CN105924554B - A kind of preparation method of polyvinylidene fluoride resin - Google Patents
A kind of preparation method of polyvinylidene fluoride resin Download PDFInfo
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- CN105924554B CN105924554B CN201610410749.2A CN201610410749A CN105924554B CN 105924554 B CN105924554 B CN 105924554B CN 201610410749 A CN201610410749 A CN 201610410749A CN 105924554 B CN105924554 B CN 105924554B
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- polyvinylidene 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
- 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
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Abstract
The invention discloses a kind of preparation methods of polyvinylidene fluoride resin, including vinylidene fluoride monomers polymerization, washing, drying, use organic and inorganic dispersant in molar ratio for 1:(1~5 in polymerization procedure) dispersant system of combination, in parts by weight, by 100 parts of deionized water, 0.003~0.09 part of dispersant system, 0.01~0.1 part of initiator, 0.001~0.1 part of chain-transferring agent, 20~38 parts of addition polymeric kettles of VDF monomer terminate reaction at 40~80 DEG C after 5~18h of polymerization reaction.For the present invention by the way of suspension polymerisation, final polyvinylidene fluoride resin obtained has excellent heat resistance.
Description
Technical field
The present invention relates to fluoropolymer-containing preparation methods, and in particular to a kind of preparation method of polyvinylidene fluoride resin.
Background technique
Kynoar (PVDF) refers to that the modification of the homopolymer or VDF and a small amount of other monomers of vinylidene (VDF) is total
Polymers.It is a kind of high molecular weight, hemicrystalline thermoplastic, has excellent mechanical property, creep-resistant property, resistance to height
Warm nature, weatherability, radiation resistance, resistance to chemical corrosion and low combustible.Based on above-mentioned excellent performance, so that PVDF has become at present
For the second largest fluoropolymer kind for being only second to polytetrafluoroethylene (PTFE) (PTFE) in fluororesin, it is widely used in petrochemical industry, metallurgy, system
Medicine, building, food, water process, the fields such as military project and aerospace, development prospect are wide.The industrialized production side of PVDF at present
Formula mainly has emulsion polymerization and suspension polymerization.The suspension polymerisation (Suspension polymerization) of vinylidene
It is cellulose ether or polyvinyl alcohol using high purity water as medium, without PFOA etc. for dispersing agent, organic peroxide causes poly-
It closes, product grain form is good, and postprocessing working procedures are simple.However the PVDF resin of suspension process preparation still remains and lotion work
The similar problem of PVDF of skill preparation: i.e. trace impurity remaining in the resin thermal stability that has seriously affected final products, this
A little impurity fail the residual initiators cleaned up or dispersing agent etc. after being derived from polymerization.
Patent US362404 proposes to improve polymerization temperature after PVDF resin particle is formed to reduce the additional amount of initiator
To improve the thermal stability of final PVDF resin, but thus legal system obtains that PVDF molecular weight is more difficult to control and molecular weight distribution becomes
It is wide.Patent CN102336854B proposes that selecting magnesium hydroxide is dispersing agent, which is easy to wash out after polymerization, thus
The thermal stability of PVDF resin is improved, but temperature is not easy to control in the course of the polymerization process for the method, there is the risk of implode, it is obtained
PVDF particle sphericity is poor, mostly random shape.Patent CN103467631 proposes to be made into one after the washing of PVDF resin
Determine the slurries of concentration, acidic materials are added and are dehydrated, thus improve the high temperature coloring resistance of PVDF resin, but the method increases
PVDF resin post-processing step, so that increased production cost and efficiency decline.Patent US7943707 is proposed in VDF critical pressure
(Pc=4.38MPa) VDF monomer is added into polymeric kettle in batches below or more it is polymerize to obtain and have excellent high resistance to
The PVDF resin of coloring, but the method controls polymerization technique and requires harsh, is made that PVDF molecular weight is more difficult to control and molecular weight
Distribution broadens.
Summary of the invention
The purpose of the present invention is overcoming the shortcomings of the prior art, a kind of simple process and low cost, thermal stability are provided
The technology of preparing of excellent PVDF resin, and in particular to a kind of preparation method of polyvinylidene fluoride resin, PVDF resin obtained
Thermal stability is improved on the basis of not influencing other performance.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme:
A kind of preparation method of polyvinylidene fluoride resin, including vinylidene fluoride monomers polymerization, washing, drying, feature exist
In: use organic and inorganic dispersant in molar ratio for 1:(1~5 in polymerization procedure) dispersant system of combination, by weight
Number, by 100 parts of deionized water, 0.003~0.09 part of dispersant system, 0.01~0.1 part of initiator, chain-transferring agent 0.001~
0.1 part, 20~38 parts of addition polymeric kettles of VDF monomer terminate reaction at 40~80 DEG C after 5~18h of polymerization reaction.
Further, organic dispersing agent is in methyl cellulose ether, hydroxyethyl ether cellulose and hydroxypropyl methyl cellulose ether
One kind.
Further, inorganic dispersant is one of calcium phosphate, aluminium hydroxide and trbasic zinc phosphate.
Further, chain-transferring agent is one of ethyl acetate, diethyl carbonate, acetone and pentamethylene, and chain-transferring agent is
0.003~0.05 part.
Further, initiator is that tert-Butyl peroxypivalate, peroxidating tert-butyl isobutyrate, dicetyl peroxydicarbonate two are different
One of propyl ester and peroxy dicarbonate di-n-propyl ester, initiator are 0.02~0.06 part.
Further, organic molar ratio with inorganic dispersant is 1:(1~3), it is inorganic using part in the course of the polymerization process
Dispersing agent replaces organic dispersing agent, obtains composite dispersing agent system, largely reduces the organic dispersing agent for being difficult to wash out and uses
Amount, while the composite dispersing agent system has excellent dispersion and colloid protection ability, to polymerization process and final PVDF particle shape
It has no adverse effects.
Further, dispersant system is 0.005~0.05 part.
Further, the reaction temperature in polymerization procedure is 50~70 DEG C, and the reaction time is 6~15h.
Further, the strong oxidizer for being 0.01%~0.1% relative to PVDF wet feed weight, washing are added in washing step
After by resulting polymers dry to get arrive PVDF resin, be added strong oxidizer promote composite dispersing agent system in it is organic
Dispersing agent decomposes, and remaining organic dispersing agent in resin is thoroughly washed out to obtain and have excellent heat resistance
PVDF resin.
Further, strong oxidizer is one of sodium peroxide, hydrogen peroxide, potassium permanganate and hypochlorous acid, and strong oxidizer is
0.03~0.05% relative to PVDF wet feed weight.
The present invention is by adopting the above-described technical solution, have the advantages that
The present invention replaces having using part inorganic dispersant in the course of the polymerization process for the mechanism for influencing PVDF thermal stability
Machine dispersing agent, obtains composite dispersing agent system, largely reduces the organic dispersing agent dosage for being difficult to wash out, while this is compound
Dispersant system has excellent dispersion and colloid protection ability, has no adverse effects to polymerization process and final PVDF particle shape.?
In washing step, strong oxidizer is added, the organic dispersing agent in composite dispersing agent system is promoted to decompose, so that remaining in resin
Organic dispersing agent can thoroughly wash out to obtain the PVDF resin with excellent heat resistance.
Specific embodiment
A kind of preparation method of polyvinylidene fluoride resin of the present invention, including vinylidene fluoride monomers polymerization, washing, drying, gather
Close and use organic and inorganic dispersant in molar ratio for 1:(1~3 in step) dispersant system that combines, organic dispersing agent is first
One of base cellulose ether, hydroxyethyl ether cellulose and hydroxypropyl methyl cellulose ether, inorganic dispersant are calcium phosphate, hydrogen-oxygen
Change one of aluminium and trbasic zinc phosphate.In parts by weight, by 100 parts of deionized water, 0.005~0.05 part of dispersant system, cause
0.02~0.06 part of agent, initiator is that tert-Butyl peroxypivalate, peroxidating tert-butyl isobutyrate, dicetyl peroxydicarbonate two are different
One of propyl ester and peroxy dicarbonate di-n-propyl ester, 0.003~0.05 part of chain-transferring agent, chain-transferring agent be ethyl acetate,
One of diethyl carbonate, acetone and pentamethylene, 20~38 parts of addition polymeric kettles of VDF monomer polymerize anti-at 50~70 DEG C
Reaction is terminated after answering 6~15h.
The strong oxidizer for being 0.03~0.05% relative to PVDF wet feed weight is added in washing step, strong oxidizer was
One of sodium oxide molybdena, hydrogen peroxide, potassium permanganate and hypochlorous acid dry resulting polymers to get PVDF is arrived after washing
Resin is added strong oxidizer and the organic dispersing agent in composite dispersing agent system is promoted to decompose, so that organic point remaining in resin
Powder can thoroughly wash out to obtain the PVDF resin with excellent heat resistance.
The present invention replaces having using part inorganic dispersant in the course of the polymerization process for the mechanism for influencing PVDF thermal stability
Machine dispersing agent, obtains composite dispersing agent system, largely reduces the organic dispersing agent dosage for being difficult to wash out, while this is compound
Dispersant system has excellent dispersion and colloid protection ability, has no adverse effects to polymerization process and final PVDF particle shape.?
In washing step, strong oxidizer is added, the organic dispersing agent in composite dispersing agent system is promoted to decompose, so that remaining in resin
Organic dispersing agent can thoroughly wash out to obtain the PVDF resin with excellent heat resistance.
Below in conjunction with specific embodiment, the present invention is furture elucidated, but these the examples are only for explaining the invention, without
It is for limiting the scope of the invention.
Embodiment 1
3000g deionized water, 0.15g dispersant system, the dispersing agent are added in the 5L vertical retort of the oblique paddle of double-deck two leaves
System is made of by 1:1 with inorganic dispersant calcium phosphate organic dispersing agent methyl cellulose ether and is configured, 0.6g peroxidating two
Temperature of reaction kettle is risen to 45 DEG C of progress polymerization reactions, end after 12h by diisopropyl carbonate, 0.09g pentamethylene, 600gVDF monomer
Only react.It will be transferred in the 20L washing kettle of jacketed after the filtering of resulting polymers slurries, 10L deionized water and opposite is added
After being warming up to 50 DEG C of washing 2h, resulting polymers are done at 80 DEG C for the potassium permanganate for being 0.01% in polymer wet feed weight
Dry 10h, finished product.The finished product yellowness index test result is shown in Table 1.
Embodiment 2
3000g deionized water, 0.3g dispersant system, the dispersing agent body are added in the 5L vertical retort of the oblique paddle of double-deck two leaves
System is made of with inorganic dispersant calcium phosphate by 1:2 organic dispersing agent methyl cellulose ether to be configured, 1.5g peroxidating new penta
Temperature of reaction kettle is risen to 60 DEG C of progress polymerization reactions, terminated after 8h by tert-butyl acrylate, 0.3g diethyl carbonate, 900gVDF monomer
Reaction.Will resulting polymers slurries filtering after be transferred in the 20L washing kettle of jacketed, be added 10L deionized water and relative to
The hypochlorous acid that polymer wet feed weight is 0.03%, it is after being warming up to 50 DEG C of washing 2h, resulting polymers are dry at 80 DEG C
10h, finished product.The finished product yellowness index test result is shown in Table 1.
Embodiment 3
3000g deionized water, 0.9g dispersant system, the dispersing agent body are added in the 5L vertical retort of the oblique paddle of double-deck two leaves
System is made of with inorganic dispersant aluminium hydroxide by 1:2 organic dispersing agent hydroxypropyl methyl cellulose ether to be configured, 1.8g mistake
The neopentanoic acid tert-butyl ester, 0.1g diethyl carbonate are aoxidized, temperature of reaction kettle is risen to 60 DEG C of progress polymerization reactions by 900gVDF monomer,
8h terminates reaction.Will resulting polymers slurries filtering after be transferred in the 20L washing kettle of jacketed, be added 10L deionized water and
The hypochlorous acid for being 0.03% relative to polymer wet feed weight, after being warming up to 50 DEG C of washing 2h, by resulting polymers at 80 DEG C
Dry 10h, finished product.The finished product yellowness index test result is shown in Table 1.
Embodiment 4
3000g deionized water, 1.5g dispersant system, the dispersing agent body are added in the 5L vertical retort of the oblique paddle of double-deck two leaves
System is made of with inorganic dispersant aluminium hydroxide by 1:3 organic dispersing agent hydroxypropyl methyl cellulose ether to be configured, 1.8g mistake
The neopentanoic acid tert-butyl ester, 1g acetone are aoxidized, temperature of reaction kettle is risen to 70 DEG C of progress polymerization reactions, terminated after 6h by 800gVDF monomer
Reaction.Will resulting polymers slurries filtering after be transferred in the 20L washing kettle of jacketed, be added 10L deionized water and relative to
The hypochlorous acid that polymer wet feed weight is 0.05%, it is after being warming up to 50 DEG C of washing 2h, resulting polymers are dry at 80 DEG C
10h, finished product.The finished product yellowness index test result is shown in Table 1.
Embodiment 5
3000g deionized water, 1.2g dispersant system, the dispersing agent body are added in the 5L vertical retort of the oblique paddle of double-deck two leaves
System is made of with inorganic dispersant trbasic zinc phosphate by 1:3 organic dispersing agent hydroxypropyl methyl cellulose ether to be configured, 1.8g peroxide
Change two diisopropyl carbonates, 1g ethyl acetate, temperature of reaction kettle is risen to 40 DEG C of progress polymerization reactions, 15h by 900gVDF monomer
Reaction is terminated afterwards.Will resulting polymers slurries filtering after be transferred in the 20L washing kettle of jacketed, be added 10L deionized water and
The sodium peroxide for being 0.05% relative to polymer wet feed weight, after being warming up to 50 DEG C of washing 2h, by resulting polymers in 80 DEG C
Lower dry 10h, finished product.The finished product yellowness index test result is shown in Table 1.
Comparative example 1
Similar to Example 1, only difference is that potassium permanganate is added without in washing process.The finished product yellowness index is surveyed
Test result is shown in Table 1.
Comparative example 2
Similar to Example 3, only difference is that the dispersant system being added is entirely hydroxypropyl methyl cellulose ether.It should
Finished product yellowness index test result is shown in Table 1.
Comparative example 3
The addition 3000g deionized water in the 5L vertical retort of the oblique paddle of double-deck two leaves, 1.5g hydroxypropyl methyl cellulose ether,
Temperature of reaction kettle is risen to 70 DEG C of progress polymerization reactions by 1.5g tert-Butyl peroxypivalate, 1g pentamethylene, 900gVDF monomer,
Reaction is terminated after 6h.It will be transferred in the 20L washing kettle of jacketed after the filtering of resulting polymers slurries, 10L deionized water be added,
After being warming up to 50 DEG C of washing 2h, resulting polymers are dried into 10h, finished product at 80 DEG C.Finished product yellowness index test knot
Fruit is shown in Table 1.
Table 1
*Test condition: weighing about 15g polymer powder in 20ml container, heats 30min in 230 DEG C of baking ovens.It selects
The test of HunterLab LabScan XE yellow colour index instrument characterizes xanthochromia degree with yellow colour index (YID1925), and index is lower,
Thermal stability is better.
Embodiment and the result of comparative example are it is expressly intended that polyvinylidene fluoride resin provided by the invention has from table 1
Excellent heat resistance.
The above is only specific embodiments of the present invention, but technical characteristic of the invention is not limited thereto.It is any with this hair
Based on bright, to solve essentially identical technical problem, essentially identical technical effect is realized, made simple change, etc.
With replacement or modification etc., all it is covered by among protection scope of the present invention.
Claims (9)
1. a kind of preparation method of polyvinylidene fluoride resin, including vinylidene fluoride monomers polymerization, washing, drying, it is characterised in that:
Use organic and inorganic dispersant in molar ratio for 1:(1~5 in the polymerization procedure) dispersant system of combination, by weight
Number, by 100 parts of deionized water, 0.003~0.09 part of dispersant system, 0.01~0.1 part of initiator, chain-transferring agent 0.001~
0.1 part, 20~38 parts of addition polymeric kettles of VDF monomer terminate reaction at 40~80 DEG C after 5~18h of polymerization reaction, described to wash
It washs and adds the strong oxidizer for being 0.01%~0.1% relative to PVDF wet feed weight in step, polymerize gained after washing
Object drying.
2. a kind of preparation method of polyvinylidene fluoride resin according to claim 1, it is characterised in that: organic dispersion
Agent is one of methyl cellulose ether, hydroxyethyl ether cellulose and hydroxypropyl methyl cellulose ether.
3. a kind of preparation method of polyvinylidene fluoride resin according to claim 1, it is characterised in that: the inorganic dispersion
Agent is one of calcium phosphate, aluminium hydroxide and trbasic zinc phosphate.
4. a kind of preparation method of polyvinylidene fluoride resin according to claim 1, it is characterised in that: the chain-transferring agent
For one of ethyl acetate, diethyl carbonate, acetone and pentamethylene, the chain-transferring agent is 0.003~0.05 part.
5. a kind of preparation method of polyvinylidene fluoride resin according to claim 1, it is characterised in that: the initiator is
Tert-Butyl peroxypivalate, peroxidating tert-butyl isobutyrate, di-isopropyl peroxydicarbonate and dicetyl peroxydicarbonate two are just
One of propyl ester, the initiator are 0.02~0.06 part.
6. a kind of preparation method of polyvinylidene fluoride resin according to claim 1, it is characterised in that: described organic and nothing
The molar ratio of machine dispersing agent is 1:(1~3).
7. a kind of preparation method of polyvinylidene fluoride resin according to claim 1, it is characterised in that: the dispersing agent body
System is 0.005~0.05 part.
8. a kind of preparation method of polyvinylidene fluoride resin according to claim 1, it is characterised in that: the polymerization procedure
In reaction temperature be 50~70 DEG C, the reaction time be 6~15h.
9. a kind of preparation method of polyvinylidene fluoride resin according to claim 1, it is characterised in that: the strong oxidizer
For one of sodium peroxide, hydrogen peroxide, potassium permanganate and hypochlorous acid, the strong oxidizer is relative to PVDF wet feed weight
0.03~0.05%.
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| CN108484814B (en) * | 2018-03-02 | 2021-04-09 | 浙江衢州巨塑化工有限公司 | Hydrophilic polyvinylidene fluoride resin |
| CN108467451B (en) * | 2018-03-02 | 2021-04-13 | 浙江衢州巨塑化工有限公司 | Preparation method of hydrophilic polyvinylidene fluoride resin |
| CN113150203B (en) * | 2021-04-07 | 2023-03-24 | 浙江巨化技术中心有限公司 | Vinylidene fluoride copolymer and preparation method thereof |
| CN115594783B (en) * | 2022-10-12 | 2023-10-17 | 万华化学集团股份有限公司 | Method for preparing lithium battery binder |
| CN115710325B (en) * | 2022-11-15 | 2024-06-25 | 万华化学集团股份有限公司 | Polyvinylidene fluoride resin for solar backboard and preparation method thereof |
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| CN102336854A (en) * | 2011-07-07 | 2012-02-01 | 浙江孚诺林化工新材料有限公司 | Preparation method for high heat resistance polyvinylidene fluoride |
| CN103524647A (en) * | 2013-08-16 | 2014-01-22 | 巨化集团技术中心 | Method for preparing polyvinylidene fluoride resin |
| CN103601827A (en) * | 2013-12-02 | 2014-02-26 | 内蒙古三爱富万豪氟化工有限公司 | Vinylidene fluoride polymer and preparation method thereof |
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| CN1587290A (en) * | 2004-07-09 | 2005-03-02 | 浙江大学 | Process for preparing acrylonitrile-chlorinated polyethylene styrene resin copolymer |
| CN102336854A (en) * | 2011-07-07 | 2012-02-01 | 浙江孚诺林化工新材料有限公司 | Preparation method for high heat resistance polyvinylidene fluoride |
| CN103524647A (en) * | 2013-08-16 | 2014-01-22 | 巨化集团技术中心 | Method for preparing polyvinylidene fluoride resin |
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