherein, the part by weight of ptfe emulsion, divinylic monomer is 10:15.
Wherein, the solid content of ptfe emulsion is 55%, and the molecular weight of tetrafluoroethylene is 4,500,000.
Its preparation method is:
(1) ptfe emulsion 1000 grams (solids content 55%) that phase legal system of fetching water is standby, deionized water 10000 grams, ammonium persulphate 10 grams, divinylic monomer (liquefaction compression monomer) 1500 grams, rosin ester 10 grams.
(2) by ptfe emulsion 1000 grams, deionized water 10000 grams, ammonium persulphate 10 grams, rosin ester 10 grams adds in reactor together, is warmed up to 70 DEG C, first passes into nitrogen replacement water oxygen gas; When continuing to be warmed up to 80 DEG C, add divinylic monomer; Reaction can will begin in a minute and occur exothermic phenomenon, controls still internal pressure within 6Mpa, and temperature is controlled between 80 DEG C-83 DEG C.React after 6 hours, pressure release blowing.
(3) solid weight part 1000 grams that (2) step has been reacted is got; then by styrene-acrylonitrile mix monomer 400 grams (weight ratio=3:1 of vinylbenzene, vinyl cyanide); di-isopropylbenzene hydroperoxide 0.15 gram; pass into nitrogen protection after 15 minutes; add iron protochloride 0.0045 gram; Sodium Pyrosulfite 0.3 gram; temperature of reaction controls at 95 DEG C; react and detect transformation efficiency more than 98% after 6 hours; blowing cohesion, washing, dry acquisition for core, take copolymer of methyl methacrylatestyrene as the resin of core with poly-(tetrafluoroethylene-grafting-divinyl).
Embodiment 4
A kind of anti-dripping melt that the present embodiment provides, the rubber graft copolymer of thermoplastification, this multipolymer has the nucleocapsid structure be made up of stratum nucleare and shell, stratum nucleare is poly-(tetrafluoroethylene-grafting-divinyl), and stratum nucleare is nano level two-phase inierpeneirating network structure, and shell is the polymer layer be polymerized by Propenoic acid, 2-methyl, isobutyl ester monomer and acrylonitrile monemer;
The raw materials of multipolymer comprises: ptfe emulsion, divinylic monomer, Propenoic acid, 2-methyl, isobutyl ester monomer and acrylonitrile monemer;
Wherein, the part by weight of ptfe emulsion, divinylic monomer is 10:7.
Wherein, the solid content of ptfe emulsion is 45%, and the molecular weight of tetrafluoroethylene is 4,200,000.
Its preparation method is:
(1) ptfe emulsion 1000 grams (solids content 45%) prepared by emulsion polymerization is got, deionized water 5000 grams, Potassium Persulphate 10 grams, divinylic monomer (liquefaction compression monomer) 700 grams, Sodium dodecylbenzene sulfonate 18 grams.
(2) by ptfe emulsion 1000 grams, deionized water 5000 grams, Potassium Persulphate 10 grams, Sodium dodecylbenzene sulfonate 18 grams adds in reactor together, is warmed up to 75 DEG C, first passes into nitrogen replacement water oxygen gas; When continuing to be warmed up to 85 DEG C, add divinylic monomer; Reaction can will begin in a minute and occur exothermic phenomenon, controls still internal pressure within 2Mpa, and temperature is controlled between 85 DEG C-90 DEG C.React after 5 hours, pressure release blowing.
(3) the solid weight part 1000 grams (2) reacted is got, then by Propenoic acid, 2-methyl, isobutyl ester monomer and acrylonitrile monemer mix monomer 800 grams (weight ratio=2:1 of Propenoic acid, 2-methyl, isobutyl ester and vinyl cyanide), di-isopropylbenzene hydroperoxide 0.1 gram, pass into nitrogen protection after 15 minutes, add iron protochloride 0.003 gram, Sodium Pyrosulfite 0.2 gram, temperature of reaction controls at 96 DEG C, react and detect transformation efficiency more than 98% after 8 hours, blowing condenses, washing, dry acquisition is to gather (tetrafluoroethylene-grafting-divinyl) for core, take copolymer of methyl methacrylatestyrene as the resin of core.
Embodiment 5
A kind of anti-dripping melt that the present embodiment provides, the rubber graft copolymer of thermoplastification, this multipolymer has the nucleocapsid structure be made up of stratum nucleare and shell, stratum nucleare is poly-(tetrafluoroethylene-grafting-divinyl), and stratum nucleare is nano level two-phase inierpeneirating network structure, and shell is the polymer layer be polymerized by butylmethacrylate monomer and acrylonitrile monemer;
The raw materials of multipolymer comprises: ptfe emulsion, divinylic monomer, butylmethacrylate monomer and acrylonitrile monemer;
Wherein, the part by weight of ptfe emulsion, divinylic monomer is 10:6.
Wherein, the solid content of ptfe emulsion is 42%, and the molecular weight of tetrafluoroethylene is 4,800,000.
Its preparation method is as follows:
(1) ptfe emulsion 1000 grams (solids content 42%) that phase legal system of fetching water is standby, deionized water 5000 grams, di-isopropylbenzene hydroperoxide 0.1 gram, iron protochloride 0.003 gram, Sodium Pyrosulfite 0.2 gram, divinylic monomer (liquefaction compression monomer) 600 grams, Sodium dodecylbenzene sulfonate 18 grams.
(2) by ptfe emulsion 1000 grams, deionized water 5000 grams, di-isopropylbenzene hydroperoxide 0.1 gram adds in reactor together with Sodium dodecylbenzene sulfonate 18 grams, pass into nitrogen protection after 15 minutes, add iron protochloride 0.003 gram, Sodium Pyrosulfite 0.2 gram, is warmed up to 70 DEG C, first passes into nitrogen replacement water oxygen gas; When continuing to be warmed up to 80 DEG C, add divinylic monomer; Reaction can will begin in a minute and occur exothermic phenomenon, controls still internal pressure within 5Mpa, and temperature is controlled between 80 DEG C-83 DEG C.React after 7 hours, pressure release blowing.
(3) solid weight part 1000 grams that (2) step has been reacted is got, then by butyl methacrylate and vinyl cyanide mix monomer 400 grams (weight ratio=3:1 of butyl methacrylate and vinyl cyanide), benzoyl peroxide 3 grams (being first dissolved in butyl methacrylate and vinyl cyanide mix monomer) temperature of reaction controls at 85 DEG C, react and detect transformation efficiency more than 98% after 5 hours, blowing cohesion, washing, dry acquisition for core, take copolymer of methyl methacrylatestyrene as the resin of core with poly-(tetrafluoroethylene-grafting-divinyl).
By the product of embodiment 1 to 5 and polycarbonate blending, make sample strip, in order to as a comparison, by tetrafluoroethylene (comparative example 1) and polycarbonate blending, make sample strip, then detect the anti-dripping melt performance of its blend, the results are shown in Table 1.
Wherein, UL94 combustion test examination criteria:
1) sample strip is vertically placed on combustion chamber;
2) sample strip puts into flame 10s, then shifts out, and detects the time t1 of the flame self-gravitation of sample strip;
3) again sample strip is put into flame, then shift out, detect second time t2 combustion time;
4) after judging to burn as indicator with cotton, can the particle of sample strip or dropping ignite article.
The product of table 1 embodiment 1 to 5 and comparative example 1 and polycarbonate-copolymerized after anti-dripping effects
As can be seen from Table 1: the present invention significantly can improve the anti-dripping melt performance of plastics.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change above-mentioned embodiment and revise.Therefore, the present invention is not limited to embodiment disclosed and described above, also should fall in the protection domain of claim of the present invention modifications and changes more of the present invention.In addition, although employ some specific terms in this specification sheets, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. the rubber graft copolymer of an anti-dripping melt, thermoplastification, it is characterized in that, described multipolymer has the nucleocapsid structure be made up of stratum nucleare and shell, described stratum nucleare is poly-(tetrafluoroethylene-grafting-divinyl), and described stratum nucleare is nano level two-phase inierpeneirating network structure, described shell is by the polymer layer of at least one monomer polymerization in alkyl methacrylate, vinylbenzene and vinyl cyanide;
The quality of described shell and the mass ratio of described stratum nucleare are (30 ~ 50): (70 ~ 50);
The raw materials of described multipolymer comprises: ptfe emulsion, divinylic monomer, alkyl methacrylate monomer, styrene monomer and acrylonitrile monemer;
Wherein, the part by weight of ptfe emulsion, divinylic monomer is (25 ~ 75): (75 ~ 25).
2. the rubber graft copolymer of anti-dripping melt according to claim 1, thermoplastification, is characterized in that: the quality of described shell and the mass ratio of described stratum nucleare are (35 ~ 45): (65 ~ 55);
The part by weight of ptfe emulsion, divinylic monomer is (30 ~ 60): (40 ~ 70).
3. the rubber graft copolymer of anti-dripping melt according to claim 1, thermoplastification, is characterized in that: described ptfe emulsion is the emulsion adopting emulsion polymerization or Aqueous phase to prepare, and the solid content of described ptfe emulsion is 30% ~ 70%.
4. the rubber graft copolymer of anti-dripping melt according to claim 1, thermoplastification, is characterized in that: the molecular weight of tetrafluoroethylene is 2,000,000 ~ 5,000,000.
5. the rubber graft copolymer of anti-dripping melt according to claim 1, thermoplastification, is characterized in that: described alkyl methacrylate monomer is at least one in methyl methacrylate monomer, β-dimethyl-aminoethylmethacrylate monomer, butylmethacrylate monomer and Propenoic acid, 2-methyl, isobutyl ester monomer.
6. the preparation method of the anti-dripping melt described in an any one of claim 1 to 5, the rubber graft copolymer of thermoplastification, it is characterized in that, comprise the following steps: the first step, the preparation of stratum nucleare: ptfe emulsion, initiator, emulsifying agent and water are added in reactor, 70 DEG C ~ 80 DEG C are warming up under atmosphere of inert gases, then divinylic monomer is added, polymerization temperature is kept to be 75 DEG C ~ 90 DEG C, polymerization pressure is 2Mpa ~ 8Mpa, after reaction 2h ~ 10h, pressure release blowing, obtained stratum nucleare emulsion;
Second step; the preparation of multipolymer: add at least one monomer in alkyl methacrylate, vinylbenzene and vinyl cyanide in the stratum nucleare emulsion that the first step obtains; initiator is added under nitrogen protection atmosphere; controlling temperature of reaction is 80 DEG C ~ 100 DEG C; after reaction 2h ~ 10h, blowing cohesion, washing, the dry obtained multipolymer with stratum nucleare-shell structure.
7. the preparation method of the rubber graft copolymer of anti-dripping melt according to claim 6, thermoplastification, it is characterized in that: in the first step, the quality of initiator and the mass ratio of divinylic monomer are (0.2 ~ 2): 100, and in the first step, the quality of emulsifying agent and the mass ratio of divinylic monomer are (1 ~ 2): 100; The mass ratio of ptfe emulsion and water is (1 ~ 5): 10.
8. the preparation method of the anti-dripping melt according to claim 6 or 7, the rubber graft copolymer of thermoplastification, it is characterized in that: in the first step, initiator is redox initiator or peroxide initiator, redox initiator is ferrous iron-di-isopropylbenzene hydroperoxide-Sodium Pyrosulfite system; Peroxide initiator is at least one in hydrogen peroxide, Potassium Persulphate, dicumyl peroxide, ammonium persulphate and benzoyl peroxide; In the first step, emulsifying agent is at least one in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate and rosin ester.
9. the preparation method of the rubber graft copolymer of anti-dripping melt according to claim 6, thermoplastification, is characterized in that: in second step, the quality of initiator and the mass ratio of divinylic monomer are (0.02 ~ 1): 1000.
10. the preparation method of the anti-dripping melt according to claim 6 or 9, the rubber graft copolymer of thermoplastification, it is characterized in that: in second step, initiator is redox initiator or peroxide initiator, redox initiator is ferrous iron-di-isopropylbenzene hydroperoxide-Sodium Pyrosulfite system; Peroxide initiator is at least one in hydrogen peroxide, Potassium Persulphate, ammonium persulphate and benzoyl peroxide.
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| 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 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN115028782A (en) * | 2021-03-08 | 2022-09-09 | 中国石油天然气股份有限公司 | Method for preparing fluorine-containing high-weather-resistance thermoplastic resin by emulsion polymerization and prepared thermoplastic resin |
| CN115043991A (en) * | 2021-03-08 | 2022-09-13 | 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 |
| 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 |
| CN115028782B (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 high-weather-resistance thermoplastic resin by emulsion polymerization method and prepared thermoplastic resin |
| CN114230720A (en) * | 2021-12-30 | 2022-03-25 | 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 |
| 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 |
| WO2024045471A1 (en) * | 2022-08-30 | 2024-03-07 | 宁德时代新能源科技股份有限公司 | Polymer with core-shell structure and preparation method therefor and use thereof, positive electrode paste, secondary battery, battery module, battery pack, and electric device |
| CN116656111A (en) * | 2023-05-30 | 2023-08-29 | 建滔覆铜板（深圳）有限公司 | Resin composition with excellent compatibility and preparation method and application thereof |
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| CN104945578B (en) | 2018-03-23 |
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