CN106632770A - Preparation method of polyvinylidene fluoride (PVDF) - Google Patents
Preparation method of polyvinylidene fluoride (PVDF) Download PDFInfo
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- CN106632770A CN106632770A CN201611206158.XA CN201611206158A CN106632770A CN 106632770 A CN106632770 A CN 106632770A CN 201611206158 A CN201611206158 A CN 201611206158A CN 106632770 A CN106632770 A CN 106632770A
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- kynoar
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers 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
- C08F114/18—Monomers containing fluorine
- C08F114/22—Vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- Medicinal Chemistry (AREA)
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of organic synthesis and particularly relates to a preparation method of PVDF. Vinyl fluoride, deionized water, initial chain transfer agents and a dispersing agent are added to a reaction kettle, evacuation and deoxygenization are performed, the temperature is raised to 20 DEG C to 150 DEG C, the kettle is refilled with vinylidene fluoride monomers until the pressure in the kettle is 1.0-6.0 MPa, and an initial chain transfer agent is added; polymerization reaction is started, the kettle is refilled with another chain transfer agent and a replenishing initiator, and after the reaction, the finished product is obtained after the obtained polymer emulsion is subjected to condensation, washing, drying and granulation. According to the preparation method of the PVDF, two kinds of chain transfer agents are firstly used in the polymerization process, a production technology of the PVDF with controllable molecular weight and distribution of the molecular weight for narrow size distribution is provided, and the technological conditions are mild and easy to control; the molecular weight of the product obtained by polymerization is uniform, the distribution is narrow, and the production efficiency is improved.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of preparation method of Kynoar.
Background technology
Kynoar (PVDF) be it is a kind of with resistance to chemical attack, it is ageing-resistant and superior mechanical processing characteristics fluorine-containing
Thermoplastic engineering plastic, by moulding process such as extrusion, injection, moldings, is processed to various products, is widely used in manufacturing work
The fields such as industry, electronics industry and water treatment field.
In view of the application of PVDF is more and more extensive, people are increasing to the demand of PVDF, and the yield for PVDF is closed
Note degree is with regard to more and more higher；Other properties of product aspect, especially in molding process, inequality of being heated, molecular weight distribution width,
Small-molecule substance easily decomposition etc. can cause mouth mold swelling, cause product mechanical property to be deteriorated, and finally cause product to turn yellow, shadow
Ring product to use.
Therefore, the yield of Kynoar how is improved, effective control improves Kynoar molecular weight and its is scattered in
For an important process in Kynoar production.
For this purpose, having done many work both at home and abroad, there are a large amount of reports at present.
Patent CN1526744A adds in the product sodium acetate and alkyl sulfonic acid potassium, and goes eliminating water and drop by being spray-dried
The impurity being mixed with low product.Because the patent does not use chain-transferring agent, initiator, product molecular weight distribution are done with potassium peroxydisulfate
Poor, unstable end-group is more, so while the yellowness index of product has declined compared with comparative example, but fall is less, effect
Fruit is not obvious.
Patent US5093427 is disclosed using methyl alcohol and prepares PVDF resins as chain-transferring agent, and methyl alcohol does not have to rate of polymerization
Affect, but be unable to the molal weight of effective control PVDF, cause molecular weight and molecualr weight distribution uncontrollable phenomenon easily occur.
United States Patent (USP) US4076929 discloses a kind of Kynoar of bimodal molecular weight distribution.It uses peroxidating two
The tert-butyl group is initiator, in the presence of surfactant, polymerisation is carried out in the case where chain-transferring agent is not added.By
In efficient chain transfer is lacked, the Kynoar for obtaining that is polymerized has the molecular weight distribution of non-constant width.
In addition patent FR2259114 is used acetone as chain-transferring agent, patent US4360652 and is turned as chain using isopropanol
Agent, CN101218264B are moved using dimethyl ether, halogenated hydrocarbons and alkane as chain-transferring agent, but is obtained using these chain-transferring agents
PVDF still have wider molecular weight distribution, its molecular weight distribution index is generally between 4-20.Substantial amounts of HMW
Component causes processing difficulties, a large amount of lower-molecular-weight components then to cause product xanthochromia and mechanical performance, chemical-resistance to reduce.
And we will also be appreciated that document is not directed to the polymerization of Kynoar from above-mentioned patent document disclosure
The product features such as time, yield, granularity；Even if in CN101218264B, giving polymerization time, particle mean size, solids content
Correction data, but in addition to polymerization time, remainder data is not improved, it follows that existing technology is to whole production
Efficiency does not make any substantial improvement.
The content of the invention
It is an object of the invention to provide a kind of preparation method of Kynoar, process is simple, effect is significant, application are wide
It is general, Kynoar molecular weight and its distribution can be effectively controlled, while the yield of Kynoar can be improved.
The preparation method of Kynoar of the present invention, step is as follows：
(1) vinylidene, deionized water, initial chain-transferring agent, dispersant are added in reactor, evacuation, deoxygenation heat up
It is 1.0-6.0MPa by adding vinylidene fluoride monomers to pressure in kettle to 20-150 DEG C, adds initial initiator；
(2) start polymerisation, add chain-transferring agent and add initiator, after reaction terminates, by the polymer for obtaining breast
Liquid Jing condenses-washs-be dried to granulation and gets product.
Described Kynoar is made up of the raw material of following parts by weight：
Described initiator is organic initiators, preferably peroxy dicarbonate dioxane esters.
The concentration of described initiator is 1-30wt%, preferably 10-15wt%.
Initial chain-transferring agent described in step (1) is unsaturated esters；Preferably alkene esters, such as ethyl acrylate.
The concentration of the initial chain-transferring agent described in step (1) is 0.001-5wt%, preferably 0.01-2wt%.
Dispersant described in step (1) is non-PFOA perfluors dispersant.
Chain-transferring agent described in step (2) is the one kind in alcohols, ketone or esters；Preferably esters, such as propionic acid second
Ester.
The concentration of the chain-transferring agent described in step (2) is 1-20wt%, preferably 5-10wt%.
Polymeric reaction temperature described in step (2) is 20-150 DEG C, and polymerization reaction time is 1-8h.
The feed postition of described raw material is to be continuously added to.
The present invention is adopted using vinylidene as raw material, with non-PFOA perfluors dispersant as auxiliary agent, by emulsion polymerization
Polyvinylidene fluoride resin of the synthesis without PFOA, solves the environmental issue of PFOA.Polymerization formula is adjusted in addition, polymerization is helped
Agent is optimized, and is not only greatly improved the uniformity of molecular weight, and the effective control molecular weight distribution of resin, solves
Polymer molecular weight and its molecular weight distribution are unable to the problem of effective control；New and effective aftertreatment technology is adopted simultaneously, it is whole
Individual aftertreatment technology separates-washs-be dried to crushing and all takes fully enclosed automatic to process from polymer, it is ensured that system
Stability, cleannes and high efficiency are a kind of high without perfluoro caprylic acid, narrow molecular weight distribution, production efficiency so as to finally give
Polyvinylidene fluoride resin.
The polyvinylidene fluoride resin product high to produce a kind of narrow molecular weight distribution, production efficiency.The present invention is using reaction
Activation energy is relatively low, end group stabilization organic initiators, using the esters chain-transferring agent to this system with top adjustment efficiency.Polymerization
When, in order to the uniformity for ensureing initiator and conditioning agent each position in kettle can guarantee that suitable reaction speed again simultaneously, this
A kind of totally two kinds of invention chain-transferring agent, the initial chain-transferring agent added before polymerization controls the chain length of strand main chain, Molecular regulator
The size of amount, another kind takes in the course of the polymerization process the chain-transferring agent that continuous dosing mode is added, the distribution of Molecular regulator amount and control
Conversion ratio processed, so as to ensure that the uniformity that molecular weight is improved while production efficiency.
Present invention discover that using the relatively low organic peroxide evocating agent of reaction activity, initial chain-transferring agent and high efficiency
Chain-transferring agent, and by the way of continuous dosing, the PVDF polymer of molecular weight uniform narrow ditribution, high efficiency is obtained
Product, and reaction condition is gentle, and molecular weight is controllable.
The present invention compared with prior art, has the advantages that：
2 kinds of chain-transferring agents are used first in the course of the polymerization process, have introduced a kind of control strand backbone chain length, improved and divide
Son amount size and its initial chain-transferring agent for adding before polymerization of distribution, another kind adjustment molecular weight uniform degree, control polymerization
A kind of chain-transferring agent that speed is added in the course of the polymerization process, there is provided the controllable narrow ditribution polyvinylidene fluoride of molecular weight and its distribution
The production technology of alkene, the process conditions are gentle, easily-controllable.The molecular weight product for obtaining that is polymerized is uniform, narrowly distributing, and production efficiency is high.
Specific embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
In the horizontal reacting kettle of 100L, add the deionized water of 60L, initial chain-transferring agent ethyl acrylate 2g, 20%
The aqueous solution 100g of perfluorocarboxylic acid base polyethers ammonium salt, evacuation, deoxygenation are qualified to oxygen content≤30ppm.Then to polymeric kettle liter
Temperature, by adding vinylidene fluoride monomers to pressure 3.0MPa in kettle, is then quickly squeezed into 100g reactions and is lived to 60 DEG C with measuring pump
Change the relatively low initial organic initiators solution (15% diisopropyl peroxidating carbonic acid hydrogen ester) of energy, start polymerisation, keep temperature
Degree, pressure are constant, after 10min, are at the uniform velocity squeezed into measuring pump, 1500g10% chain-transferring agent solution (conditioning agent is ethyl propionate)
Initiator solution is added with 300g 15%, 2h has beaten.In polymerization process, keep kettle temperature kettle pressure constant, it is certain when reaching
After reacting dose, stop reaction.Cohesion, washing, dry, granulation, test and pack.
Embodiment 2
It is that initial chain tra nsfer dosage is changed to 5g with the difference of embodiment 1, adds chain tra nsfer dosage and be changed to 3000g5% chains turn
Move agent solution.
Embodiment 3
It is to add chain-transferring agent to be changed to ethyl acetate with the difference of embodiment 1.
Comparative example 1
It is that initial chain-transferring agent addition is 0g with the difference of embodiment 1.
Comparative example 2
In the horizontal reacting kettle of 100L, add the deionized water of 60L, initial chain-transferring agent be ethyl propionate 2g, 20%
Aqueous solution 100g, evacuation, the deoxygenation of perfluorocarboxylic acid base polyethers ammonium salt, is qualified to oxygen content≤30ppm.Then to polymeric kettle liter
To 135 DEG C, by adding vinylidene fluoride monomers to pressure 3.0MPa in kettle, quickly squeeze into 100g with measuring pump initially has power traction to temperature
Agent solution (15% peroxidized t-butyl perbenzoate) is sent out, starts polymerisation, after 10min, at the uniform velocity squeezed into measuring pump
1500g10% chain-transferring agent solution (conditioning agent is ethyl propionate) and 300g 15% add initiator solution, and 2h has beaten.Polymerization
In course of reaction, keep kettle temperature kettle pressure constant, after certain reacting dose is reached, stop reaction.Condense, wash, be dried, make
Grain, tests and packs.
Comparative example 3
In the horizontal reacting kettle of 100L, add the deionized water of 60L, initial chain-transferring agent be ethyl propionate 2g, 20%
Aqueous solution 100g, evacuation, the deoxygenation of perfluorocarboxylic acid base polyethers ammonium salt, is qualified to oxygen content≤30ppm.Then to polymeric kettle liter
To 135 DEG C, by adding vinylidene fluoride monomers to pressure 3.0MPa in kettle, quickly squeeze into 100g with measuring pump initially has power traction to temperature
Send out agent solution (15% peroxidized t-butyl perbenzoate), start polymerisation, 135 DEG C of reaction temperature, reaction pressure 3MPa,
After 10min, at the uniform velocity squeeze into 1500g10% chain-transferring agent solution (conditioning agent is acetone) with measuring pump and 300g 15% is added and drawn
Agent solution is sent out, 2h has beaten.In polymerization process, keep kettle temperature kettle pressure constant, after certain reacting dose is reached, stop anti-
Should.Cohesion, washing, dry, granulation, test and pack.
Embodiment 1 compared with Example 2 compared with, it can be seen that increase initial chain-transferring agent, reduce efficiently being adjusted in polymerization process
The concentration of section agent solution, is conducive to a certain extent the control of molecular size range and molecular weight distribution；Embodiment 1, embodiment
2nd, embodiment 3 is compared with comparative example 1, comparative example 2, comparative example 3, it can be seen that be conducive to changing using initial alkenes chain-transferring agent
Kind product pliability is that the elongation at break of product is higher；Embodiment 1, embodiment 2, embodiment 3, can compared with comparative example 1
To find out, initial chain-transferring agent is added, be conducive to improving molecular size range and its distribution, narrower molecular weight distribution can be obtained
Product；Embodiment 1, embodiment 2, embodiment 3 are compared with comparative example 2, it can be seen that during using low-activation energy initiator, instead
Answer speed partially slow, low production efficiency；Embodiment 1, embodiment 2, embodiment 3 are compared with comparative example 3, it can be seen that using low
Molecular weight wider distribution and low production efficiency during the chain-transferring agent of activation energy initiator and high adjustment efficiency；
The polymerization situation of above-mentioned each example, molecular weight and molecular weight distribution and elongation at break are shown in table 1.
The Kynoar data of table 1 compare
Claims (10)
1. a kind of preparation method of Kynoar, it is characterised in that step is as follows：
(1) vinylidene, deionized water, initial chain-transferring agent, dispersant are added in reactor, evacuation, deoxygenation are warming up to
20-150 DEG C, be 1.0-6.0MPa by adding vinylidene fluoride monomers to pressure in kettle, adds initial initiator；
(2) start polymerisation, add chain-transferring agent and add initiator, after reaction terminates, by the polymer emulsion Jing for obtaining
Condense-wash-be dried to granulation to get product.
2. the preparation method of Kynoar according to claim 1, it is characterised in that Kynoar is by following weight
The raw material of number is made：
3. the preparation method of Kynoar according to claim 1 and 2, it is characterised in that described initiator is organic
Initiator.
4. the preparation method of Kynoar according to claim 3, it is characterised in that the concentration of described initiator is
1-30wt%.
5. the preparation method of Kynoar according to claim 1, it is characterised in that the initial chain described in step (1)
Transfer agent is unsaturated esters.
6. the preparation method of Kynoar according to claim 1, it is characterised in that the initial chain described in step (1)
The concentration of transfer agent is 0.001-5wt%.
7. the preparation method of Kynoar according to claim 1, it is characterised in that the dispersant described in step (1)
For non-PFOA perfluors dispersant.
8. the preparation method of Kynoar according to claim 1, it is characterised in that the chain tra nsfer described in step (2)
Agent is the one kind in alcohols, ketone or esters.
9. the preparation method of Kynoar according to claim 1, it is characterised in that the chain tra nsfer described in step (2)
The concentration of agent is 1-20wt%.
10. the preparation method of Kynoar according to claim 1, it is characterised in that the polymerization described in step (2)
Reaction temperature is 20-150 DEG C, and polymerization reaction time is 1-8h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102134292A (en) * | 2011-01-07 | 2011-07-27 | 山东东岳神舟新材料有限公司 | Preparation method for polyvinylidene fluoride with high molten fluidity |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134292A (en) * | 2011-01-07 | 2011-07-27 | 山东东岳神舟新材料有限公司 | Preparation method for polyvinylidene fluoride with high molten fluidity |
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