CN103351446B - A kind of preparation method of high-tensile-strengtpolyvinylidene polyvinylidene fluoride - Google Patents

A kind of preparation method of high-tensile-strengtpolyvinylidene polyvinylidene fluoride Download PDF

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CN103351446B
CN103351446B CN201310317382.6A CN201310317382A CN103351446B CN 103351446 B CN103351446 B CN 103351446B CN 201310317382 A CN201310317382 A CN 201310317382A CN 103351446 B CN103351446 B CN 103351446B
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CN103351446A (en
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兰军
张建新
李斌
王先荣
余金龙
赵少春
高家勇
白鲸
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Zhonghao Chenguang Research Institute of Chemical Industry Co Ltd
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Abstract

The present invention relates to the polymerization process of a kind of high-tensile-strengtpolyvinylidene polyvinylidene fluoride (PVDF).It is characterized in that, adopt organo-peroxide as initiator, using lower paraffin hydrocarbons as molecular weight regulator, make vinylidene (VDF) and optional comonomer carry out radical polymerization at low temperatures and prepare the PVDF homopolymer of high tensile or the method for multipolymer.The polyvinylidene fluoride resin degree of crystallinity obtained is high, molecular weight is high, tensile strength is greater than 60MPa.

Description

A kind of preparation method of high-tensile-strengtpolyvinylidene polyvinylidene fluoride
Technical field
The present invention relates to organic chemistry filed, be specifically related to a kind of preparation method of fluoropolymer.
Background technology
Polyvinylidene difluoride (PVDF) (PVDF) resin mainly refers to the multipolymer of a small amount of fluorine-containing vinyl monomer of vinylidene fluoride homopolymer or vinylidene and other, PVDF resin has the characteristic of fluoro-resin and resins for universal use concurrently, except there is good chemical resistance, high thermal resistance, scale resistance, weathering resistance, resistance to x radiation x performance, also there is the properties such as piezoelectricity, dielectricity, pyroelectricity, be the large product that in current fluoro-containing plastic, output is at the second place, global annual capacity is more than 4.3 ten thousand tons.PVDF application mainly concentrates on petrochemical complex, the electric and large field of fluorocarbon coating three, chemical resistant properties, processibility and the antifatigue good due to PVDF and creep properties are one of best materialss of the pump of petrochemical equipment fluid handling system entirety or lining, valve, pipeline, pipe line parts, storage tank and heat exchanger.Its good chemical stability, electrical insulation capability, make the equipment of making can meet TOCS and flame-retardancy requirements, be widely used in storage and the conveying of high-purity chemicals in semi-conductor industry, adopt porous-film, gel, barrier film etc. that PVDF resin makes in recent years, apply in the lithium secondary battery, this purposes becomes one of the fastest market of PVDF demand growth at present.PVDF is one of main raw material of fluorocarbon coating, with it for fluorocarbon coating prepared by raw material developed into for the 6th generation, because PVDF resin has superpower weathering resistance, can life-time service out of doors, service free, such coating is widely used in power house, airport, motorway, Highrise buildings etc.; In addition PVDF resin can also with other resin alloy modifications, as PVDF and ABS resin is blended obtains matrix material, be widely used in building, automobile decoration, appliance shell etc.
Polyvinylidene difluoride (PVDF) polymerization technique is developed so far does very large improvement.Using inorganic peroxides such as persulphates as initiator, there is unstable end group in the PVDF of preparation, thus causes poor heat stability, and combinations color and lustre is poor.US3,193,539 disclose employing ditertiary butyl peroxide (DTBP) [(CH 3) 3c-O-O-C (CH 3) 3] as the temperature of reaction of initiator initiated polymerization PVDF resin be 120 ~ 145 DEG C, pressure is 2.1 ~ 6.9MPa.Adopt DTBP as initiator for reaction temperature drift, the degree of crystallinity of obtained PVDF is low, and defect is many, then its tensile strength is low.With di-isopropyl peroxy dicarbonate fat (IPP) [(CH 3) 2cHOCOOOOCOCH (CH 3) 2] for the temperature of initiator synthesis PVDF is low, PVDF Resin crystallization degree is high, but at high temperature exists and easily remove hydrogen fluoride and cause thermolability.US 5093427 discloses and prepares PVDF resin using methyl alcohol as molecular weight regulator, and methyl alcohol does not affect rate of polymerization, but can not the molar mass of effective control PVDF.
Summary of the invention
The present invention adopts redox system to reduce as initiator the degree of crystallinity that temperature of reaction improves PVDF, reduces defect, improves the tensile strength of resin.Select a kind of molecular weight regulator to seal resinous terminal, thus improve the thermostability of resin, improve combinations color and lustre.
For the weak point of this area, the object of the invention is the preparation method proposing a kind of high-tensile-strengtpolyvinylidene polyvinylidene fluoride.
Another object of the present invention is the polymkeric substance that the described preparation method of proposition prepares.
The technical scheme realizing above-mentioned purpose of the present invention is:
A preparation method for high-tensile-strengtpolyvinylidene polyvinylidene fluoride, under initiator and molecular weight regulator existence condition, in aqueous dispersion, makes vinylidene (VDF) and another kind of comonomer carry out radical polymerization,
Wherein, described initiator is selected from the one in percarbonic acid two (2-ethylhexyl ester), dilauroyl peroxide, the peroxidation-2-ethyl acid tert-butyl ester, azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile).Preferred azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride.
Because inorganic initiator systems brings thermally labile group to resinous terminal, and bring inorganic impurity into resin, cause resin-made for shade deviation, the kick off temperature that the present invention's azo-initiator used kick off temperature low (kick off temperature 40-75 DEG C) adopts lower than prior art, be more conducive to generate high-crystallinity resins, improve its tensile strength.
Wherein, the add-on of described initiator is that mass body volume concentrations is 0.1 ~ 1g/L in aqueous dispersion, adopts the mode added continuously to add.The consumption of initiator not only affects speed of reaction (answering speed to be 1.5g/L.min ~ 4.5g/L.min in the technical program) and molecular weight, also has a significant impact Emulsion particle size.Initiator amount difference has different impacts to letex polymerization.Initiator amount is too low, then output per single reactor can reduce.The optimum yield of the technical program is that 13Kg(is based on 50L reactor), if the amount of initiator is very little, output only has the 1/4-3/4 of optimum yield.Initiator is few, and speed of response is slow, and gained polyvinylidene difluoride (PVDF) ethylene molecule amount is low, and intensity also can reduce.System viscosity increases.Initiator amount increases, and in polymerization system, initiator concentration increases, and the initial stage forms free radical number and increases, and speed of reaction increases, but interparticle collision probability increases, and the frequency of chain termination increases, and the molecular-weight average of polymkeric substance is low.When initiator amount is excessive, the stability of emulsion polymerization process is easily made to reduce, mainly because excessive initiator and emulsifying agent serve electrolytical effect.
Wherein, described molecular weight regulator is hydrogen, methane, ethane, propane, one or more in iso-pentane, monochloro methane, methylene dichloride, trichloromethane and tetracol phenixin.
Wherein, the mass body volume concentrations of described molecular weight regulator in aqueous dispersion is 0.2 ~ 0.5g/L.Add with segmentation feed postition.The molecular weight of these molecular weight regulator polyvinylidene difluoride (PVDF), can make the end group of polyvinylidene fluoride resin be converted into-CF 2h, thus the thermostability adding PVDF resin, reduce the defect of PVDF molecule, thus improve the tensile strength of PVDF resin, and also can improve the properties for follow of resin.The present invention preferably adopts methane, ethane, monochloro methane, methylene dichloride, trichloromethane and tetracol phenixin.In order to obtain the molecular weight expected, the add-on of molecular weight regulator is relevant with company's transfer efficiency of amount of initiator and molecular weight regulator.The amount of molecular weight regulator is very few, and the PVDF molecular resin amount of preparation is excessive, but end group can not be converted into-CF to greatest extent 2h, thus the poor heat stability causing PVDF resin, increase the defect of PVDF molecule, thus reduce the tensile strength of PVDF resin, and also can be unfavorable for the following process of resin.Molecular weight regulator is too much, cause rate of polymerization low, and the molecular weight of resin is little, reduces the tensile strength of resin.
Wherein, described another kind of comonomer is one or more in tetrafluoroethylene, R 1216, trifluorochloroethylene, perfluoroalkyl vinyl ether.
Described another kind of comonomer quality is 0% ~ 10% of vinylidene quality.
Described preparation method, specifically comprises the steps:
(1) in reactor, pH adjusting agent, paraffin and water is added, the emulsion of obtained Quality of Paraffin Waxes volumetric concentration 0. ~ 1.0g/L, pH adjusting agent mass body volume concentrations 0.5 ~ 2.0g/L;
(2) in step (1) described reactor, add the mix monomer of vinylidene and another kind of comonomer, make the pressure of described reactor reach 2.0 ~ 6.0MPa; Polymerization temperature is 40 ~ 75 DEG C,
3) at the temperature of the pressure of 2.0 ~ 6.0MPa and 40 ~ 75 DEG C, in step (2) described reactor, add initiator initiated polymerization, then add molecular weight regulator wherein;
(4) in step (3) described reactor, add mix monomer, the pressure maintained in described reactor is constant in batches; Add initiator continuously, until polyreaction terminates;
(5) resulting polymers is carried out condensing, wash and obtaining the polyvinylidene fluoride resin of high strength by reaction after terminating.
Wherein, described pH value regulator is selected from the one in Sodium phosphate dibasic, borax, bicarbonate of ammonia.
Wherein, add in described step (3) that initiator is whole initiator add-on 1 ~ 5%, all the other initiators add in step (4).
Particularly, initiator is mixed with the 1wt%-10wt% aqueous solution in (3) by described step, adds reactor.Initiator is mixed with the aqueous solution in (4) by step, and concentration controls, for 3wt ‰ ~ 8 ‰, to add reactor continuously.Volume pump can be adopted to add with the speed of 5ml/min ~ 20ml/min.
The polymkeric substance that preparation method of the present invention prepares.The polyvinylidene fluoride resin tensile strength obtained is greater than 60MPa.
Beneficial effect of the present invention is:
Adopt azo-initiator, compared to inorganic initiator conventional in prior art, accelerate rate of polymerization, and product color is better, intensity improves; By controlling kind and the add-on of molecular weight regulator, controlling the molecular weight of product, ensureing that the polyvinylidene difluoride (PVDF) prepared has good mechanical property.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.If do not specialize, reagent used in embodiment is conventional commercial reagent, the conventional means that technique means used in embodiment is well known to those skilled in the art.
The performance test methods of polyvinylidene difluoride (PVDF) is as follows:
(1) Determination of Crystallinity of PVDF resin
Use the DSC2920 of TA instrument Japan Co., Ltd. as device, carry out DSC mensuration (Differential Scanning Calorimetry mensuration) with following condition.Draw the baseline calculating caloric receptivity 60 DEG C ~ melting final temperature (about 190 DEG C), if the crystallization melting caloric of PVDF is 104.7 (J/g), calculate degree of crystallinity.
Sample weight: about 5mg
Planchet: aluminium dish
Heat-up rate: 5 DEG C/min
Sweeping gas: nitrogen
Gas flow: 20ml/min.
(2) the Weight-average molecular flow measurement of PVDF resin
PVDF resin is dissolved in DMF with the concentration of 1.0mg/ml, obtains test liquid, use this test liquid of 50ml, carry out GPC mensuration under the following conditions, obtain its weight-average molecular weight (PMMA conversion).
Device: HLC-8220GPC(TOSOH Co., Ltd)
Post: Shodex KF-606M, KF-601
Mobile phase: 0.6ml/min DMF
Detector: differential refraction detector
(3) tensile strength testing method is according to ASTM D638.
(4) fusing point testing method is according to ASTM D3148.
Embodiment 1
Intermittent type free radical emulsion of the present invention preparation is carried out, to prepare polyvinylidene fluoride resin in the autoclave of 50L.Add 30L deionized water in a kettle., add solid paraffin 20g, borax 35g.Then in reactor, the air of vapor space is first less than 30ppm with nitrogen replacement to oxygen level.Then utilize vinylidene (VDF) monomer replacement reaction kettle, make its oxygen level be less than 20ppm.In reactor, the perfluoro ammonium caprylate aqueous solution of 300g5wt% is added by volume pump.Unlatching reactor stirs, and reactor liquidus temperature is risen to 45 DEG C.Membrane compressor is adopted to add pure vinylidene (VDF) to reactor pressure 4.0MPa.
The aqueous solution adding the azo-bis-iso-dimethyl of the 5wt% of 20g starts initiation reaction.In reaction process, maintain reactor pressure 4.0MPa with adding vinylidene (VDF) monomer, temperature of reaction 45 DEG C, adds molecular weight regulator methane 12g.Volume pump is adopted to add with the speed of 10ml/min the aqueous solution initiator that concentration is the azo-bis-iso-dimethyl of 5wt ‰ continuously in reaction process.Reaction times is 130min, stops stirring, and reclaims unreacted mix monomer in reactor, and releases emulsion.Emulsion solid content is 26.1%.Speed of reaction is 2.6g/ (L.min).Washed by emulsion mechanical coalescence, vacuum-drying, sample presentation detected result is in table 1.
The present embodiment output is 13Kg, and molecular weight of product Mw is 4,100,000; The emulsion particle diameter of the technical program synthesis is large, and median size is 0.26 μm.General molecular weight is larger, and emulsion particle diameter is larger.The median size of conventional polyvinylidene fluoride emulsion is about 0.22 μm.
Comparative example 1
The basis of embodiment 1 is reduced the amount adding initiator continuously.Volume pump is adopted to add with the speed of 5ml/min the aqueous solution initiator that concentration is the azo-bis-iso-dimethyl of 2wt ‰ continuously in reaction process.Speed of response is slow, and to late phase reaction speed close to zero, stopped reaction.Charging capacity only has 2/3 of expectation.Reaction times is 180min, and emulsion solid content is 17.5%.Speed of reaction is 1.2g/ (L.min).Washed by emulsion mechanical coalescence, vacuum-drying, sample presentation detected result is in table 1.The median size of product polyvinylidene fluoride emulsion is 0.22 μm.If the amount of initiator very little, then output per single reactor can reduce, and this contrast output only has 6Kg.Initiator is few, and speed of response is slow, and gained polyvinylidene difluoride (PVDF) ethylene molecule amount is low, and intensity also can reduce.
Comparative example 2
Temperature of reaction to 75 DEG C is improved on the basis of embodiment 1, and other conditions are constant.Reaction times is 90min.Emulsion solid content is 26.4%, and speed of reaction is 3.8g/ (L.min).Washed by emulsion mechanical coalescence, vacuum-drying, sample presentation detected result is in table 1.The median size of product polyvinylidene fluoride emulsion is 0.22 μm.
Table 1 detected result
Project Unit Embodiment 1 Comparative example 1 Comparative example 2
Fusing point 166 167 166
Degree of crystallinity % 68 63 59
Molecular weight Ten thousand 356 312 239
Tensile strength MPa 62.5 58.3 51.0
Embodiment 2
Intermittent type free radical emulsion of the present invention preparation is carried out, to prepare polyvinylidene fluoride resin in the autoclave of 50L.Add 30L deionized water in a kettle., add whiteruss 15g, borax 35g.Then in reactor, the air of vapor space is first less than 30ppm with nitrogen replacement to oxygen level.Then utilize vinylidene (VDF) monomer replacement reaction kettle, make its oxygen level be less than 20ppm.In reactor, the perfluoro ammonium caprylate aqueous solution of 300g5wt% is added by volume pump.Unlatching reactor stirs, and reactor liquidus temperature is risen to 55 DEG C.Membrane compressor is adopted to add pure vinylidene (VDF) to reactor pressure 4.0MPa.
The aqueous solution adding the azo-bis-isobutyrate hydrochloride of the 5wt% of 15g starts initiation reaction.In reaction process, maintain reactor pressure 4.0MPa with adding vinylidene (VDF) monomer, temperature of reaction 55 DEG C, adds molecular weight regulator methane 12g.Volume pump is adopted to add with the speed of 10ml/min the aqueous solution initiator that concentration is the azo-bis-isobutyrate hydrochloride of 7.5wt ‰ continuously in reaction process.After reaction reaches predetermined charging capacity, stop stirring, reclaim unreacted mix monomer in reactor, and release emulsion.Reaction times is 110min, and emulsion solid content is 26.1%.Speed of reaction is 3.0g/ (L.min).Washed by emulsion mechanical coalescence, vacuum-drying, sample presentation detected result is in table 2.
Molecular weight of product Mw is 4,100,000, and median size is 0.26 μm.
Embodiment 3
Intermittent type free radical emulsion of the present invention preparation is carried out, to prepare polyvinylidene fluoride resin in the autoclave of 50L.Add 30L deionized water in a kettle., add whiteruss 15g, borax 35g.Then in reactor, the air of vapor space is first less than 30ppm with nitrogen replacement to oxygen level.Then utilize vinylidene (VDF) and the mix monomer replacement reaction kettle of R 1216 (HFP), make its oxygen level be less than 20ppm.In reactor, the perfluoro ammonium caprylate aqueous solution of 300g5wt% is added by volume pump.Unlatching reactor stirs, and reactor liquidus temperature is risen to 55 DEG C.Membrane compressor is adopted to add the mix monomer (R 1216 is 8.5% of vinylidene quality) of vinylidene (VDF) and R 1216 (HFP) to reactor pressure 4.0MPa.
The aqueous solution adding the azo-bis-isobutyrate hydrochloride of the 5wt% of 20g starts initiation reaction.In reaction process, maintain reactor pressure 4.0MPa with adding vinylidene (VDF) monomer, temperature of reaction 55 DEG C, adds molecular weight regulator methane 12g.Volume pump is adopted to add with the speed of 10ml/min the aqueous solution initiator that concentration is the azo-bis-isobutyrate hydrochloride of 9wt ‰ continuously in reaction process.After reaction reaches predetermined charging capacity, stop stirring, reclaim unreacted mix monomer in reactor, and release emulsion.Reaction times is 115min, and emulsion solid content is 27.5%.Speed of reaction is 3.2g/ (L.min).Washed by emulsion mechanical coalescence, vacuum-drying, sample presentation detected result is in table 2.
Molecular weight of product Mw is 4,100,000, and median size is 0.26 μm.
Table 2 detected result
Project Unit Embodiment 2 Embodiment 3
Fusing point 166 148
Degree of crystallinity % 67.5 65.2
Molecular weight Ten thousand 348 362
Tensile strength MPa 61.3 60.8
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.

Claims (8)

1. a preparation method for high-tensile-strengtpolyvinylidene polyvinylidene fluoride, under initiator and molecular weight regulator existence condition, in aqueous dispersion, makes vinylidene (VDF) and another kind of comonomer carry out radical polymerization; It is characterized in that, comprise the steps:
(1) in reactor, pH value regulator, paraffin and water is added, the emulsion of obtained Quality of Paraffin Waxes volumetric concentration 0 ~ 1.0g/L, pH adjusting agent mass body volume concentrations 0.5 ~ 2.0g/L;
(2) in step (1) described reactor, add the mix monomer of vinylidene and another kind of comonomer, make the pressure of described reactor reach 2.0 ~ 6.0MPa; Polymerization temperature is 40 ~ 55 DEG C;
(3) at the temperature of the pressure of 2.0 ~ 6.0MPa and 40 ~ 75 DEG C, in step (2) described reactor, add initial initiator initiated polymerization, then add molecular weight regulator wherein;
(4) in step (3) described reactor, add mix monomer, the pressure maintained in described reactor is constant in batches; Add initiator continuously, until polyreaction terminates; Described initiator is selected from the one in dilauroyl peroxide, azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile);
(5) resulting polymers is carried out condensing, wash and obtaining the polyvinylidene fluoride resin of high strength by reaction after terminating;
Wherein, add in described step (3) that initiator is whole initiator add-on 1 ~ 5%, all the other initiators add in step (4).
2. preparation method according to claim 1, is characterized in that, the add-on of described initiator is that mass body volume concentrations is 0.1 ~ 1g/L in aqueous dispersion.
3. preparation method according to claim 1, is characterized in that, described molecular weight regulator is hydrogen, methane, ethane, propane, one or more in iso-pentane, monochloro methane, methylene dichloride, trichloromethane and tetracol phenixin.
4. the preparation method according to claim 1 or 3, is characterized in that, the mass body volume concentrations of described molecular weight regulator in aqueous dispersion is 0.2 ~ 0.5g/L.
5. the preparation method according to any one of claim 1-3, described another kind of comonomer is one or more in tetrafluoroethylene, R 1216, trifluorochloroethylene, perfluoroalkyl vinyl ether;
Described another kind of comonomer quality is 8.5% ~ 10% of vinylidene quality.
6. preparation method according to claim 1, is characterized in that, described pH value regulator is selected from the one in Sodium phosphate dibasic, borax, bicarbonate of ammonia.
7. the preparation method according to claim 1 or 6, is characterized in that, initiator is mixed with the 1wt%-10wt% aqueous solution in (3) by described step, adds reactor.
8. the preparation method according to claim 1 or 6, is characterized in that, initiator is mixed with the aqueous solution in (4) by described step, and concentration controls, for 3wt ‰ ~ 8 ‰, to add reactor continuously.
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CN103709304A (en) * 2013-12-26 2014-04-09 中昊晨光化工研究院有限公司 Preparation method of high-strength fluorine-containing polymer
CN103755850B (en) * 2013-12-30 2016-04-27 山东华夏神舟新材料有限公司 A kind of preparation method of the polyvinylidene fluoride resin for sun power backboard membrane
CN103755858B (en) * 2013-12-30 2016-04-27 山东华夏神舟新材料有限公司 A kind of solution polymerization process of polyvinylidene fluoride copolymer
CN104558306B (en) * 2014-12-15 2017-05-03 东莞市长安东阳光铝业研发有限公司 Preparation method of polyvinylidene fluoride resin
CN104829773B (en) * 2015-05-25 2016-09-14 山东森福新材料有限公司 A kind of modified polytrifluorochloroethylene and preparation method thereof

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