CN102516439B - Wide molecular weight distribution 26 type fluororubber and preparation method thereof - Google Patents
Wide molecular weight distribution 26 type fluororubber and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a wide molecular weight distribution 26 type fluororubber and a preparation method thereof, and belongs to the technical field of polymer material fluoroelastomer synthesis. The fluororubber is characterized in that the dispersiveness index MWD of the fluororubber is 4-15. The preparation method comprises: in two reaction kettles, carrying out nitrogen blowing oxygen removing, adding deionized water, an emulsifier, a pH value regulator and a chain transfer agent, introducing a comonomer, stirring and heating, and changing the type of the added initiator and intermittently supplying the chain transfer agent in the polymerization process; conveying the resulting emulsions to a mixing reactor according to a certain proportion after the reaction is performed for 4-7 hours; adding a pre-mixed monomer and an additive to continuously produce. The emulsions in the mixing reactor are subjected to condensation, washing, drying, extrusion forming and packaging. With the wide molecular weight distribution 26 type fluororubber and the preparation method thereof, the molecular weight distribution range is optimized, and the vulcanization rate is improved, such that the crude rubber has excellent processing property and excellent storage stability, and the vulcanized rubber has ultrahigh mechanical performance and excellent low compression permanent deformation.
Description
Technical field
The invention belongs to macromolecular material fluoroelastomer synthesis technical field, be specially 26 type viton of wide molecular weight distribution and preparation method thereof.
Background technology
Viton refers to the synthetic polymer fluoroelastomer that contains fluorine atom on the carbon atom of main chain or side chain, due to the characteristics that contain fluorine element in its molecular structure, there is excellent thermotolerance, chemical-resistant, Weather-resistant and good physical and mechanical properties, be widely used in the departments such as automobile, metallurgy, petrochemical complex, electromechanics, aerospace, domestic 26 type viton are equivalent to the like product Viton A of du pont company, be the copolymer of vinylidene (VDF) and R 1216 (HFP), fluorine content is 66%.
The ubiquitous problem of current 26 type viton is that rheological property is poor, and processing characteristics is bad.While being mainly manifested in molding, mold flow properties is poor, fouling is many, sulfuration is uneven, insufficient formability, open the mould difficulty, goods have current mark and take out the limit phenomenon, affect the performance of the finished product.In view of this, develop the viton with excellent processing characteristics and become the task of top priority.
In order to obtain the excellent machinability of viton.Can, by developing new processing aid to improve its mobility, release property and thermostability, still tend to like this cause the size distortion of finished product and tear strength to descend on the one hand.Can, by the emulsion of when synthetic, widening range of molecular weight distributions or polymerization different molecular weight, then by the outer interworking of still, increase range of molecular weight distributions on the other hand.Molecular weight distribution (MWD) is one of fundamental characteristics of determining viton rheological property and end-use.
MWD is generally known as dispersed index, means the ratio of weight-average molecular weight and number-average molecular weight, and the curve that can obtain by gel chromatography fully is described.
Doing a lot of improvements aspect the processing characteristics that improves viton both at home and abroad, the patent that can be mentioned has:
Patent CN1104464C discloses a kind of method that improves the viton processing characteristics, and the composition that the method obtains viton by the lipid acid monoamide that adds 0.1-5 part weight improves demolding performace with this.
Patent CN1203112C discloses a kind of method that improves the viton processing characteristics, the method by the aqueous liquid dispersion from fluoroelastomer copolymer by this multipolymer condensation out and to the multipolymer agglutinator that the obtains operation of mixing one side drying on one side, improve its sulfuration stability to the thing that dissolves each other that adds vulcanizing agent and vulcanization accelerator in agglutinator.
Patent examined patent publication 56-59895 communique discloses a kind of method that improves the viton processing characteristics, the method adopts in the 1st stage of polymerization and uses water soluble starter, produce viton in the 2nd stage with two sections polymerization processs of oil-soluble initiator, the method improves its processing characteristics to change polymerization formula.
Patent CN101429264A discloses a kind of method that improves the viton processing characteristics, and the method, by the chain end group at viton, introducing organic group, obtains wider molecular weight distribution, with this, improves processing characteristics.
Patent US6790915B1 discloses a kind of method that improves the viton processing characteristics, the ultra-low Mooney viscosity of the method employing peroxide curable (
<30) viton improves processing characteristics.
Open patent 2000-34381 communique discloses a kind of method that improves the viton processing characteristics, the method is solidified altogether by 3 kinds of fluoroelastomers that mooney viscosity is different, obtain fluorine-containing rubber, with the peroxide cure of this viton, combine to improve processibility.
Summary of the invention
In view of the above-mentioned problems in the prior art, the object of the invention is to design 26 type viton of a kind of wide molecular weight distribution and preparation method thereof are provided, viton prepared by this method, when keeping the high-strength mechanical performance, has been optimized processing characteristics, has a good application prospect.
The described 26 type viton with wide molecular weight distribution, is characterized in that this viton has very wide molecular weight distribution, its dispersed index M WD=4-15.
26 type viton of described wide molecular weight distribution, is characterized in that the dispersed index M WD=6-12 of described viton, preferably 7-10.
The preparation method of 26 type viton of described wide molecular weight distribution comprises the following steps:
1) purge the nitrogen deoxygenation in two airtight polymerization reaction kettle A, B, add deionized water, emulsifying agent, pH adjusting agent and chain-transfer agent;
2) to adding respectively the R 1216 that weight ratio is 25-40:60-75 in two reactor A, B: vinylidene fluoride monomers, open and stir, to reaction pressure be 3.0 – 7.0Mpa, heating up and making temperature of reaction is 120 ℃ of 65 –;
3) in two reactor A, B, add respectively initiator 1 and 2 to start reaction, the R 1216 that is simultaneously 1/3～3/5 by the mass ratio of premix in medial launder/vinylidene mixed gas is added in reactor A, B continuously by compressor, makes the still internal pressure keep constant; Add initiator 3 in reaction 30-60min backward reactor A, after added chain-transfer agent every 1.0-3.0 hour in reactor A, B;
4) reaction was delivered to the emulsion in two reactor A, B in mixing kettle by pressure controlled valve after 4-7 hour, the mixed gas of premix in medial launder is added in reactor A, B continuously by compressor simultaneously, pre-assigned same isocyatic initiator, emulsifying agent, deionized water, pH adjusting agent are injected to reactor A, B continuously by volume pump, keep the still internal pressure, homo(io)thermism, enter next reaction time;
5) emulsion in mixing kettle is condensed to rear washing, oven dry with magnesium chloride, through cold feeding machine formed package.
The preparation method of 26 type viton of described wide molecular weight distribution, is characterized in that the weight part of emulsifying agent in the deionized water of every 100 weight parts is 0.1-5.0, preferably 0.5-3, more preferably 1-2; The weight part of initiator is 0.001-3.2, preferably 0.1-2.5, more preferably 1-1.5; The weight part of pH adjusting agent is 0.05-0.68, preferably 0.2-0.5, more preferably 0.3-0.4; The weight part of chain-transfer agent is 0.0005-1.5, preferably 0.01-1.0, more preferably 0.1-0.5; The weight part of monomer is 70-100, preferably 80-90.
The preparation method of 26 type viton of described wide molecular weight distribution, is characterized in that polymerization stirring velocity used is 300-800r/min, preferably 400-700r/min, more preferably 500-600r/min; Polymerization reaction pressure used is 3.0 – 7.0Mpa, preferably 3.5 – 6.5Mpa, more preferably 4 – 5Mpa; Temperature of reaction is 120 ℃ of 65 –, and preferably 75 – is 100 ℃, and more preferably 80 – is 90 ℃.
The preparation method of 26 type viton of described wide molecular weight distribution is characterized in that: initiator 1 is ammonium persulphate, and initiator 3 is di-isopropyl peroxydicarbonate, and initiator 2 is the beta-hydroxyethyl tert-butyl peroxide.
The preparation method of 26 type viton of described wide molecular weight distribution, is characterized in that described emulsifying agent is ammonium perfluorocaprylate, and described pH adjusting agent is Sodium phosphate dibasic; Described chain-transfer agent: in reactor A, being diethyl malonate, is iso-pentane in reactor B.
The preparation method of 26 type viton of described wide molecular weight distribution, it is characterized in that described viton adopts the semi continuous method preparation of letex polymerization, add chain-transfer agent every 1-3h 1 time in two reactor A, B, every 7-9 hour, the emulsion in mixing kettle is once condensed.
The preparation method of 26 type viton of described wide molecular weight distribution, is characterized in that reactor A and reactor B are 4/3～5/3 to the speed ratio of discharging in mixing kettle.
The preparation method of 26 type viton of described wide molecular weight distribution, it is characterized in that the R 1216 added respectively in two reactor A, B: the vinylidene weight ratio is 30-35:65-70.
26 type viton of above-mentioned wide molecular weight distribution and preparation method thereof, adopt the method for semi-continuous emulsion polymerizing, the kind that adds by initiator in the control polymerization process, the adding kind and add mode of chain-transfer agent, improve polymer molecular structure, stable end groups, and the approach be mixed outward by the Continuous Flow still, optimize range of molecular weight distributions, improve vulcanization rate, make rubber have good processibility and package stability, cross-linked rubber has the mechanical property of superelevation and excellent low compression set.The method has continuously, the distinguishing feature of stable, efficient, energy-conservation, low-dimensional.
The percentage composition related in present specification unless otherwise indicated, all refers to weight percentage.
Embodiment
Followingly reach corresponding test by embodiment the invention will be further described.
Embodiment 1
Purge the nitrogen deoxygenation in the airtight polymerization reaction kettle that is 50L at two capacity, make in still oxygen level lower than 20ppm; Add the 30Kg deionized water, 300g ammonium perfluorocaprylate, 60g Sodium phosphate dibasic, 7.2Kg R 1216,16.8Kg vinylidene.Add diethyl malonate 20g in the A still, add iso-pentane 15g in the B still, open stirring rake, rotating speed is 350r/min, is warming up to 105 ℃; Squeeze into the 50g ammonium persulphate with volume pump in reactor A, squeeze into the initiation reaction of 130g beta-hydroxyethyl tert-butyl peroxide in reactor B, by medial launder, every now and then to reactor A, in B, additional mass is than being that 5/12 R 1216/vinylidene mixed gas take that to maintain reacting kettle inner pressure constant be 5.5MPa; Add initiator di-isopropyl peroxydicarbonate 100g in the backward reactor A of 50min; Interval 1.5h adds diethyl malonate 40g in reactor A, and interval 2.2h adds iso-pentane 140g in reactor B; React and by pressure controlled valve, the emulsion in reactor A, B is delivered in mixing kettle after 4.5 hours, speed ratio is 3/2, by the comonomer of premix in medial launder, by compressor, add continuously in reactor simultaneously, pre-assigned same isocyatic initiator, emulsifying agent, deionized water, pH adjusting agent are injected to reactor continuously by volume pump, keep the still internal pressure, homo(io)thermism; Emulsion in mixing kettle is condensed to rear washing, oven dry with magnesium chloride, through cold feeding machine formed package.Measure dispersed index (ratio of weight-average molecular weight and the number-average molecular weight) MWD=6.6 of this viton through GPC.
Embodiment 2
Purge the nitrogen deoxygenation in the airtight polymerization reaction kettle that is 50L at two capacity, make in still oxygen level lower than 20ppm; Add the 30Kg deionized water, 300g ammonium perfluorocaprylate, 60g Sodium phosphate dibasic, 9.2Kg R 1216,15.8Kg vinylidene.Add diethyl malonate 20g in the A still, add iso-pentane 15g in the B still, open stirring rake, rotating speed is 450r/min, is warming up to 105 ℃; Squeeze into the 90g ammonium persulphate with volume pump in reactor A, squeeze into the initiation reaction of 100g beta-hydroxyethyl tert-butyl peroxide in reactor B, by medial launder, every now and then to reactor A, in B, additional mass is than being that 6/10 R 1216/vinylidene mixed gas take that to maintain reacting kettle inner pressure constant be 6.0MPa; Add initiator di-isopropyl peroxydicarbonate 60g in the backward reactor A of 40min; Interval 1.5h adds diethyl malonate 55g in reactor A, and interval 2.0h adds iso-pentane 120g in reactor B; React and by pressure controlled valve, the emulsion in reactor A, B is delivered in mixing kettle after 4.5 hours, speed ratio is 3/2, by the comonomer of premix in medial launder, by compressor, add continuously in reactor simultaneously, pre-assigned same isocyatic initiator, emulsifying agent, deionized water, pH adjusting agent are injected to reactor continuously by volume pump, keep the still internal pressure, homo(io)thermism; Emulsion in mixing kettle is condensed to rear washing, oven dry with magnesium chloride, through cold feeding machine formed package.Measure the dispersed index M WD=4.4 of this viton through GPC.
Embodiment 3
Purge the nitrogen deoxygenation in the airtight polymerization reaction kettle that is 50L at two capacity, make in still oxygen level lower than 20ppm; Add the 30Kg deionized water, 300g ammonium perfluorocaprylate, 60g Sodium phosphate dibasic, 6.9Kg R 1216,21.1Kg vinylidene.Add diethyl malonate 20g in the A still, add iso-pentane 15g in the B still, open stirring rake, rotating speed is 550r/min, is warming up to 105 ℃; Squeeze into the 40g ammonium persulphate with volume pump in reactor A, squeeze into the initiation reaction of 150g beta-hydroxyethyl tert-butyl peroxide in reactor B, by medial launder, every now and then to reactor A, in B, additional mass is than being that 1/3 R 1216/vinylidene mixed gas take that to maintain reacting kettle inner pressure constant be 6.8MPa; Add initiator di-isopropyl peroxydicarbonate 105g in the backward reactor A of 45min; Interval 1.5h adds diethyl malonate 60g in reactor A, and interval 3.0h adds iso-pentane 130g in reactor B; React and by pressure controlled valve, the emulsion in reactor A, B is delivered in mixing kettle after 5.5 hours, speed ratio is 3/2, by the comonomer of premix in medial launder, by compressor, add continuously in reactor simultaneously, pre-assigned same isocyatic initiator, emulsifying agent, deionized water, pH adjusting agent are injected to reactor continuously by volume pump, keep the still internal pressure, homo(io)thermism; Emulsion in mixing kettle is condensed to rear washing, oven dry with magnesium chloride, through cold feeding machine formed package.Measure the dispersed index M WD=7.3 of this viton through GPC.
Embodiment 4
Purge the nitrogen deoxygenation in the airtight polymerization reaction kettle that is 50L at two capacity, make in still oxygen level lower than 20ppm; Add the 30Kg deionized water, 300g ammonium perfluorocaprylate, 60g Sodium phosphate dibasic, 8.2Kg R 1216,17.4Kg vinylidene.Add diethyl malonate 20g in the A still, add iso-pentane 15g in the B still, open stirring rake, rotating speed is 650r/min, is warming up to 105 ℃; Squeeze into the 120g ammonium persulphate with volume pump in reactor A, squeeze into the initiation reaction of 120g beta-hydroxyethyl tert-butyl peroxide in reactor B, by medial launder, every now and then to reactor A, in B, additional mass is than being that 1/2 R 1216/vinylidene mixed gas take that to maintain reacting kettle inner pressure constant be 5.5MPa; 2.0h add initiator di-isopropyl peroxydicarbonate 30g in backward reactor A; Interval 1.5h adds diethyl malonate 40g in reactor A, and interval 3.0h adds iso-pentane 130g in reactor B; React and by pressure controlled valve, the emulsion in reactor A, B is delivered in mixing kettle after 6 hours, speed ratio is 3/2, by the comonomer of premix in medial launder, by compressor, add continuously in reactor simultaneously, pre-assigned same isocyatic initiator, emulsifying agent, deionized water, pH adjusting agent are injected to reactor continuously by volume pump, keep the still internal pressure, homo(io)thermism; Emulsion in mixing kettle is condensed to rear washing, oven dry with magnesium chloride, through cold feeding machine formed package.Measure the dispersed index M WD=4.1 of this viton through GPC.
Embodiment 5
Purge the nitrogen deoxygenation in the airtight polymerization reaction kettle that is 50L at two capacity, make in still oxygen level lower than 20ppm; Add the 30Kg deionized water, 300g ammonium perfluorocaprylate, 60g Sodium phosphate dibasic, 7.7Kg R 1216,16.3Kg vinylidene.Add diethyl malonate 20g in the A still, add iso-pentane 15g in the B still, open stirring rake, rotating speed is 400r/min, is warming up to 95 ℃; Squeeze into the 70g ammonium persulphate with volume pump in reactor A, squeeze into the initiation reaction of 120g beta-hydroxyethyl tert-butyl peroxide in reactor B, by medial launder, every now and then to reactor A, in B, additional mass is than being that 7/15 R 1216/vinylidene mixed gas take that to maintain reacting kettle inner pressure constant be 6.0MPa; 1.8h add initiator di-isopropyl peroxydicarbonate 70g in backward reactor A; Interval 1.5h adds diethyl malonate 60g in reactor A, and interval 3.0h adds iso-pentane 155g in reactor B; React and by pressure controlled valve, the emulsion in reactor A, B is delivered in mixing kettle after 5.7 hours, speed ratio is 3/2, by the comonomer of premix in medial launder, by compressor, add continuously in reactor simultaneously, pre-assigned same isocyatic initiator, emulsifying agent, deionized water, pH adjusting agent are injected to reactor continuously by volume pump, keep the still internal pressure, homo(io)thermism; Emulsion in mixing kettle is condensed to rear washing, oven dry with magnesium chloride, through cold feeding machine formed package.Measure the dispersed index M WD=5.8 of this viton through GPC.
Embodiment 6
Be similar to the polymerization process of embodiment 1, difference is that the rotating speed of stirring rake is 600r/min, and temperature of reaction is 95 ℃, and the usage quantity of ammonium perfluorocaprylate is 400g.Measure the dispersed index M WD=7.3 of this viton through GPC.
Contrast 1
Be similar to the polymerization process of embodiment 2, difference only is in reactor A disposablely first to add a kind of initiator ammonium persulfate 150g.Measure the dispersed index M WD=3.1 of this viton through GPC.
Contrast 2
Be similar to the polymerization process of embodiment 3, difference only is in reactor A disposablely first to add a kind of initiator di-isopropyl peroxydicarbonate 105g.Measure the dispersed index M WD=3.5 of this viton through GPC.
Contrast 3
Be similar to the polymerization process of embodiment 4, difference is to add diethyl malonate 160g one time every 3.8h in reactor A.Measure the dispersed index M WD=3.3 of this viton through GPC.
Contrast 4
Be similar to the polymerization process of embodiment 5, difference is to add iso-pentane 190g one time every 3.5h in reactor B.Measure the dispersed index M WD=3.8 of this viton through GPC.
Claims (9)
1. the preparation method who has 26 type viton of wide molecular weight distribution, is characterized in that this viton has very wide molecular weight distribution, dispersed index M WD=7-15, and its preparation method comprises the following steps:
1) purge the nitrogen deoxygenation in two airtight polymerization reaction kettle A, B, add deionized water, emulsifying agent, pH adjusting agent and chain-transfer agent;
2) to adding respectively the R 1216 that weight ratio is 25-40:60-75 in two reactor A, B: vinylidene fluoride monomers, open and stir, to reaction pressure be 3.0 – 7.0MPa, heating up and making temperature of reaction is 120 ℃ of 65 –;
3) in two reactor A, B, add respectively initiator 1 and 2 to start reaction, the R 1216 that is simultaneously 1/3～3/5 by the mass ratio of premix in medial launder/vinylidene mixed gas is added in reactor A, B continuously by compressor, makes the still internal pressure keep constant; Add initiator 3 in reaction 30-60min backward reactor A, after added chain-transfer agent every 1.0-3.0 hour in reactor A, B; Initiator 1 is ammonium persulphate, and initiator 3 is di-isopropyl peroxydicarbonate, and initiator 2 is the beta-hydroxyethyl tert-butyl peroxide;
4) reaction was delivered to the emulsion in two reactor A, B in mixing kettle by pressure controlled valve after 4-7 hour, the mixed gas of premix in medial launder is added in reactor A, B continuously by compressor simultaneously, pre-assigned same isocyatic initiator, emulsifying agent, deionized water, pH adjusting agent are injected to reactor A, B continuously by volume pump, keep the still internal pressure, homo(io)thermism, enter next reaction time;
5) emulsion in mixing kettle is condensed to rear washing, oven dry with magnesium chloride, through cold feeding machine formed package.
2. the preparation method with 26 type viton of wide molecular weight distribution as claimed in claim 1, the weight part that it is characterized in that emulsifying agent in the deionized water of every 100 weight parts is 0.1-5.0, the weight part of initiator is 0.001-3.2, the weight part of pH adjusting agent is 0.05-0.68, the weight part of chain-transfer agent is 0.0005-1.5, and the weight part of monomer is 70-100.
3. the preparation method with 26 type viton of wide molecular weight distribution as claimed in claim 1, is characterized in that the weight part of emulsifying agent in the deionized water of every 100 weight parts is 0.5-3; The weight part of initiator is 0.1-2.5, and the weight part of pH adjusting agent is 0.2-0.5, and the weight part of chain-transfer agent is 0.01-1.0, and the weight part of monomer is 80-90.
4. the preparation method with 26 type viton of wide molecular weight distribution as claimed in claim 1, is characterized in that polymerization stirring velocity used is 300-800r/min, and polymerization reaction pressure used is 3.0 – 7.0Mpa, and temperature of reaction is 120 ℃ of 65 –.
5. the preparation method with 26 type viton of wide molecular weight distribution as claimed in claim 1, is characterized in that polymerization stirring velocity used is 400-700r/min, and polymerization reaction pressure used is 3.5 – 6.5Mpa, and temperature of reaction is 100 ℃ of 75 –.
6. the preparation method with 26 type viton of wide molecular weight distribution as claimed in claim 1, is characterized in that described emulsifying agent is ammonium perfluorocaprylate, and described pH adjusting agent is Sodium phosphate dibasic; Described chain-transfer agent: in reactor A, being diethyl malonate, is iso-pentane in reactor B.
7. the preparation method with 26 type viton of wide molecular weight distribution as claimed in claim 1, it is characterized in that described viton adopts the semi continuous method preparation of letex polymerization, add chain-transfer agent every 1-3h 1 time in two reactor A, B, every 7-9 hour, the emulsion in mixing kettle is once condensed.
8. the preparation method with 26 type viton of wide molecular weight distribution as claimed in claim 1, is characterized in that reactor A and reactor B are 4/3～5/3 to the speed ratio of discharging in mixing kettle.
9. the preparation method with 26 type viton of wide molecular weight distribution as claimed in claim 1, it is characterized in that the R 1216 added respectively in two reactor A, B: the vinylidene weight ratio is 30-35:65-70.
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