CN106674406A - Preparation method and modification method of flexible low-melting point vinylidene fluoride copolymer - Google Patents
Preparation method and modification method of flexible low-melting point vinylidene fluoride copolymer Download PDFInfo
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- CN106674406A CN106674406A CN201611265569.6A CN201611265569A CN106674406A CN 106674406 A CN106674406 A CN 106674406A CN 201611265569 A CN201611265569 A CN 201611265569A CN 106674406 A CN106674406 A CN 106674406A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
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- C08F214/22—Vinylidene fluoride
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- C08F2/12—Polymerisation in non-solvents
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Abstract
The invention relates to a vinylidene fluoride copolymer, in particular to a preparation method and a modification method of a flexible low-melting point vinylidene fluoride copolymer. The preparation method comprises the following steps: (1) adding deionized water and a dispersing agent into a reaction kettle, vacuumizing and deoxidizing; (2) raising the temperature to the reaction temperature, beginning to introduce an initial mixed monomer, adding an initiator and a molecular weight regulator after completion of the introduction, performing a polymerization reaction, continuously introducing a supplementing mixed monomer during the reaction, supplementing the molecular weight regulator for many times, stopping the reaction after completion of the introduction of the supplementing mixed monomer to obtain vinylidene fluoride copolymer resin; (3) condensing, washing and drying the vinylidene fluoride copolymer resin to obtain the flexible low-melting point vinylidene fluoride copolymer; during modification, maleic anhydride or itaconic acid are grafted, and a grafting initiator is compounded from potassium persulfate and BPO. By the preparation method, melt fracture in the polymer processing process can be effectively eliminated, material accumulation at a mouth die is reduced, and the surface finish of a product is improved; the modification method is high in grafting rate, and the modified product is good in bonding performance.
Description
Technical field
The present invention relates to a kind of vinylidene fluoride copolymers, and in particular to a kind of system of flexible low melting point vinylidene fluoride copolymers
Preparation Method and its method of modifying.
Background technology
Thermoplastic resin, particularly polyolefin, in extrusion, when especially extruding in the form of a film, in extruder
It is possible that irregular flowing, causes surface defect, so as to damage the mechanical performance or optical property of thin film at die head exit.
Less than critical shear rate, extrudate is smooth, and is higher than that this speed is observed that obvious surface defect.These lack
Fall into, be referred to as " melt fracture ", the film that extrusion and blow molding is obtained can be caused to lose its transparency and glossiness and mechanicalness
Energy.
Mineral or organic filler are normally incorporated in thermoplastic resin.However, the filler for adding has promotes appearance surfaces
The tendency of defect.In this case, processing aid proposed in prior art is not largely effective, that is to say, that, it is impossible to
Extrusion defect is enough significantly reduced, or is necessary to add a larger quantities.
The fluorocarbon polymer of low-surface-energy, it is incompatible with resin, there is certain adhesive force with metal, in polyene hydrocarbon processing temperature
Do not crystallize under degree, die surfaces can be spread over, form Dynamic coating so that the passivation of flowing peak, be not likely to produce melt fracture, while
The deposition of resin and other auxiliary agents in die surfaces in avoiding processing.
Describe heterogeneous polyvinylidene fluoride copolymers thing in US 20100298487A1 and CN 200780006550.2 to use
In extrusion aid, with different molecular weight fraction, but its fusing point is higher, it is impossible to match with the polyolefinic processing technique in part,
Limit use range.
Known PVDF provides excellent mechanical stability, very high chemical inertness and good ageing resistance, therefore,
It is widely portable to chemical industry, electrical engineering, building field.It is well known, however, that PVDF is difficult to be bonded with other materials,
Limit its application.The radiation grafting by unsaturated polar monomer described in CN 200780036984.7 and functionalization
Vinylidene fluoride copolymer, can be greatly enhanced the interlayer adhesion force of PVDF in multilamellar fuel hose, while can obtain higher
Linear velocity is coextruded, but it need to first pass through premix, and melt pelletization carries out again irradiation grafting reaction, is drawn with improving general radical
Send out the low problem of the percent grafting of agent routine grafting, therefore complex process, high cost.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of system of flexible low melting point vinylidene fluoride copolymers
Preparation Method, obtained copolymer environmental protection does not contain PFOA, and molecular weight distribution is easy to adjustment, can effectively eliminate polymerization with melt viscosity
Melt fracture in the thing course of processing, mitigates accumulation in mouth model, improves product surface fineness；Present invention simultaneously provides it is simple easily
Capable method of modifying.
The preparation method of flexible low melting point vinylidene fluoride copolymers of the present invention, step is as follows：
(1) deionized water, dispersant, evacuation, deoxygenation are added in reactor；
(2) reaction temperature is warming up to, starts to be passed through initial mixing monomer, be passed through after finishing, add initiator and molecular weight
Regulator carries out polyreaction, is uninterruptedly passed through in course of reaction and adds mix monomer, and adds molecular-weight adjusting several times
Agent, adds after mix monomer is passed through and finishes, and stopped reaction obtains vinylidene copolymer resinses；
(3) vinylidene copolymer resinses condensed, washed, be dried, obtain described flexible low melting point vinylidene fluoride copolymers；
Wherein, initial mixing monomer and the mixture for adding mix monomer and being vinylidene fluoride monomers and comonomer.
Wherein：
Described dispersant is made up of non-fluorine anion surfactant and nonionic surfactant, and anionic surface is lived
Property agent and nonionic surfactant mass ratio be 1：3~4, wherein, anion surfactant is sulfate or sulfonate,
Nonionic surfactant is ether or ester.
Described deoxygenation is deoxygenation to oxygen content≤20ppm.
The consumption of described comonomer be initial mixing monomer with add the 5~40% of mix monomer gross mass；Initially
In mix monomer, comonomer accounts for the 10~40% of initial mixing monomer gross mass；In adding mix monomer, comonomer accounts for benefit
Plus the 5~30% of mix monomer gross mass.
Described initial mixing method for preparing monomer is：Comonomer is initially charged in initial slot, vinylidene is subsequently adding
Monomer, mix homogeneously.
Described mix monomer preparation method of adding is：Add and be initially charged in groove comonomer, be subsequently adding vinylidene
Monomer, mix homogeneously.
Described comonomer is fluorothene, trifluoro-ethylene, CTFE, tetrafluoroethene or hexafluoropropene.It is preferred that six
Fluoropropene.
Initiator is new peroxide tert-butyl caprate, the new heptanoic acid tert-butyl ester of peroxidating, tert-Butyl peroxypivalate, peroxide
Change di-t-butyl, di-isopropyl peroxydicarbonate or peroxy dicarbonate di-n-propyl ester；Consumption is initial mixing monomer and benefit
Plus the 0.01~1% of mix monomer gross mass.
Described molecular weight regulator is acetone, ethyl propionate, butyl propionate, diethyl malonate, ethyl acetate, acetic acid
Butyl ester or methyl acetate；Its consumption be initial mixing monomer with add the 0.1~10.0% of mix monomer gross mass.
Described polymeric reaction temperature is 30~120 DEG C, and pressure is 1.0~4.5MPa.
Preferably, described polymeric reaction temperature is 45~90 DEG C, and pressure is 2.0~4.0MPa.
Described baking temperature is 80~100 DEG C, and the time is 8~10h.
The method of modifying of described flexible low melting point vinylidene fluoride copolymers is as follows：
By flexible low melting point vinylidene fluoride copolymers powder, unsaturated polar monomer and fusion-grafting initiator at a high speed
Mix homogeneously in mixer, using automatic charging equipment, the feeding in double screw rod extruder, while evacuation, residual to remove
The HF volatile matters produced in the unreacted unsaturated polar monomer for staying and course of reaction, traction, cooling, pelletizing.
Wherein：
Unsaturated polar monomer is maleic anhydride or itaconic acid；Its consumption is flexible low melting point vinylidene fluoride copolymers powder
Material, unsaturated polar monomer and fusion-grafting are with the 1~3% of initiator gross mass.
Fusion-grafting initiator is formed by potassium peroxydisulfate and BPO compoundings, wherein, potassium peroxydisulfate is with the mass ratio of BPO
4：1~2；Its consumption is flexible low melting point vinylidene fluoride copolymers powder, unsaturated polar monomer and fusion-grafting initiator
The 0.1~2% of gross mass.
In sum, beneficial effects of the present invention are as follows：
(1) present invention is adjusted by the feed postition of molecular weight regulator, make obtained vinylidene fluoride copolymers keep with
Heterogeneous PVDF suitable molecular weight distribution and rheological behavior, use range is wide, for polymer processing aidses, can effectively disappear
Except the melt fracture in polymer processing, mitigate accumulation in mouth model, improve product surface fineness, brightness.The polymer
Can be polyolefin, styrene resin, polyester, polrvinyl chloride and blending resin.Obtained vinylidene fluoride copolymers also can use
In preparing flexible pipe, flexible optical fibre sheath.Additionally, the present invention is by adopting compounding radical initiator (potassium peroxydisulfate and BPO), directly
Being connected in melting extrusion granulation process the vinylidene fluoride copolymers to preparing carries out graft modification, and percent grafting is high, grafted maleic
Acid anhydride or itaconic acid, improve its adhesive property with other resins, widen its use range, for the preparation of multilayer materials,
Process is simple, with cost advantage.
(2) preparation method of the present invention is emulsion polymerisation process, and preparation process is simple, environmental protection does not contain PFOA, and makes
Vinylidene fluoride copolymers product fusing point, molecular weight distribution and the melt viscosity for obtaining is easy to adjustment, and pliability is good.
Specific embodiment
With reference to embodiment, the present invention will be further described.
The all raw materials used in embodiment unless otherwise specified, are commercial.
Embodiment 1
The preparation method of flexible low melting point vinylidene fluoride copolymers is as follows：
By taking 10L reactors as an example, add the sodium lauryl sulphate/Polyethylene Glycol of 6L deionized waters, 50g 30wt% hard
(both mass ratioes are 1 to fat acid ester compounding aqueous dispersant:3), evacuation, deoxygenation heats reactor to oxygen content≤20ppm
To 35 DEG C, initial mixing monomer is added, initial mixing monomer is the mixture of tetrafluoroethene and vinylidene, wherein, tetrafluoro second
The consumption of alkene is the 20% of initial mixing monomer gross mass.When pressure reaches 4.0 ± 0.1MPa, add 3g initiator peroxidating new
The capric acid tert-butyl ester and 3g acetone.Reaction starts, and adds in reactor and adds mix monomer, adds mix monomer for tetrafluoroethene
With the mixture of vinylidene, wherein, the consumption of tetrafluoroethene is add mix monomer gross mass 5%.Keep pressure constant,
2g molecular weight regulator acetone is added per 20min clocks, total is added 6 times, stop adding when adding 1.5kg to add mix monomer
Enter, stopped reaction when keeping reaction temperature to reaction pressure to be down to 2.0MPa.After copolymer emulsion is further across cohesion washing,
It is placed in 80 DEG C of vacuum drying oven and is dried 8h.60 eye mesh screens are filtered to remove agglomerated grain, and with micromill fine powder is ground into, and can be used for
Polymer processing aidses, or extruding graft pelletize is carried out for the preparation of multi-layer flexible pipe, preparation process is as follows：
By dried copolymer powder, maleic anhydride, potassium peroxydisulfate/BPO, (both mass ratioes are 4:1) compounding freedom
Base initiator is sufficiently mixed uniformly in high-speed mixer, then using automatic charging equipment, feeds in double screw rod extruder
Material, barrel temperature be respectively 180 DEG C, 190 DEG C, 220 DEG C, 210 DEG C, 190 DEG C (head), vacuum -0.10MPa is residual to remove
The volatile matters such as the HF produced in the unreacted grafted monomers that stay and course of reaction, screw speed is 100rpm, the extruded machine of material
After melting graft reaction, then draw, cool down, pelletizing, obtain graft modification vinylidene fluoride copolymers product, infrared analysiss show：
0.58% grafting degree.
The consumption of described maleic anhydride is the 3% of copolymer powder, maleic anhydride and potassium peroxydisulfate/BPO gross masses.
The consumption of described potassium peroxydisulfate/BPO is copolymer powder, maleic anhydride and potassium peroxydisulfate/BPO gross masses
0.5%.
Embodiment 2
The preparation method of flexible low melting point vinylidene fluoride copolymers is as follows：
By taking 10L reactors as an example, add the sodium lauryl sulphate/Polyethylene Glycol of 6L deionized waters, 50g 30wt% hard
(both mass ratioes are 1 to fat acid ester compounding aqueous dispersant:4), evacuation, deoxygenation heats reactor to oxygen content≤20ppm
To 65 DEG C, initial mixing monomer is added, initial mixing monomer is the mixture of hexafluoropropene and vinylidene, wherein, hexafluoro third
The consumption of alkene is the 10% of initial mixing monomer gross mass.When pressure reaches 3.5 ± 0.1MPa, add 3g initiator peroxidating new
The capric acid tert-butyl ester and 3.5g ethyl propionates.Reaction starts, and adds in reactor and adds mix monomer, adds mix monomer for six
The mixture of fluoropropene and vinylidene, wherein, the consumption of hexafluoropropene is add mix monomer gross mass 10%.Keep pressure
Power is constant, and per 20min clocks 2.5g molecular weight regulator ethyl propionates are added, and adds six times, and when 1.5kg is added mix monomer is added
When stop adding, keep reaction temperature to reaction pressure stopped reaction when being down to 2.0MPa.Copolymer emulsion is further across solidifying
After poly- washing, it is placed in 90 DEG C of vacuum drying oven and is dried 10h.60 eye mesh screens are filtered to remove agglomerated grain, are ground into micromill
Fine powder, can be used for polymer processing aidses, or carry out extruding graft pelletize for the preparation of multi-layer flexible pipe, and preparation process is as follows：
By dried copolymer powder, maleic anhydride, potassium peroxydisulfate/BPO, (both mass ratioes are 3:1) compounding freedom
Base initiator is sufficiently mixed uniformly in high-speed mixer, then using automatic charging equipment, feeds in double screw rod extruder
Material, barrel temperature be respectively 190 DEG C, 195 DEG C, 230 DEG C, 215 DEG C, 195 DEG C (head), vacuum -0.10MPa is residual to remove
The volatile matters such as the HF produced in the unreacted grafted monomers that stay and course of reaction, screw speed is 100rpm, the extruded machine of material
After melting graft reaction, then draw, cool down, pelletizing, obtain graft modification vinylidene fluoride copolymers product, infrared analysiss show：
0.65% grafting degree.
The consumption of described maleic anhydride is the 2% of copolymer powder, maleic anhydride and potassium peroxydisulfate/BPO gross masses.
The consumption of described potassium peroxydisulfate/BPO is copolymer powder, maleic anhydride and potassium peroxydisulfate/BPO gross masses
1%.
Embodiment 3
The preparation method of flexible low melting point vinylidene fluoride copolymers is as follows：
By taking 10L reactors as an example, add the sodium lauryl sulphate/Polyethylene Glycol of 6L deionized waters, 50g 30wt% hard
(both mass ratioes are 1 to fat acid ester compounding aqueous dispersant:3), evacuation, deoxygenation heats reactor to oxygen content≤20ppm
To 110 DEG C, initial mixing monomer is added, initial mixing monomer is the mixture of trifluoro-ethylene and vinylidene, wherein, trifluoro second
The consumption of alkene is the 25% of initial mixing monomer gross mass.When pressure reaches 2.5 ± 0.1MPa, 3g initiators peroxidating two is added
The tert-butyl group and 3g acetone.Reaction starts, in reactor add add mix monomer, add mix monomer for trifluoro-ethylene with it is inclined
The mixture of fluorothene, wherein, the consumption of trifluoro-ethylene is add mix monomer gross mass 20%.Keep pressure constant, often
20min clocks add 2g molecular weight regulator acetone, add six times.Stop adding when adding 1.5kg to add mix monomer, keep
Stopped reaction when reaction temperature to reaction pressure is down to 2.0MPa.After copolymer emulsion is further across cohesion washing, it is placed in true
100 DEG C of empty baking oven is dried 8h.60 eye mesh screens are filtered to remove agglomerated grain, and with micromill fine powder is ground into, and can be used to be polymerized
Thing processing aid, or extruding graft pelletize is carried out for the preparation of multi-layer flexible pipe, preparation process is as follows：
By dried copolymer powder, itaconic acid, potassium peroxydisulfate/BPO, (both mass ratioes are 2:1) compounding free radical
Initiator is sufficiently mixed uniformly in high-speed mixer, then using automatic charging equipment, the feeding in double screw rod extruder,
Barrel temperature be respectively 180 DEG C, 190 DEG C, 220 DEG C, 210 DEG C, 190 DEG C (head), vacuum -0.10MPa, to remove residual
The volatile matters such as the HF produced in unreacted grafted monomers and course of reaction, screw speed is 100rpm, and the extruded machine of material is melted
After graft reaction, then draw, cool down, pelletizing, obtain graft modification vinylidene fluoride copolymers product, infrared analysiss show：0.48%
Grafting degree.
The consumption in described itaconic acid is the 1.5% of copolymer powder, itaconic acid and potassium peroxydisulfate/BPO gross masses.
The consumption of described potassium peroxydisulfate/BPO is copolymer powder, itaconic acid and potassium peroxydisulfate/BPO gross masses
1.5%.
Embodiment 4
The preparation method of flexible low melting point vinylidene fluoride copolymers is as follows：
By taking 10L reactors as an example, add the sodium lauryl sulphate/Polyethylene Glycol of 6L deionized waters, 50g 30wt% hard
(both mass ratioes are 2 to fat acid ester compounding aqueous dispersant:7), evacuation, deoxygenation heats reactor to oxygen content≤20ppm
To 80 DEG C, initial mixing monomer is added, initial mixing monomer is the mixture of hexafluoropropene and vinylidene, wherein, hexafluoro third
The consumption of alkene is the 40% of initial mixing monomer gross mass.When pressure reaches 3.5 ± 0.1MPa, add 3g initiator peroxidating new
Heptanoic acid tert-butyl ester and 3.5g ethyl propionates.Reaction starts, and adds in reactor and adds mix monomer, adds mix monomer for six
The mixture of fluoropropene and vinylidene, wherein, the consumption of hexafluoropropene is add mix monomer gross mass 28%.Keep pressure
Power is constant, and per 20min clocks 2.5g molecular weight regulator ethyl propionates are added, and adds six times.Mix monomer is added when 1.5kg is added
When stop adding, keep reaction temperature to reaction pressure stopped reaction when being down to 2.0MPa.Copolymer emulsion is further across solidifying
After poly- washing, it is placed in 80 DEG C of vacuum drying oven and is dried 8h.60 eye mesh screens are filtered to remove agglomerated grain, are ground into carefully with micromill
Powder, can be used for polymer processing aidses, or carry out extruding graft pelletize for the preparation of multi-layer flexible pipe, and preparation process is as follows：
By dried copolymer powder, itaconic acid, potassium peroxydisulfate/BPO, (both mass ratioes are 3:1) compounding free radical
Initiator is sufficiently mixed uniformly in high-speed mixer, then using automatic charging equipment, the feeding in double screw rod extruder,
Barrel temperature be respectively 190 DEG C, 195 DEG C, 230 DEG C, 215 DEG C, 195 DEG C (head), vacuum -0.10MPa, to remove residual
The volatile matters such as the HF produced in unreacted grafted monomers and course of reaction, screw speed is 100rpm, and the extruded machine of material is melted
After graft reaction, then draw, cool down, pelletizing, obtain graft modification vinylidene fluoride copolymers product, infrared analysiss show：0.50%
Grafting degree.
The consumption in described itaconic acid is the 2% of copolymer powder, itaconic acid and potassium peroxydisulfate/BPO gross masses.
The consumption of described potassium peroxydisulfate/BPO is the 1% of copolymer powder, itaconic acid and potassium peroxydisulfate/BPO gross masses.
Comparative example 1
By taking 10L reactors as an example, add the sodium lauryl sulphate/Polyethylene Glycol of 6L deionized waters, 50g 30wt% hard
(both mass ratioes are 1 to fat acid ester compounding aqueous dispersant:4), evacuation, deoxygenation heats reactor to oxygen content≤20ppm
To 65 DEG C, initial mixing monomer is added, initial mixing monomer is the mixture of hexafluoropropene and vinylidene, wherein, hexafluoro third
The consumption of alkene is the 10% of initial mixing monomer gross mass.When pressure reaches 3.5 ± 0.1MPa, add 3g initiator peroxidating new
The capric acid tert-butyl ester, it is disposable to add 18.5g ethyl propionates.Reaction starts, and adds in reactor and adds mix monomer, adds mixed
The mixture that monomer is hexafluoropropene and vinylidene is closed, wherein, the consumption of hexafluoropropene is to add mix monomer gross mass
10%.Keep pressure constant, stop adding when adding 1.5kg to add mix monomer, keep reaction temperature to drop to reaction pressure
To stopped reaction during 2.0MPa.After copolymer emulsion is further across cohesion washing, it is placed in 90 DEG C of vacuum drying oven and is dried 10h.60
Eye mesh screen is filtered to remove agglomerated grain, and with micromill fine powder is ground into, and can be used for polymer processing aidses, or is extruded
Grafting pelletize is used for the preparation of multi-layer flexible pipe, and preparation process is as follows：
Dried copolymer powder, maleic anhydride, radical initiator BPO are sufficiently mixed in high-speed mixer
It is even, then using automatic charging equipment, the feeding in double screw rod extruder, barrel temperature be respectively 180 DEG C, 190 DEG C, 220
DEG C, 210 DEG C, 190 DEG C (head), vacuum -0.10MPa, to remove the unreacted grafted monomers of residual and course of reaction in produce
The volatile matters such as raw HF, screw speed is 100rpm, after the extruded machine melting graft reaction of material, then draw, cool down, pelletizing,
Graft modification vinylidene fluoride copolymers product is obtained, infrared analysiss show：0.25% grafting degree.
The consumption of described maleic anhydride is copolymer powder, maleic anhydride and radical initiator BPO gross masses
0.5%.
The consumption of described radical initiator BPO is copolymer powder, maleic anhydride and the total matter of radical initiator BPO
The 3% of amount.
Comparative example 2
By taking 10L reactors as an example, add the sodium lauryl sulphate/Polyethylene Glycol of 6L deionized waters, 50g 30wt% hard
(both mass ratioes are 2 to fat acid ester compounding aqueous dispersant:7), evacuation, deoxygenation heats reactor to oxygen content≤20ppm
To 80 DEG C, initial mixing monomer is added, initial mixing monomer is the mixture of hexafluoropropene and vinylidene, wherein, hexafluoro third
The consumption of alkene is the 5% of initial mixing monomer gross mass.When pressure reaches 3.5 ± 0.1MPa, add 3g initiator peroxidating new
Heptanoic acid tert-butyl ester and 3.5g ethyl propionates.Reaction starts, and adds in reactor and adds mix monomer, adds mix monomer for six
The mixture of fluoropropene and vinylidene, wherein, the consumption of hexafluoropropene is add mix monomer gross mass 4%.Keep pressure
Power is constant, and per 20min clocks 2.5g molecular weight regulator ethyl propionates are added, and adds six times.Mix monomer is added when 1.5kg is added
When stop adding, keep reaction temperature to reaction pressure stopped reaction when being down to 2.0MPa.Copolymer emulsion is further across solidifying
After poly- washing, it is placed in 80 DEG C of vacuum drying oven and is dried 8h.60 eye mesh screens are filtered to remove agglomerated grain, are ground into carefully with micromill
Powder, can be used for polymer processing aidses, or carry out extruding graft pelletize for the preparation of multi-layer flexible pipe, and preparation process is as follows：
Dried copolymer powder, itaconic acid, radical initiator potassium peroxydisulfate are fully mixed in high-speed mixer
Close uniform, then using automatic charging equipment, the feeding in double screw rod extruder, barrel temperature be respectively 190 DEG C, 195 DEG C,
230 DEG C, 215 DEG C, 195 DEG C (head), vacuum -0.10MPa, to remove the unreacted grafted monomers of residual and course of reaction in
The volatile matters such as the HF of generation, screw speed is 100rpm, after the extruded machine melting graft reaction of material, then draws, cools down, cuts
Grain, obtains graft modification vinylidene fluoride copolymers product, and infrared analysiss show：0.15% grafting degree.
The consumption in described itaconic acid is copolymer powder, itaconic acid and radical initiator potassium peroxydisulfate gross mass
4%.
The consumption of described radical initiator potassium peroxydisulfate is copolymer powder, itaconic acid and radical initiator over cure
The 0.1% of sour potassium gross mass.
Graft modification vinylidene fluoride copolymers prepared by above example and comparative example, using it is three-layer co-extruded go out technique system
Standby following structure multilayer pipe (external diameter：10mm)：
PVDF DS206 (100 μm)/graft modification vinylidene fluoride copolymers (50 μm)/PE (500 μm), wherein PVDF
DS206 is that company produces PVDF homopolymer resins.
PE layers are outer layer.PVDF DS206 layers are internal layer.Extruded with 35m/min in following condition：
PVDF DS206 layers：235 DEG C, graft modification vinylidene fluoride copolymers layer：235 DEG C, PE layers：230℃.
Multilayer pipe bonding force is peeled off by circumference and measured.
Embodiment 1, embodiment 2, embodiment 3, embodiment 4 are as a result vinylidenes compared with comparative example 1, comparative example 2
Molecular weight of copolymer distribution is easily controllable, and percent grafting is high, and the molecular weight distribution and product other performance of above-mentioned each example are shown in table 1.
Wherein rheology viscosity is capillary rheology viscosity, at 230 DEG C, shear rate 100s-1Under the conditions of measure.As it can be seen from table 1 with
Comparative example 1 compares, and embodiment 2, can Effective Regulation range of molecular weight distributions by changing molecular-weight adjusting mode；With comparative example 2
Relatively, embodiment 4 is combined by adjustment initial mixing monomer with the ratio for adding mix monomer, can Effective Regulation melting range.
The multilayer pipe bonding force data ratio of the vinylidene fluoride copolymers performance data of table 1 and graft modification vinylidene fluoride copolymers
Compared with
Claims (10)
1. a kind of preparation method of flexible low melting point vinylidene fluoride copolymers, it is characterised in that：Step is as follows：
(1) deionized water, dispersant, evacuation, deoxygenation are added in reactor；
(2) reaction temperature is warming up to, starts to be passed through initial mixing monomer, be passed through after finishing, add initiator and molecular-weight adjusting
Agent carries out polyreaction, is uninterruptedly passed through in course of reaction and adds mix monomer, and adds molecular weight regulator several times, mends
Plus mix monomer is passed through after finishing, stopped reaction obtains vinylidene copolymer resinses；
(3) vinylidene copolymer resinses condensed, washed, be dried, obtain described flexible low melting point vinylidene fluoride copolymers；
Wherein, initial mixing monomer and the mixture for adding mix monomer and being vinylidene fluoride monomers and comonomer.
2. the preparation method of flexible low melting point vinylidene fluoride copolymers according to claim 1, it is characterised in that：Dispersant
It is made up of non-fluorine anion surfactant and nonionic surfactant, anion surfactant and non-ionic surface active
The mass ratio of agent is 1：3~4, wherein, anion surfactant is sulfate or sulfonate, and nonionic surfactant is ether
Or ester.
3. the preparation method of flexible low melting point vinylidene fluoride copolymers according to claim 1, it is characterised in that：Copolymerization list
The consumption of body be initial mixing monomer with add the 5~40% of mix monomer gross mass；In initial mixing monomer, comonomer is accounted for
The 10~40% of initial mixing monomer gross mass；In adding mix monomer, comonomer account for add mix monomer gross mass 5~
30%.
4. the preparation method of the flexible low melting point vinylidene fluoride copolymers according to claim 1 or 3, it is characterised in that：Altogether
Polycondensation monomer is fluorothene, trifluoro-ethylene, CTFE, tetrafluoroethene or hexafluoropropene.
5. the preparation method of flexible low melting point vinylidene fluoride copolymers according to claim 1, it is characterised in that：Initiator
For new peroxide tert-butyl caprate, the new heptanoic acid tert-butyl ester of peroxidating, tert-Butyl peroxypivalate, di-t-butyl peroxide, mistake
Aoxidize two diisopropyl carbonates or peroxy dicarbonate di-n-propyl ester；Consumption be initial mixing monomer with add the total matter of mix monomer
The 0.01~1% of amount.
6. the preparation method of flexible low melting point vinylidene fluoride copolymers according to claim 1, it is characterised in that：Molecular weight
Regulator is acetone, ethyl propionate, butyl propionate, diethyl malonate, ethyl acetate, butyl acetate or methyl acetate；Its use
Measure for initial mixing monomer with add the 0.1~10.0% of mix monomer gross mass.
7. the preparation method of flexible low melting point vinylidene fluoride copolymers according to claim 1, it is characterised in that：Polymerization is anti-
Temperature is answered for 30~120 DEG C, pressure is 1.0~4.5MPa.
8. the method for modifying of the flexible low melting point vinylidene fluoride copolymers described in a kind of claim 1, it is characterised in that：By flexibility
Low melting point vinylidene fluoride copolymers powder, unsaturated polar monomer and fusion-grafting initiator mix in high-speed mixer
It is even, using automatic charging equipment to feeding in double screw rod extruder, while evacuation, unsaturated with the unreacted for removing residual
The HF volatile matters produced in polar monomer and course of reaction, traction, cooling, pelletizing.
9. the method for modifying of flexible low melting point vinylidene fluoride copolymers according to claim 8, it is characterised in that：It is unsaturated
Polar monomer is maleic anhydride or itaconic acid；Its consumption is flexible low melting point vinylidene fluoride copolymers powder, unsaturated polarity list
Body and fusion-grafting are with the 1~3% of initiator gross mass.
10. the method for modifying of flexible low melting point vinylidene fluoride copolymers according to claim 8, it is characterised in that：Melting
Grafting initiator is formed by potassium peroxydisulfate and BPO compoundings, wherein, potassium peroxydisulfate is 4 with the mass ratio of BPO：1~2；Its consumption
For flexible low melting point vinylidene fluoride copolymers powder, unsaturated polar monomer and fusion-grafting initiator gross mass 0.1~
2%.
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| CN112538130A (en) * | 2020-12-07 | 2021-03-23 | 常熟三爱富中昊化工新材料有限公司 | Vinylidene fluoride copolymer and preparation method and application thereof |
| CN112625165A (en) * | 2019-10-08 | 2021-04-09 | 中昊晨光化工研究院有限公司 | Trifluoroethylene modified fluororesin and preparation method thereof |
| CN114716617A (en) * | 2022-04-29 | 2022-07-08 | 安徽大学 | High-hydrophilicity PVDF material and preparation method thereof |
| CN116217781A (en) * | 2023-04-26 | 2023-06-06 | 山东惠畅新材料有限公司 | Fluoropolymer processing aid PPA and preparation method thereof |
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| CN110343211A (en) * | 2018-04-03 | 2019-10-18 | 浙江省化工研究院有限公司 | A kind of polyvinylidene fluoride copolymer resin and preparation method thereof |
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| CN112538130A (en) * | 2020-12-07 | 2021-03-23 | 常熟三爱富中昊化工新材料有限公司 | Vinylidene fluoride copolymer and preparation method and application thereof |
| CN114716617A (en) * | 2022-04-29 | 2022-07-08 | 安徽大学 | High-hydrophilicity PVDF material and preparation method thereof |
| CN114716617B (en) * | 2022-04-29 | 2023-10-17 | 安徽大学 | High-hydrophilicity PVDF material and preparation method thereof |
| CN116217781A (en) * | 2023-04-26 | 2023-06-06 | 山东惠畅新材料有限公司 | Fluoropolymer processing aid PPA and preparation method thereof |
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