CN102336854B - Preparation method for high heat resistance polyvinylidene fluoride - Google Patents
Preparation method for high heat resistance polyvinylidene fluoride Download PDFInfo
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Abstract
Provided is a preparation method for high heat resistance polyvinylidene fluoride, which belongs to the technical field of fluorochemical industry. The method is characterized by comprising the following steps: 1) blowing nitrogen into an enclosed polymerization kettle to remove oxygen and adding deionized water, magnesium hydroxide, diisopropyl peroxydicarbonate, diethyl malonate and vinylidene fluoride; 2) under the conditions that reaction pressure is 3.0 to 7.0 MPa and reaction temperature is 45 to 120 DEG C, starting a stirring paddle, with a rotating speed being 350 to 750 r/min, and allowing an obtained mixture to react for 4 to 6 hours so as to prepare a polyvinylidene fluoride slurry; 3) rinsing the polyvinylidene fluoride slurry with deionized water until foams disappear, allowing the conductivity of rinsing liquid to decrease to less than 1 mu s/cm, and carrying out vacuum drying at a temperature of 90 to 100 DEG C for 15 to 20 hours so as to prepare a finished product. According to the invention, suspension polymerization is employed in the preparation method; a finally prepared polyvinylidene fluoride resin is loose and has greatly reduced possibility of adhering to the kettle and excellent high temperature resistance
Description
Technical field
The invention belongs to the fluorine chemical technical field, be specially the preparation method of high heat resistance polyvinylidene fluoride.
Background technology
Polyvinylidene difluoride (PVDF) (PVDF) refers to the homopolymer of vinylidene (VDF) or the multipolymer of vinylidene (VDF) and other a small amount of fluorine-containing vinyl monomers, and it is the thermoplastic engineering plastic of a kind of high molecular, hemicrystalline, high tenacity.Usually, the relative molecular mass of PVDF is 40～600,000, fluorine content 59%, and degree of crystallinity 60%～80%, its repeating unit is (CH
2-CF
2-)
nThe alternative arrangement of group.Because fluorine atom has the strongest electronegativity (4.0) the strong chemical bond (485KJ/mol) that becomes bond energy maximum in the covalent single bond of C-F in addition, fluorine atom has lower polarizability, less model moral gas radius and distribute relatively more symmetrical.Therefore PVDF has high chemical stability, highly insulativity, high light transmittance, high-wearing feature, high thermal resistance, radiation resistance, weathering resistance, low-refraction, low combustible, low pressure are electrical.The structure of comprehensive PVDF makes it have remarkable physical and chemical performance, has become the second largest kind that is only second to polytetrafluoroethylene (PTFE) in the fluoro-resin at present, is widely used in petrochemical industry, metallurgy, pharmacy, building, food, environmental protection, military project, the fields such as aerospace, DEVELOPMENT PROSPECT is wide.The mode of production of PVDF mainly contains emulsion polymerization, suspension polymerization, solution polymerization process and supercritical polymerization method etc. at present, and is wherein general in industrial production with emulsion polymerization and suspension polymerization.
In the emulsion polymerization, the VDF monomer carries out polymerization in the presence of fluorine-containing salt tensio-active agent, and this system mainly is comprised of monomer, initiator, emulsifying agent, chain-transfer agent, paraffin and deionized water.Add paraffin and can stablize the PVDF micella in polymerization process, after question response finished, filtration, cleaning, drying obtained particle diameter less than 1 micron powder.The advantage of the method is that (75-130 ℃) carries out polymerization under higher temperature, and polymerization velocity is very fast; Shortcoming is that emulsifying agent is expensive, and emulsion needs the postprocessing working procedures such as cohesion, washing, dehydration, drying, and production cost is higher, and the PVDF molecular weight distribution of preparation is wider, and thermostability is relatively poor.The patent that this respect can be mentioned has: US 4076929, and US 4025709.
The VDF monomer passes through dispersion agent in the suspension polymerization in water-soluble dispersion system, initiator, and the effect of chain-transfer agent at a lower temperature (45～120 ℃) is polymerized.The PVDF molecular chain of comparing suspension polymerization with letex polymerization is more regular, and side chain is few, and degree of crystallinity is higher under the condition of identical weight-average molecular weight, and molecular weight distribution is narrower, fusing point higher (〉=3-5 ℃), and swelling capacity is less in the chemical solvents; The suspended dispersed system can reduce the deposition of PVDF on reactor wall in addition, does not also need in the last handling process to condense this procedure, and production cost is lower.The dispersion agent that adsorbs on the granular resin is few, and product purity is high, can directly be used for granulation.
Current, a lot of technology are arranged all in the thermotolerance of making great efforts to improve PVDF, but without exception be all to be that the combination of emulsifying agent (tensio-active agent), initiator and chain-transfer agent by selecting all kinds of qualities improves technique, and major part all is to adopt the mode of letex polymerization to produce PVDF.The preferential oil-soluble initiator that adopts is such as benzoyl peroxide, ditertiary butyl peroxide, dialkyl peroxydicarbonates, peresters in the letex polymerization; The ionic surface active agent that organic acid or alkali are derived; Can not produce the chain-transfer agent of unsettled chain end group owing to thermal treatment.
Patent US4360652 discloses the emulsion polymerisation process of a kind of VDF, and it is chain-transfer agent that the method adopts Virahol.
Patent FR2259114 discloses the emulsion polymerisation process of a kind of VDF, and it is initiator that the method adopts peroxy dicarbonate salt, and acetone is chain-transfer agent.
Patent EP169328 discloses the emulsion polymerisation process of a kind of VDF, and the method adopts trichlorofluoromethane as chain-transfer agent.
Patent CN1532212A discloses the emulsion polymerisation process of a kind of VDF, and the method adopts HFA161 as chain-transfer agent.
Patent EP169328 discloses the emulsion polymerisation process of a kind of VDF, and the method adopts di-isopropyl peroxydicarbonate (IPP) as initiator.
Patent EP387938 discloses the emulsion polymerisation process of a kind of VDF, and the method adopts ammonium persulphate as initiator, and ethyl acetate is as chain-transfer agent.
Patent FR264446 discloses the emulsion polymerisation process of a kind of VDF, and the method adopts alkyl acetates as chain-transfer agent, does not use emulsifying agent.
Patent US5929152 discloses the emulsion polymerisation process of a kind of VDF, and the method adopts adds the thermostability that bismuth salt improves PVDF.
Patent FR1298572 discloses the emulsion polymerisation process of a kind of VDF, and the method adopts interpolation barium salt or strontium salt to improve the thermostability of PVDF.
Patent US3728303 discloses the emulsion polymerisation process of a kind of VDF, and the method adopts interpolation sodium-chlor, Repone K, sodium chlorate, Potcrate to improve the thermostability of PVDF.
Patent CN1526744A discloses the emulsion polymerisation process of a kind of VDF, and the method utilizes Potassium Persulphate to carry out polymerization as initiator in aqueous dispersions, improves the thermostability of PVDF by adding sodium acetate and optional alkylsulphonic acid potassium.
Summary of the invention
In view of the above-mentioned problems in the prior art, the object of the invention is to design the preparation method's that a kind of high heat resistance polyvinylidene fluoride is provided technical scheme, the polyvinylidene difluoride (PVDF) that makes of method has excellent high temperature resistant tint permanence thus.
The preparation method of described high heat resistance polyvinylidene fluoride is characterized in that may further comprise the steps:
1) in airtight polymerization reaction kettle, purges the nitrogen deoxygenation, add deionized water, magnesium hydroxide, di-isopropyl peroxydicarbonate, diethyl malonate, vinylidene, the consumption of described deionized water is the 125-200% of vinylidene quality, the consumption of described magnesium hydroxide is the 0.05-0.18% of vinylidene quality, the consumption of described di-isopropyl peroxydicarbonate is the 0.015-2.0% of vinylidene quality, and the consumption of described diethyl malonate is the 0.15-2.3% of vinylidene quality;
2) reaction pressure is 3.0 – 7.0Mpa, and temperature of reaction is 120 ℃ of 45 –, opens stirring rake, and rotating speed is 350 – 750r/min, finishes reaction after 4-6 hour, makes the polyvinylidene difluoride (PVDF) slurry;
3) with the polyvinylidene difluoride (PVDF) slurry with deionized water wash to lather collapse, the washings specific conductivity is down to below the 1 μ s/cm, and then at 90-100 ℃ of lower vacuum-drying 15-20 hour, makes finished product.
The preparation method of described high heat resistance polyvinylidene fluoride is characterized in that: vinylidene adds at twice, adds the 30-50% of predetermined dose during beginning; React after 1-1.5 hour, slowly add rest part, keep pressure at 3.0 – 7.0Mpa, continue to finish reaction behind the insulation polyase 13-5 hour.
The preparation method of described high heat resistance polyvinylidene fluoride is characterized in that: diethyl malonate adds in batches, adds the 50-70% of predetermined dose before polymerization begins; Rest part is after reaction 1-1.5 hour, and interval 40min divides 3 equivalent to add, and keeps pressure at 3.0 – 7.0Mpa, adds the follow-up continuation of insurance temperature polymerization of end and finishes reaction after 1.5-3 hour.
The preparation method of described high heat resistance polyvinylidene fluoride is characterized in that in the step 1): the consumption of described deionized water is the 130-180% of vinylidene quality, preferred 150-170%.
The preparation method of described high heat resistance polyvinylidene fluoride is characterized in that in the step 1): the consumption of described magnesium hydroxide is the 0.08-0.15% of vinylidene quality, preferred 0.10-0.13%.
The preparation method of described high heat resistance polyvinylidene fluoride is characterized in that in the step 1): the consumption of described di-isopropyl peroxydicarbonate is the 0.02-1.5% of vinylidene quality, preferred 0.5-1.2%, more preferably 0.75-1.0%.
The preparation method of described high heat resistance polyvinylidene fluoride is characterized in that in the step 1): the consumption of described diethyl malonate is the 0.5-1.5% of vinylidene quality, preferred 0.8-1.2%.
The preparation method of described high heat resistance polyvinylidene fluoride is characterized in that step 2) in: reaction pressure 3.5 – 6.5Mpa, preferred 4.0 – 6.0Mpa, more preferably 4.5 – 5.5Mpa.
The preparation method of described high heat resistance polyvinylidene fluoride is characterized in that step 2) in: temperature of reaction is 100 ℃ of 50 –, 90 ℃ of preferred 55 –, and more preferably 60 – 80 ℃.
The preparation method of described high heat resistance polyvinylidene fluoride is characterized in that step 2) in: rotating speed is 400 – 700r/min, preferred 500 – 650r/min, more preferably 550 – 600r/min.
The present invention selects the preparation method of suspension polymerization, and a kind of new dispersion agent-magnesium hydroxide is provided, and selects organic initiators and chain-transfer agent to the PVDF better heat stability, and then regulates the distribution of molecular weight in dosage and the interpolation time control polymerization process; The in addition pattern by temperature and stir speed (S.S.) telomerized polymer, at last by post-processing technology with dispersion agent, the content of chain-transfer agent is down to minimum.
Adopting the present invention to carry out the used dispersion agent of VDF homopolymerization is magnesium hydroxide, and this dispersion agent stirs configuration by sodium hydroxide solution and magnesium chloride solution after with the 2:1 molar ratio reaction and forms, and the pH value is between 11～12.Dispersant dosage has larger impact to resin particle size, and consumption is too small, and resin particle is too thick, easily conglomeration, and chain-transfer agent is not easy stripping, brings considerable influence to aftertreatment; Consumption is excessive, and resin particle is too thin, self is not easy to be dissolved.
Adopting the present invention to carry out the used initiator of VDF homopolymerization is highly active organo-peroxide-di-isopropyl peroxydicarbonate (IPP).Adopt the PVDF thermostability of this class initiator preparation will get well without organic initiators such as ammonium persulphate.The consumption of initiator is very large to the performance impact of the rate of polymerization of VDF and PVDF.Initiator amount is too small, and rate of polymerization is too slow, is unfavorable for suitability for industrialized production; Initiator amount is excessive, and rate of polymerization is too fast, and polyreaction is unstable, and molecular weight and productive rate all descend.
Adopting the present invention to carry out the used chain-transfer agent of VDF homopolymerization is diethyl malonate.Chain-transfer agent can be used to control the molecular weight of polymkeric substance, and the size of its consumption and joining day, the thermostability of molecular weight distribution and PVDF had profound influence to rate of polymerization.The chain-transfer agent consumption is excessive, and the radical termination chance increases, and it is fast to stop speed, and molecular weight reduces, and shows as melt mass flow rate and increases, and limiting viscosity reduces, and elongation at break improves.The little then molecular weight of chain-transfer agent consumption increases, and reaction is difficult to control, and productive rate is low.The adding mode of chain-transfer agent and joining day also can affect molecular weight and the distribution of PVDF.It is that the molecular weight that can effectively control polymkeric substance can not produce detrimentally affect to its rate of polymerization and thermostability again that suitable chain-transfer agent adds principle, and be added in the reactor is optimal selection in batches.
Adopt the present invention to carry out the used deionized water specific conductivity of VDF homopolymerization and be generally less than 0.5 μ s/cm.Specific conductivity is too high to cause the unstable of suspension system easily, and can affect performance and the color and luster of PVDF.
The preparation method of above-mentioned high heat resistance polyvinylidene fluoride, adopt the mode of suspension polymerization, vinylidene fluoride monomers is under the effect of dispersion agent magnesium hydroxide, take di-isopropyl peroxydicarbonate as initiator, diethyl malonate is that chain-transfer agent generates the polyvinylidene difluoride (PVDF) particle by radical polymerization in aqueous medium.The polyvinylidene fluoride resin that adopts the present invention finally to make is loose, and sticking still amount significantly reduces, and has excellent high thermal resistance (xanthochromia index YI is far below currently available products scope " 28-40 ").
Embodiment
It is following that the invention will be further described by embodiment and corresponding test.
Embodiment 1
Be to purge the nitrogen deoxygenation in the airtight polymerization reaction kettle of 20L at capacity, make that oxygen level is lower than 50ppm in the still.Add the 12Kg deionized water, 3.9g magnesium hydroxide, 1.8g di-isopropyl peroxydicarbonate, 50g diethyl malonate, 2.5Kg vinylidene, be warming up to 47 ℃, open stirring rake, rotating speed is 700r/min, keep after 1 hour, slowly add the 4.5Kg vinylidene, pressure is remained on about 5.6MPa, interval 40min divides each 15g of interpolation diethyl malonate 3 times simultaneously.Add the polymerization of the follow-up continuation of insurance temperature of end and finish reaction after 2.5 hours.With the polyvinylidene difluoride (PVDF) slurry with deionized water wash until lather collapse, the washings specific conductivity is down to below the 1 μ s/cm, and then 90 ℃ of lower vacuum-dryings 15 hours, makes finished product.
Embodiment 2
Be to purge the nitrogen deoxygenation in the airtight polymerization reaction kettle of 20L at capacity, make that oxygen level is lower than 50ppm in the still.Add the 12Kg deionized water, 9.2g magnesium hydroxide, 145g di-isopropyl peroxydicarbonate, 100g diethyl malonate, 3.5Kg vinylidene, be warming up to 60 ℃, open stirring rake, rotating speed is 500r/min, keep after 1.5 hours, slowly add the 3.8Kg vinylidene, pressure is remained on about 6.6MPa, interval 40min divides each 15g of interpolation diethyl malonate 3 times simultaneously.Add the polymerization of the follow-up continuation of insurance temperature of end and finish reaction after 1.5 hours.With the polyvinylidene difluoride (PVDF) slurry with deionized water wash until lather collapse, the washings specific conductivity is down to below the 1 μ s/cm, and then 96 ℃ of lower vacuum-dryings 18 hours, makes finished product.
Embodiment 3
Be to purge the nitrogen deoxygenation in the airtight polymerization reaction kettle of 20L at capacity, make that oxygen level is lower than 50ppm in the still.Add the 12Kg deionized water, 10.5g magnesium hydroxide, 60g di-isopropyl peroxydicarbonate, 30g diethyl malonate, 3.2Kg vinylidene, be warming up to 66 ℃, open stirring rake, rotating speed is 620r/min, keep after 1.1 hours, slowly add the 4Kg vinylidene, pressure is remained on about 5.6MPa, interval 40min divides each 10g of interpolation diethyl malonate 3 times simultaneously.Add the polymerization of the follow-up continuation of insurance temperature of end and finish reaction after 2 hours.With the polyvinylidene difluoride (PVDF) slurry with deionized water wash until lather collapse, the washings specific conductivity is down to below the 1 μ s/cm, and then 100 ℃ of lower vacuum-dryings 20 hours, makes finished product.
Comparative example 1
Similar to Example 3, only difference is that the add-on of magnesium hydroxide is 30g.
Embodiment 4
Be to purge the nitrogen deoxygenation in the airtight polymerization reaction kettle of 20L at capacity, make that oxygen level is lower than 50ppm in the still.Add the 12Kg deionized water, 13.5g magnesium hydroxide, 145g di-isopropyl peroxydicarbonate, 80g diethyl malonate, 3.2Kg vinylidene, be warming up to 70 ℃, open stirring rake, rotating speed is 650r/min, keep after 1 hour, slowly add the 4.2Kg vinylidene, pressure is remained on about 6.0MPa, interval 40min divides each 25g of interpolation diethyl malonate 3 times simultaneously.Add the polymerization of the follow-up continuation of insurance temperature of end and finish reaction after 2.7 hours.With the polyvinylidene difluoride (PVDF) slurry with deionized water wash until lather collapse, the washings specific conductivity is down to below the 1 μ s/cm, and then 100 ℃ of lower vacuum-dryings 18 hours, makes finished product.
Comparative example 2
Similar to Example 4, only difference is that the first add-on of diethyl malonate is 100g, and 3 additional amounts of interval 40min are 40g.
Embodiment 5
Be to purge the nitrogen deoxygenation in the airtight polymerization reaction kettle of 20L at capacity, make that oxygen level is lower than 50ppm in the still.Add the 12Kg deionized water, 10.0g magnesium hydroxide, 65g di-isopropyl peroxydicarbonate, 35g diethyl malonate, 3.0Kg vinylidene, be warming up to 62 ℃, open stirring rake, rotating speed is 580r/min, keep after 1.2 hours, slowly add the 4Kg vinylidene, pressure is remained on about 5.0MPa, interval 40min divides each 10g of interpolation diethyl malonate 3 times simultaneously.Add the polymerization of the follow-up continuation of insurance temperature of end and finish reaction after 2.0 hours.With the polyvinylidene difluoride (PVDF) slurry with deionized water wash until lather collapse, the washings specific conductivity is down to below the 1 μ s/cm, and then 100 ℃ of lower vacuum-dryings 18 hours, makes finished product.
Comparative example 3
Similar to Example 5, only difference is that the add-on of magnesium hydroxide is 25g, and the add-on of di-isopropyl peroxydicarbonate is 145g, and diethyl malonate is disposable adding before the reaction beginning only, and add-on is 200g.
In any of above-described embodiment, adhere to and block in the still that all do not induce reaction in polymerization process and after finishing.
In 265 ℃, the measurement result of the xanthochromia test of 1h is listed in the table below in 1 in the lump with the polyvinylidene difluoride (PVDF) of above-described embodiment and comparative example preparation.
Can find clearly that from the embodiment of above-mentioned table 1 and the result of comparative example high heat resistance polyvinylidene fluoride provided by the invention has excellent high thermal resistance.
Claims (10)
1. the preparation method of high heat resistance polyvinylidene fluoride is characterized in that may further comprise the steps:
1) in airtight polymerization reaction kettle, purges the nitrogen deoxygenation, add deionized water, magnesium hydroxide, di-isopropyl peroxydicarbonate, diethyl malonate, vinylidene, the consumption of described deionized water is the 125-200% of vinylidene quality, the consumption of described magnesium hydroxide is the 0.05-0.18% of vinylidene quality, the consumption of described di-isopropyl peroxydicarbonate is the 0.015-2.0% of vinylidene quality, and the consumption of described diethyl malonate is the 0.15-2.3% of vinylidene quality;
Vinylidene adds at twice, adds the 30-50% of predetermined dose during beginning; React after 1-1.5 hour, slowly add rest part, keep pressure at 3.0 – 7.0MPa, continue to finish reaction behind the insulation polyase 13-5 hour;
Diethyl malonate adds in batches, adds the 50-70% of predetermined dose before polymerization begins; Rest part is after reaction 1-1.5 hour, and interval 40min divides 3 equivalent to add, and keeps pressure at 3.0 – 7.0MPa, adds the follow-up continuation of insurance temperature polymerization of end and finishes reaction after 1.5-3 hour;
2) reaction pressure is 3.0 – 7.0MPa, and temperature of reaction is 120 ℃ of 45 –, opens stirring rake, and rotating speed is 350 – 750r/min, finishes reaction after 4-6 hour, makes the polyvinylidene difluoride (PVDF) slurry;
3) with the polyvinylidene difluoride (PVDF) slurry with deionized water wash to lather collapse, the washings specific conductivity is down to below the 1 μ S/cm, and then at 90-100 ℃ of lower vacuum-drying 15-20 hour, makes finished product.
2. the preparation method of high heat resistance polyvinylidene fluoride as claimed in claim 1, it is characterized in that in the step 1): the consumption of described deionized water is the 130-180% of vinylidene quality.
3. the preparation method of high heat resistance polyvinylidene fluoride as claimed in claim 1, it is characterized in that in the step 1): the consumption of described deionized water is the 150-170% of vinylidene quality.
4. the preparation method of high heat resistance polyvinylidene fluoride as claimed in claim 1, it is characterized in that in the step 1): the consumption of described magnesium hydroxide is the 0.08-0.15% of vinylidene quality.
5. the preparation method of high heat resistance polyvinylidene fluoride as claimed in claim 1, it is characterized in that in the step 1): the consumption of described magnesium hydroxide is the 0.10-0.13% of vinylidene quality.
6. the preparation method of high heat resistance polyvinylidene fluoride as claimed in claim 1, it is characterized in that in the step 1): the consumption of described di-isopropyl peroxydicarbonate is the 0.02-1.5% of vinylidene quality.
7. the preparation method of high heat resistance polyvinylidene fluoride as claimed in claim 1, it is characterized in that in the step 1): the consumption of described diethyl malonate is the 0.5-1.5% of vinylidene quality.
8. the preparation method of high heat resistance polyvinylidene fluoride as claimed in claim 1 is characterized in that step 2) in: reaction pressure 3.5 – 6.5MPa.
9. the preparation method of high heat resistance polyvinylidene fluoride as claimed in claim 1 is characterized in that step 2) in: temperature of reaction is 100 ℃ of 50 –.
10. the preparation method of high heat resistance polyvinylidene fluoride as claimed in claim 1 is characterized in that step 2) in: rotating speed is 400 – 700r/min.
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| JP5916562B2 (en) * | 2012-08-22 | 2016-05-11 | 株式会社クレハ | Method for producing vinylidene fluoride polymer |
| CN102875711B (en) * | 2012-09-20 | 2014-05-14 | 中昊晨光化工研究院有限公司 | Condensing washing method of polyvinylidene fluoride emulsion |
| CN103524647B (en) * | 2013-08-16 | 2016-10-12 | 巨化集团技术中心 | A kind of preparation method of polyvinylidene fluoride resin |
| CN104710550A (en) * | 2013-12-11 | 2015-06-17 | 浙江蓝天环保高科技股份有限公司 | High molecular weight polyvinylidene fluoride resin and preparation method thereof |
| CN104497190B (en) * | 2014-12-29 | 2016-09-21 | 浙江孚诺林化工新材料有限公司 | A kind of preparation method of the partial fluorine ethylene polymer for lithium ion battery electrode material binding agent |
| CN105461837A (en) * | 2015-12-18 | 2016-04-06 | 常熟三爱富振氟新材料有限公司 | Preparation method of polyvinylidene fluoride ultrafiltration membrane |
| CN105924554B (en) * | 2016-06-12 | 2018-12-25 | 巨化集团技术中心 | A kind of preparation method of polyvinylidene fluoride resin |
| CN110317286A (en) * | 2018-03-30 | 2019-10-11 | 浙江蓝天环保高科技股份有限公司 | A method of improving polyvinylidene fluoride resin degree of purity |
| CN112159595B (en) * | 2020-10-16 | 2021-11-23 | 深圳市久和丝印器材有限公司 | Rubber head for pad printing of different types of hand surface plate glass and preparation method thereof |
| CN116375915A (en) * | 2023-04-03 | 2023-07-04 | 乳源东阳光氟树脂有限公司 | Method for preparing ultra-high molecular weight PVDF resin by supercritical polymerization process |
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| CN101003589A (en) * | 2007-01-12 | 2007-07-25 | 天津市精英有机聚合物有限公司 | Method for preparing polyvinylidene fluoride, and copolymer |
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