CN108503738A - A kind of polyvinylidene fluoride resin and the preparation method and application thereof - Google Patents
A kind of polyvinylidene fluoride resin and the preparation method and application thereof Download PDFInfo
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- CN108503738A CN108503738A CN201810338996.5A CN201810338996A CN108503738A CN 108503738 A CN108503738 A CN 108503738A CN 201810338996 A CN201810338996 A CN 201810338996A CN 108503738 A CN108503738 A CN 108503738A
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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
- 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
- C08F214/18—Monomers containing fluorine
- C08F214/22—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
- 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
- C08F214/18—Monomers containing fluorine
- C08F214/28—Hexyfluoropropene
Abstract
The invention discloses a kind of polyvinylidene fluoride resins and the preparation method and application thereof.The preparation method of the Kynoar includes the following steps：Polyvinylidene fluoride resin is prepared using continuous emulsion polymerization, is specifically divided into three phases：First stage：Vinylidene fluoride monomers obtain homopolymerization PVDF resins through homopolymerization；Second stage：Vinylidene fluoride monomers and modified monomer obtain copolymerization PVDF resins through copolymerization；Phase III：Vinylidene fluoride monomers obtain homopolymerization PVDF and/or copolymerization PVDF resins with modified monomer through homopolymerization and/or vinylidene fluoride monomers through copolymerization；Obtain the polyvinylidene fluoride resin.Polyvinylidene fluoride resin of the present invention not only has flexible and toughness well, and with homopolymerization PVDF resins excellent mechanical property and barrier property, while also having good processing performance, can be used for preparing offshore oil delivery Lining Hose.
Description
Technical field
The invention belongs to polymeric material field more particularly to a kind of polyvinylidene fluoride resin (PVDF) and its preparation sides
Method.
Background technology
Offshore oil delivery hose needs to cope with very harsh condition during oil-gas transportation, and liner needs are in direct contact
Crude oil, delivery temperature are up to 130 DEG C, and discharge pressure is also very high (such as up to 70MPa).Therefore this requires inner lining materials to have
Excellent mechanical property, high temperature resistance and chemical barrier.And it need to be in the transport, installation and the course of work of hose
(such as -20 DEG C) bear bending, impact and the outer force effect of distortion under cryogenic conditions, therefore this needs inner lining material to have again
Good flexibility.
To meet the above performance requirement, external major chemical enterprise develops several polymer material in hose
Lining, mainly there is PE (HDPE, XLPE), PA11 and PVDF.Earliest oil hose liner layer uses PE materials, due to its heatproof
Grade is low, is gradually replaced by PA materials, and PA heatproofs are also only capable of reaching 80~90 DEG C, gradually develop into PVDF materials now.
Compared to first two material, PVDF is a kind of thermoplastic fluoropolymer of high-crystallinity, has good mechanical performance, oil resistant
Property, osmotic-pressure-tolerant, resistance to foaming and resistance to H2S and CO2The performance of equal sour gas.Meanwhile also just because of PVDF resins
High crystalline has seriously affected its flexibility.On the other hand, the casing play contacted with PVDF in petroleum pipeline is a kind of spiral helicine
Metal interlocks winding layer, and there are a large amount of gaps, if PVDF molecular weight is too small, mobility is very good, and polymer melt is easy to ooze
Between the gap for entering casing play, petroleum pipeline flexibility is influenced, to the induction point as fracture, while being also to ensure PVDF materials
Mechanical strength, oil hose often use ultra high molecular weight resin with PVDF resins, this brings difficulty to Downstream processing again.
Patent US 005429849 is total to by the way that the homopolymerization PVDF and 25~75wt% of 25~75wt% are copolymerized PVDF resins
It is mixed, the composition material that cryogenic mechanical is had excellent performance is obtained, cable or petroleum pipeline are mainly used for.But the Combined machining that the method obtains
Performance is unsatisfactory.
Patent US 20010055658Al and US 20160017136Al is blended by the way that homopolymerization PVDF to be copolymerized together to PVDF,
And the mode that plasticizer is added obtains PVDF compositions, mechanical performance, high and low temperature resistance and the flexibility of resulting composition are all
There is good improvement.But the small molecule plasticizer that the patent uses is easy to be extracted by hydro carbons during oil transportation, finally makes
Extraction is shunk at hose embrittlement and joint, risk is brought to oil transportation.
Above method is all that the physical modification method that carries out improves the comprehensive of resin have PVDF resins on the basis of
Performance is closed, to meet the application on petroleum pipeline.But this method needs several different resins (or adding plasticizer) carrying out object
Reason is blended, and mixed process is time-consuming and laborious, and mixed uniformity can not ensure well.
Patent CN88100574 discloses vinylidene and chlorotrifluoroethylene heterophasic copolymer, and the heterophasic copolymer is
Institute's group in the matrix being made of the quasi- polymer of vinylidene is scattered in by the elastomer spherula of vinylidene and chlorotrifluoroethylene
At.But the copolymer is flexible, but insufficient strength, and processing performance is bad.
Invention content
The object of the present invention is to provide a kind of polyvinylidene fluoride resins and the preparation method and application thereof, and the PVDF resins are not only
With good flexible and toughness, and with homopolymerization PVDF resins excellent mechanical property and barrier property, while also having
Good processing performance can be used for preparing offshore oil delivery Lining Hose.
First purpose provided by the invention is to provide a kind of preparation method of polyvinylidene fluoride resin.
The preparation method of polyvinylidene fluoride resin provided by the invention, includes the following steps：Using continuous emulsion polymerization
Polyvinylidene fluoride resin is prepared, three phases are specifically divided into：
First stage：Vinylidene fluoride monomers obtain homopolymerization PVDF resins through homopolymerization；
Second stage：Vinylidene fluoride monomers and modified monomer obtain copolymerization PVDF resins through copolymerization；
Phase III：Vinylidene fluoride monomers obtain homopolymerization with modified monomer through homopolymerization and/or vinylidene fluoride monomers through copolymerization
PVDF and/or copolymerization PVDF resins；
Obtain the polyvinylidene fluoride resin.
In above-mentioned preparation method, the Viscosity of the polyvinylidene fluoride resin can be 1.3~1.8dL/g；
The intrinsic viscosity for the copolymerization PVDF resins that the homopolymerization PVDF resins and second stage that the first stage obtains obtain
Can be 1.4~1.9dL/g, such as 1.87dL/g, 1.68dL/g or 1.44dL/g；Homopolymerization PVDF that the phase III obtains and/
Or the intrinsic viscosity of copolymerization PVDF resins can be 0.5~0.8dL/g, such as 0.53dL/g, 0.64dL/g or 0.78dL/g.It is described solid
It is that PVDF resins are made into n,N-Dimethylformamide (DMF) solution of a concentration of 0.4g/dL to have viscosity, in 30 DEG C of water-bath
In, the viscosity that is measured using dark type viscometer.
In above-mentioned preparation method, the polyvinylidene fluoride resin obtains homopolymerization PVDF resins, second-order by the first stage
The homopolymerization PVDF and/or copolymerization PVDF resins composition that the copolymerization PVDF resins and phase III that section obtains obtain；
It is in terms of 100% by total mass percentage of the polyvinylidene fluoride resin；The first stage obtains equal
The mass percentage of poly- PVDF resins is 30~90%；The quality percentage for the copolymerization PVDF resins that the second stage obtains contains
Amount is 5~45%；Homopolymerization PVDF that the phase III obtains and/or the mass percentage for being copolymerized PVDF resins be 5~
25%.
Preferably, it is in terms of 100% by total mass percentage of the polyvinylidene fluoride resin；The first stage obtains
The mass percentage of the homopolymerization PVDF resins arrived is 50~70%；The quality for the copolymerization PVDF resins that the second stage obtains
Percentage composition is 20~40%；The mass percentage of homopolymerization PVDF and/or copolymerization PVDF resins that the phase III obtains
It is 10~15%.
Any one of specifically, the polyvinylidene fluoride resin can be following 1) -6)：
1) it is in terms of 100% by total mass percentage of the polyvinylidene fluoride resin；Made from the first stage
The mass percentage of homopolymerization PVDF resins is 50~70%；The quality percentage of second stage copolymerization PVDF resins obtained
Content is 20~35%；Homopolymerization PVDF made from the phase III and/or the mass percentage for being copolymerized PVDF resins are 10
~15%；
2) it is in terms of 100% by total mass percentage of the polyvinylidene fluoride resin；Made from the first stage
The mass percentage of homopolymerization PVDF resins is 50~60%；The quality percentage of second stage copolymerization PVDF resins obtained
Content is 27~35%；Homopolymerization PVDF made from the phase III and/or the mass percentage for being copolymerized PVDF resins are 13
~15%；
3) it is in terms of 100% by total mass percentage of the polyvinylidene fluoride resin；Made from the first stage
The mass percentage of homopolymerization PVDF resins is 60~70%；The quality percentage of second stage copolymerization PVDF resins obtained
Content is 20~27%；Homopolymerization PVDF made from the phase III and/or the mass percentage for being copolymerized PVDF resins are 10
~13%；
4) it is in terms of 100% by total mass percentage of the polyvinylidene fluoride resin；Made from the first stage
The mass percentage of homopolymerization PVDF resins is 50%；The mass percentage of second stage copolymerization PVDF resins obtained
It is 35%；Homopolymerization PVDF made from the phase III and/or the mass percentage for being copolymerized PVDF resins are 15%；
5) it is in terms of 100% by total mass percentage of the polyvinylidene fluoride resin；Made from the first stage
The mass percentage of homopolymerization PVDF resins is 60%；The mass percentage of second stage copolymerization PVDF resins obtained
It is 27%；Homopolymerization PVDF made from the phase III and/or the mass percentage for being copolymerized PVDF resins are 13%；
6) it is in terms of 100% by total mass percentage of the polyvinylidene fluoride resin；Made from the first stage
The mass percentage of homopolymerization PVDF resins is 70%；The mass percentage of second stage copolymerization PVDF resins obtained
It is 20%；Homopolymerization PVDF made from the phase III and/or the mass percentage for being copolymerized PVDF resins are 10%.
In above-mentioned preparation method, the second stage and/or in the phase III, the modified monomer accounts for the stage (i.e.
Second stage or second stage and phase III, that is, what is added is the stage of mix monomer) all monomers (vinylidene fluoride monomers and
Modified monomer) molar content can be 10~50%, concretely 10%, 40% or 50%.
In the polyvinylidene fluoride resin, the mass percentage (modified monomer macroscopic view content) of the modified monomer can be
3~15%, preferably 5~12%.
The modified monomer is the fluorine-containing vinyl monomer in addition to vinylidene, including but not limited to：Vinyl fluoride, trifluoro second
Alkene, chlorotrifluoroethylene (CTFE), 1,2- difluoroethylenes, tetrafluoroethene (TFE), hexafluoropropene (HFP), perfluor (alkyl vinyl)
At least one in ether, perfluor (1,3- dioxole) and perfluor (2,2- dimethyl -1,3- dioxole) (PDD)
Kind；Perfluor (alkyl vinyl) ether can be perfluor (methyl ethylene) ether (PMVE), perfluor (ethyl vinyl) ether
(PEVE) or perfluor (propyl ethylene base) ether (PPVE).
In above-mentioned preparation method, the method specifically comprises the following steps：
1) vinylidene fluoride monomers carry out the homopolymerization of first stage in the emulsification system that water and emulsifier are formed, and obtain homopolymerization
PVDF resins；
2) mixed gas that vinylidene fluoride monomers and modified monomer are added in the system obtained to step 1) carries out second-order
The copolymerization of section obtains copolymerization PVDF resins；
3) the mixed of vinylidene fluoride monomers or vinylidene fluoride monomers and modified monomer is added in the system obtained to step 2)
Homopolymerization and/or copolymerization that gas carries out the phase III are closed, homopolymerization PVDF resins and/or copolymerization PVDF resins are obtained；
Step 1)-step 3) existing for initiator and chain-transferring agent under the conditions of carry out；
4) it takes out the lotion that step 3) obtains and obtains the polyvinylidene fluoride resin through cohesion, washing and drying.
In above-mentioned preparation method, the emulsifier can be Sodium perfluorooctanoate, Perfluorooctanoic acid potassium salt or perfluorooctanoic acid.It is described
Emulsifier can be three phases whole total monomer weight 0.05~0.5%, concretely 0.08%, 0.16% or
0.32%.Steps are as follows for the addition of the emulsifier：It is added at one time before step 1) reaction.
The initiator can be oil soluble peroxides initiator, including but not limited to：Tert-Butyl peroxypivalate, mistake
Aoxidize tert-butyl isobutyrate, di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester, dicetyl peroxydicarbonate diethylester
Deng.The dosage of the initiator can be the 0.1~1% of three phases whole total monomer weight, concretely 0.16%, 0.32%
Or 1%.The addition step of the initiator can be as follows：The initiator is added portionwise during the reaction, and step 1) reaction is opened
The 50% of initiator total weight is added before beginning, reaction proceeds to 1/3 that monomer consumption is three phases whole total monomer weight
When add 20~30% (such as 20%, 25%) of initiator total weight, it is that three phases are whole that reaction, which proceeds to monomer consumption,
Total monomer weight 2/3 when add 10~20% (such as 10%, 13%) of initiator total weight, added when being reacted to the phase III
10~20% (such as 20%, 15%, 16%) of initiator total weight.
The chain-transferring agent can be acetone, ethyl acetate, diethyl carbonate, diethyl malonate, diethyl succinate or
Dipropyl succinate.The dosage of the chain-transferring agent can be the 3~10% of three phases whole total monomer weight.The chain tra nsfer
Steps are as follows for the addition of agent：The chain-transferring agent is added portionwise during the reaction, and chain tra nsfer is added before starting in step 1) reaction
5~10% (such as 8%, 10%) of agent total weight, it is three phases whole total monomer weight that reaction, which proceeds to monomer consumption,
3~5% (such as 4%, 5%) of chain-transferring agent total weight are added when 1/3, it is that three phases are whole that reaction, which proceeds to monomer consumption,
Total monomer weight 2/3 when add 2~5% (such as 4%, 3%, 5%) of chain-transferring agent total weight, be reacted into the phase III
When add 80~90% (such as 84%, 80%) of chain-transferring agent total weight.
Above-mentioned preparation method, the reaction temperature of step 1)-step 3) can be 60~100 DEG C, concretely 75~85 DEG C,
75℃、80℃、85℃；Reaction pressure can be 1.0~3.0MPa, concretely 1.6~2.0MPa, 1.6MPa, 1.8MPa or
2.0MPa。
In step 1), stop when vinylidene fluoride monomers consumption is the 50~75% of three phases whole total monomer weight
Reaction；
In step 2), stop reaction when mix monomer consumption is the 20~40% of three phases whole total monomer weight；
In step 3), vinylidene fluoride monomers or mix monomer consumption be three phases whole total monomer weight 10~
Stop reaction when 15%.
Second object of the present invention is to provide the Kynoar that preparation method described in any one of the above embodiments is prepared
Resin.
Third object of the present invention is to provide above-mentioned polyvinylidene fluoride resins in preparing offshore oil delivery Lining Hose
Using.
Fourth object of the present invention is to provide a kind of offshore oil delivery hose, and liner material is above-mentioned Kynoar tree
Fat.
The present invention has the advantages that：
The high molecular weight homopolymerization PVDF resins that first stage generates can keep the mechanical performance and chemical barrier of PVDF resins
Property；The elastic PVDF resins that second stage generates, which can be used as impact modifier, improves the erosion-resisting characteristics of whole resin, while one
The overall crystallinity for determining reduction PVDF resins in degree increases its flexibility；The low molecular weight PVDF copolymerization tree that phase III generates
Fat can be used as plasticizer, improve the processing performance of resin to a certain extent, while again can be to avoid using small molecule plasticizer
The problem of precipitation.In addition, PVDF resins prepared by this method, the PVDF resins that each stage generates have good compatibility.
Test method of the present invention is as follows:
(1) determination of modified monomer macroscopic view content
Modified monomer macroscopic view content of the present invention refers to modified monomer relative to PVDF trees obtained by three stage polymerizations
Mass content in fat total amount.PVDF resins are taken to be dissolved in deuterium band DMSO, using Nuclear Magnetic Resonance test resin nuclear-magnetism fluorine spectrum
(19F-NMR), modified monomer content is calculated by the ratio between peak area.
(2) tensile property is tested
The tensile property of resin is tested according to 1040.1~3-2006 of national standard GB/T.
(3) shock resistance is tested
According to the impact property of 179 test materials of ISO.
(4) measurement of intrinsic viscosity
High molecular weight PVDF resin is made into n,N-Dimethylformamide (DMF) solution that concentration (C) is 0.4g/dL,
In 30 DEG C of water-bath, the delivery time of pure solvent and resin solution, respectively T are surveyed using dark type viscometer0And Ts, and by with
Lower formula calculates the intrinsic viscosity η of resin：
η=1/C × ln (Ts/T0)
C is solution concentration, unit in formula：g/dl
(5) critical shear rate
Critical shear rate is the shear rate for starting to generate flow instabilities in extrusion molding in polymer.It is unstable
Phenomena such as flowing will lead to extrudate rough surface, uneven, helically twisted or even melt fracture.Under the conditions of 220 DEG C, adopt
The extrusion performance of PVDF resins is tested with capillary rheometer, is observed melt fracture situation, is detected its critical shear rate.
(6) resistance to organic media permeability
The extrusion film that thickness is 100 μm is made in resin, is 130 DEG C in temperature, under conditions of pressure is 100bar, surveys
The permeability of methane in the film.
Specific implementation mode
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1 prepares polyvinylidene fluoride resin
2500g deionized waters and perfluorooctanoic acid emulsifier are added in 5L vertical retorts (rotating speed 300rpm), then
To polymerization kettle temperature raising and VDF monomers are added, after kettle kettle temperature to be polymerized reaches 75 DEG C, kettle pressure reaches 1.6MPa, by auxiliary agent pump plus
Enter initiator di-isopropyl peroxydicarbonate and chain-transferring agent acetone start to react, monomer in reaction process, initiator and
The feed postition of chain-transferring agent is shown in Table 1, and is kept reaction kettle kettle temperature kettle pressure to stablize to reaction and is finished, wherein the first stage works as
Stop reaction when vinylidene fluoride monomers consumption is 50% (300g VDF) of three phases whole total monomer weight；Second stage
Stop reaction when mix monomer consumption is 35% (210g mix monomers) of three phases whole total monomer weight；Third rank
Section stops reaction when mix monomer consumption is 15% (90g mix monomers) of three phases whole total monomer weight.Reaction
Lotion is taken out after the completion, is obtained PVDF naval stores through cohesion, washing, drying steps, and be tested for the property to it, is shown in Table 2.
In the present embodiment, the intrinsic viscosity of homopolymerization PVDF made from the first and second stage is 1.87dL/g；Phase III is made
PVDF intrinsic viscosity be 0.53dL/g.
It is in terms of 100% by total mass percentage of PVDF naval stores；Homopolymerization polyvinylidene fluoride made from first stage
The mass percentage of olefine resin is 50%；The mass percentage of second stage copolymerization polyvinylidene fluoride resin obtained
It is 35%；The mass percentage of phase III copolymerization polyvinylidene fluoride resin obtained is 15%.
Embodiment 2 prepares polyvinylidene fluoride resin
2800g deionized waters and Perfluorooctanoic acid potassium salt emulsifier are added in 5L vertical retorts (rotating speed 350rpm), then
To polymerization kettle temperature raising and VDF monomers are added, after kettle kettle temperature to be polymerized reaches 80 DEG C, kettle pressure reaches 1.8MPa, by auxiliary agent pump plus
Enter initiator dicetyl peroxydicarbonate diethylester and chain-transferring agent ethyl acetate start to react, in reaction process monomer, initiator with
And the feed postition of chain-transferring agent is shown in Table 1, and is kept reaction kettle kettle temperature kettle pressure to stablize to reaction and is finished, wherein the first stage
Stop reaction when vinylidene fluoride monomers consumption is 60% (360g VDF) of three phases whole total monomer weight；Second-order
Section stops reaction when mix monomer consumption is 27% (160g mix monomers) of three phases whole total monomer weight；Third
Stage stops reaction when VDF monomer consumptions are 13% (80g VDF) of three phases whole total monomer weight.Reaction is completed
After take out lotion, obtain PVDF naval stores through cohesion, washing, drying steps, and be tested for the property to it, be shown in Table 2.
In the present embodiment, the intrinsic viscosity of homopolymerization PVDF made from the first and second stage is 1.68dL/g；Phase III is made
PVDF intrinsic viscosity be 0.64dL/g.
It is in terms of 100% by total mass percentage of polyvinylidene fluoride resin；Homopolymerization made from first stage gathers inclined fluorine
The mass percentage of vinyl is 60%；The quality percentage of second stage copolymerization polyvinylidene fluoride resin obtained contains
Amount is 27%；The mass percentage of homopolymerization Kynoar made from the phase III is 13%.
Embodiment 3 prepares polyvinylidene fluoride resin
3000g deionized waters and Sodium perfluorooctanoate emulsifier are added in 5L vertical retorts (rotating speed 400rpm), then
To polymerization kettle temperature raising and VDF monomers are added, after kettle kettle temperature to be polymerized reaches 85 DEG C, kettle pressure reaches 2.0MPa, by auxiliary agent pump plus
Enter initiator tert-Butyl peroxypivalate and chain-transferring agent diethyl carbonate starts to react, monomer, initiator in reaction process
And the feed postition of chain-transferring agent is shown in Table 1, and is kept reaction kettle kettle temperature kettle pressure to stablize to reaction and is finished, wherein the first rank
Section stops reaction when vinylidene fluoride monomers consumption is 70% (420g VDF) of three phases whole total monomer weight；Second
Stage stops reaction when mix monomer consumption is 20% (120g mix monomers) of three phases whole total monomer weight；The
Three stages stopped reaction when VDF monomer consumptions are 10% (60gVDF) of three phases whole total monomer weight.It has reacted
At rear taking-up lotion, PVDF naval stores is obtained through cohesion, washing, drying steps, and be tested for the property to it, be shown in Table 2.
In the present embodiment, the intrinsic viscosity of homopolymerization PVDF made from the first and second stage is 1.44dL/g；Phase III is made
PVDF intrinsic viscosity be 0.78dL/g.
It is in terms of 100% by total mass percentage of polyvinylidene fluoride resin；Homopolymerization made from first stage gathers inclined fluorine
The mass percentage of vinyl is 70%；The quality percentage of second stage copolymerization polyvinylidene fluoride resin obtained contains
Amount is 20%；The mass percentage of phase III copolymerization polyvinylidene fluoride resin obtained is 10%.
Comparative example 1
Similar to Example 1, only is not both no longer to add chain-transferring agent acetone when reacting the phase III.Specific formula
And technological parameter refers to table 1.
The final performance of product is shown in Table 2.
Comparative example 2
Similar to Example 2, only is not both that second stage only adds VDF monomers, and the reaction of three stage polymerizations generates
Product is PVDF homopolymers.Specific formula and technological parameter refer to table 1.
The final performance of product is shown in Table 2.
Comparative example 3
Similar to Example 1, only is not both the mix monomer that first stage reaction begins to add VDF and CTFE.
Specific formula and technological parameter refer to table 1.
The final performance of product is shown in Table 2.
Comparative example 4
Similar to Example 1, only is not both the mix monomer that first stage reaction begins to add VDF and CTFE,
And mix monomer mol ratio is VDF/CTFE=95:5.Specific formula and technological parameter refer to table 1.
The results of property of table 2, Examples and Comparative Examples PVDF naval stores
By embodiment in table 2 and the result of comparative example it is expressly intended that PVDF copolymers provided by the invention, have compared with
High intensity, flexibility and good organic solvent-resistant permeability, while there is preferable processing performance.
Claims (10)
1. a kind of preparation method of polyvinylidene fluoride resin, it includes the following steps：It is prepared using continuous emulsion polymerization poly- inclined
Fluoroethylene resin is specifically divided into three phases：
First stage：Vinylidene fluoride monomers obtain homopolymerization PVDF resins through homopolymerization；
Second stage：Vinylidene fluoride monomers and modified monomer obtain copolymerization PVDF resins through copolymerization；
Phase III：Vinylidene fluoride monomers obtain homopolymerization PVDF with modified monomer through homopolymerization and/or vinylidene fluoride monomers through copolymerization
And/or copolymerization PVDF resins；
Obtain the polyvinylidene fluoride resin.
2. preparation method according to claim 1, it is characterised in that：The Viscosity of the polyvinylidene fluoride resin is
1.3~1.8dL/g；
The intrinsic viscosity for the copolymerization PVDF resins that the homopolymerization PVDF resins and second stage that the first stage obtains obtain is 1.4
~1.9dL/g；
The homopolymerization PVDF and/or be copolymerized the intrinsic viscosity of PVDF resins as 0.5~0.8dL/g that the phase III obtains.
3. preparation method according to claim 1 or 2, it is characterised in that：The polyvinylidene fluoride resin is by the first stage
Obtain homopolymerization PVDF resins, the copolymerization PVDF resins that second stage obtains and the homopolymerization PVDF that the phase III obtains and/or copolymerization
PVDF resins form；
It is in terms of 100% by total mass percentage of the polyvinylidene fluoride resin；The homopolymerization that the first stage obtains
The mass percentage of PVDF resins is 30~90%；The mass percentage for the copolymerization PVDF resins that the second stage obtains
It is 5~45%；The mass percentage of homopolymerization PVDF and/or copolymerization PVDF resins that the phase III obtains are 5~25%.
4. preparation method according to any one of claim 1-3, it is characterised in that：The second stage and/or described
In phase III, the molar content that the modified monomer accounts for the stage all monomers is 10~50%；
In the polyvinylidene fluoride resin, the mass percentage of the modified monomer is 3~15%；
The modified monomer be vinyl fluoride, trifluoro-ethylene, chlorotrifluoroethylene, 1,2- difluoroethylenes, tetrafluoroethene, hexafluoropropene,
Perfluor (alkyl vinyl) ether, perfluor (1,3- dioxole) and perfluor (2,2- dimethyl -1,3- dioxole)
At least one of.
5. according to the preparation method described in any one of claim 1-4, it is characterised in that：The method specifically includes following step
Suddenly：
1) vinylidene fluoride monomers carry out the homopolymerization of first stage in the emulsification system that water and emulsifier are formed, and obtain homopolymerization PVDF
Resin；
2) mixed gas that vinylidene fluoride monomers and modified monomer are added in the system obtained to step 1) carries out second stage
Copolymerization obtains copolymerization PVDF resins；
3) gaseous mixture of vinylidene fluoride monomers or vinylidene fluoride monomers and modified monomer is added in the system obtained to step 2)
Body carries out the homopolymerization and/or copolymerization of phase III, obtains homopolymerization PVDF resins and/or copolymerization PVDF resins；
Step 1)-step 3) existing for initiator and chain-transferring agent under the conditions of carry out；
4) it takes out the lotion that step 3) obtains and obtains the polyvinylidene fluoride resin through cohesion, washing and drying.
6. preparation method according to claim 5, it is characterised in that：The emulsifier is Sodium perfluorooctanoate, perfluoro caprylic acid
Potassium or perfluorooctanoic acid；The emulsifier is the 0.05~0.5% of three phases whole total monomer weight；The emulsifier
Addition steps are as follows：It is added at one time before step 1) reaction；
The initiator is oil soluble peroxides initiator；The oil-soluble initiator is tert-Butyl peroxypivalate, mistake
Aoxidize tert-butyl isobutyrate, di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester or dicetyl peroxydicarbonate diethyl
Ester；The dosage of the initiator is the 0.1~1% of three phases whole total monomer weight；The addition step of the initiator is such as
Under：The initiator is added portionwise during the reaction, and step 1) reaction is added the 50% of initiator total weight before starting, reaction
The 20~30% of initiator total weight is added when proceeding to 1/3 that monomer consumption is three phases whole total monomer weight, instead
The 10~20% of initiator total weight is added when should proceed to 2/3 that monomer consumption is three phases whole total monomer weight,
The 10~20% of initiator total weight are added when being reacted to the phase III；
The chain-transferring agent is acetone, ethyl acetate, diethyl carbonate, diethyl malonate, diethyl succinate or succinic acid
Dipropyl；The dosage of the chain-transferring agent is the 3~10% of three phases whole total monomer weight；The addition of the chain-transferring agent
Steps are as follows：The chain-transferring agent is added portionwise during the reaction, and chain-transferring agent total weight is added before starting in step 1) reaction
5~10%, reaction proceed to monomer consumption be three phases whole total monomer weight 1/3 when add chain-transferring agent gross weight
The 3~5% of amount, it is total that reaction adds chain-transferring agent when proceeding to 2/3 that monomer consumption is three phases whole total monomer weight
The 80~90% of chain-transferring agent total weight are added in the 2~5% of weight when being reacted into the phase III.
7. preparation method according to claim 5 or 6, it is characterised in that：The reaction temperature of step 1)-step 3) be 60~
100 DEG C, reaction pressure is 1.0~3.0MPa；
In step 1), stop when vinylidene fluoride monomers consumption is the 50~75% of three phases whole total monomer weight anti-
It answers；
In step 2), stop reaction when mix monomer consumption is the 20~40% of three phases whole total monomer weight；
In step 3), when vinylidene fluoride monomers or mix monomer consumption are the 10~15% of three phases whole total monomer weight
When stop reaction.
8. the polyvinylidene fluoride resin that the preparation method described in any one of claim 1-7 is prepared.
9. application of the polyvinylidene fluoride resin according to any one of claims 8 in preparing offshore oil delivery Lining Hose.
10. a kind of offshore oil delivery hose, it is characterised in that：Its liner material is polyvinylidene fluoride resin according to any one of claims 8.
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