CN104098719B - Terminating method in a kind of reactive polymer still preventing generation gel in still - Google Patents
Terminating method in a kind of reactive polymer still preventing generation gel in still Download PDFInfo
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- CN104098719B CN104098719B CN201310121411.1A CN201310121411A CN104098719B CN 104098719 B CN104098719 B CN 104098719B CN 201310121411 A CN201310121411 A CN 201310121411A CN 104098719 B CN104098719 B CN 104098719B
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Abstract
The invention discloses terminating method in a kind of reactive polymer still preventing from producing in still gel, the method to add in alcohols, phenols or carboxylic-acid one or more in the reactor completed at active anionic polymerization as terminator, at 10 ~ 80 DEG C, termination reaction 0.1 ~ 20min; It is fast that the method stops speed, and stop Be very effective, accurately can control molecular weight, starting material are easy to get, and can prevent from producing gel in still.
Description
Technical field
The invention discloses terminating method in a kind of reactive polymer still preventing from producing in still gel, belong to Polymer Synthesizing field.
Background technology
The polymerization of conjugated diene or vinyl-arene or copolymerization belong to the anionoid polymerization making initiator with organic alkali metal mostly.The feature of anionoid polymerization is: monomer is once be initiated, and transfer reaction will begin in a minute, and forms ion pair, monomer constantly inserts in ion pair, if do not have terminator to be stopped, as long as there is monomer to exist, transfer reaction will go on always, until all monomers all run out of.In order to control suitable molecular weight, terminator just must be taked transfer reaction to be stopped.Stop having again in still and stop stopping two kinds outward with still, the outer termination of still does not need to consider the impact of terminator on next batch of material polymerization in polymeric kettle, generally can adopt the alcohol etc. of water and band reactive hydrogen.Use water as the outer terminator of still, not only economy but also environmental protection.But still stops outward a small amount of reactive polymer remained in after discharging in polymeric kettle to be stopped, when carrying out polymerization or the copolymerization of next still, as long as add monomer in polymeric kettle, these reactive polymers will participate in the polyreaction newly adding monomer, so continue, form extremely macromolecular polymkeric substance, namely gel.Gel is difficult to dissolve in conventional solvent, and hot workability is poor, and still can exist with the form of solid granule in general hot procedure, cause fabricated product poor surface smoothness, goods inside exists flaw.
CN9110350.6 describes and in appropriate solvent, with anionic polymerization initiator, monovalent anion is polymerized and forms polymkeric substance, and make it stop, comprising adding terminator, polymerization is stopped, terminator adopts hydrogen or its isotropic substance, borine, ammonia, halogen, containing O-H base and the hydrocarbon be directly connected on triple bond or two double key carbons and silane, preferred hydrogen, as terminator, adopts alcohol to make terminator and can disturb down batch molecular weight control that polymerization is expected.
CN01816364.5 discloses and a kind ofly prepares the vinyl-arene of selective hydrogenation and the method for conjugated diene block copolymer.Wherein be referred to and stop living chain terminal by the one in alcohol, hydrogen and composition thereof, wherein: (I) is if stop polymkeric substance with alcohol, and this alcohol is straight chain alcohol, then with alcohol: living chain terminal mol ratio is that the amount of 0.05-1.2 is to stop living chain terminal; (II) is if stop polymkeric substance with alcohol, and this alcohol is branched-chain alcoho, then with alcohol: the mol ratio of living chain terminal is that the amount of 0.05-3.0 is to stop living chain terminal; (III) is if stop polymkeric substance with alcohol, and this alcohol is the mixture of straight chain alcohol and branched-chain alcoho, then with straight chain alcohol: the mol ratio of living chain terminal is that the amount of 0.05-1.2 is to stop living chain terminal.Add the catalyzer prepared with carboxylic acid cobalt and aluminum alkyls after termination again and carry out selective hydrogenation, prepare hydropolymer.
CN96118387.X discloses a kind of styrene-butadiene block copolymer and preparation method thereof.Adopt Multistep feeding method stage feeding polymerization, and add terminator or coupling agent in latter stage.Obtained line style or star-shaped sbs respectively, solves the problems such as styrene content in multipolymer is high, for the preparation of tackiness agent or pressure sensitive adhesive.Terminator used is water or ethanol, adds when discharging, and terminating method belongs to still and stops outward.
CN92114489X is the improvement to conjugated diolefin polymer method of hydrotreating, after synthesizing a kind of reactive polymer, polymerization is stopped by adding hydrogen, take this to generate a kind of alkalimetal hydride, when there is no its lithium of hydrocarbon and alkoxyl group lithium, add two (cyclopentadienyl) titanium compound of at least one and carry out selective hydrogenation, prepare hydropolymer.
CN92110490.1 provides a kind of hydrogenation of conjugated diolefin polymer to improve one's methods, and after composite reactive polymkeric substance, adds hydrogen and stops polymerization, then carry out hydrogenation, when hydrogenation with phenylformic acid alkyl ester as promotor, obtain hydropolymer.
Stop material to shift out polymeric kettle described in CN01816364.5, CN92114489X, CN92110490.1 to enter in hydrogenator and carry out, be not carry out in polymerization reactor, therefore can not affect the polyreaction of lower batch of material.
Summary of the invention
The present invention is directed to the termination of living polymerization in prior art all to stop outward at still, very easily gel is produced in polymeric kettle, the defect of the production of the lower batch of material of impact, it is fast that object is to provide a kind of termination speed, stop Be very effective, accurately can control molecular weight, what starting material were easy to get prevents terminating method in the interior reactive polymer still producing gel of still, and the method can effectively reduce polymerization cost.
The invention provides terminating method in a kind of reactive polymer still preventing from producing in still gel, the method to add in alcohols, phenols or carboxylic-acid one or more in the reactor completed at active anionic polymerization as terminator, at 10 ~ 80 DEG C, termination reaction 0.1 ~ 20min;
When alcohols selected separately by described terminator, the mol ratio of the living chain terminal in alcohol and reactive polymer is 0.1 ~ 2.0:1; During independent selection phenols, the mol ratio of phenolic hydroxyl group and active chain end is 0.5 ~ 2.0:1; During independent selection carboxylic-acid, the mol ratio of carboxyl and active chain end is 0.5 ~ 2.0:1; When selecting two or more mixing terminator in alcohols, phenols or carboxylic-acid, hydroxyl+phenolic group+carboxyl in terminator: the mol ratio of active chain end is 0.5 ~ 2.0:1;
Described alcohols is for comprising C
1~ C
8primary alconol, 2-methyl-2-propanol, in 2-methyl-2-butanols or 3,7-dimethyl-3-octanol one or more; Described phenols comprises one or more in 2,6-bis--t-butyl-4-methylphenol, 2,4,6-tri-butyl-phenols or 1,3,5-trimethylammonium-2,4,6-(3,5-di-t-butyl-4-hydroxyphenylmethyl) benzene; Described acids comprises formic acid, branched C
5~ C
20one or more in carboxylic acid, phenylformic acid or phthalic acid;
The solvent that polymerization adopts comprises one or more in hexane, cyclohexane or C6 oil.
Preferred terminator comprises: C
1~ C
8primary alconol, 2-methyl-2-propanol, 2-methyl-2-butanols, 3,7-dimethyl-3-octanols, 2,6-bis--t-butyl-4-methylphenols, 2,4,6-tri-butyl-phenol, 1,3,5-trimethylammonium-2,4,6-(3,5-di-t-butyl-4-hydroxyphenylmethyl) benzene, formic acid, branched C
5~ C
20one or both or three kinds in carboxylic acid, phenylformic acid or phthalic acid.
Preferred C
1~ C
8primary alconol comprise methyl alcohol, ethanol, n-propyl alcohol, n-butanols, n-amylalcohol, isooctyl alcohol, 2-propyl group-1-amylalcohol and 2,2-dimethyl-1-propyl alcohol.
Preferred branched C
5~ C
20carboxylic acid comprises isocaprylic acid and tertiary capric acid.
When alcohols selected separately by described terminator, the mol ratio of the living chain terminal in alcohol and reactive polymer is preferably 0.95 ~ 1.10:1; During independent selection phenols, the mol ratio of phenolic hydroxyl group and active chain end is preferably 0.9 ~ 1.1:1; During independent selection carboxylic-acid, the mol ratio of carboxyl and active chain end is preferably 1.1 ~ 1.3:1; When selecting two or more mixing in alcohols, phenols or carboxylic-acid, hydroxyl+phenolic group+carboxyl in terminator: the mol ratio of active chain end is preferably 0.9 ~ 1.3:1.
Termination reaction of the present invention carrys out Indicator Reaction according to the change of reaction solution color usually, and be such as orange with the reactive polymer that butyllithium causes, color disappears the indicator signal that can be terminated as reactive polymer.
Termination reaction of the present invention is directly contacted with terminator by reactive polymer in polymeric kettle and polymkeric substance after must stopping; Gaseous state terminator, ensures that gaseous state terminator fully contacts with reactive polymer; Liquid terminator directly can add in polymeric kettle or with after appropriate solvent dilution with liquid state when adding reactive polymer and add; Solid-state terminator adds polymeric kettle and directly can add solid terminator or add by dissolution with solvents form slurry or be made into terminator solution with appropriate solvent and add.
Beneficial effect of the present invention: traditional termination nearly all adopts still to stop outward, the condition that still stops outward does not have to stop harshness in still, but the outer termination of still always has a small amount of active residue residual in still, the polymerization participating in lower batch of polymerization material very easily produces gel, the generation of gel not only needs timing to take the cleaning that equipment carries out gel apart, work consuming, consumption manpower, also having partial gel enters in final polymeric articles with glue, because gel is insoluble in common solvent, at high temperature also not melting, therefore with the polymeric articles of gel when being processed into other goods, gel can become small-particle to remain in product surface with inner, make product surface smooth finish poor, intrinsic strength declines, have a strong impact on the quality of goods.Stop in still of the prior art can not being called in real still and stop, generally reactive polymer need be moved in polymeric kettle hydrogenator and carry out termination reaction with alcohol or hydrogen again.Product after stopping with hydrogen to coordinate with hydrogenation catalyst as hydrogenating reduction agent and carries out hydrogenation reaction; Need separately to add reductive agent after stopping with alcohol to pass into hydrogen again and add hydrogenation catalyst and carry out hydrogenation reaction; Its termination is not carry out in polymeric kettle, therefore always has a small amount of active residue in polymeric kettle, and the polymerization that these active residue participate in lower batch of material generates gel, can't resolve the defect easily producing gel in still all the time.The present invention screens through great many of experiments, optimize polymer solvent and the terminator of best of breed, the terminator selected in the inventive method has certain solvability at selected polymer solvent, ensure that terminator fully disperses at short notice in active polymers solution, prevent the too low or too high of terminator partial concn in the polymer, and cause coupling; The boiling point difference of the polymer solvent simultaneously selected and terminator wants large, when excessive terminator remains in polymer solvent, avoids forming azeotrope with polymer solvent, or close with polymer solvent boiling point, is difficult to the problem removing residual terminator by distillation mode; In addition, selected terminator activity is higher, can effectively Quick stop reactive polymer and inactivation activities residue, very effective to suppressing the generation of gel in still, and accurately can control molecular weight, generation side reaction is few, terminator range of choice is wide, really achieve the interior termination of still of reactive polymer, can be time saving and energy saving, save polymerization cost.
Embodiment
Following examples illustrate the present invention, instead of restriction scope of invention.
In the embodiment of the present invention, stop effect and judge according to the disappearance of reactive polymer color; The mensuration of gel content: after sample is dissolved for some time in toluene, filters with G5 sintered glass filter, and staying aperture is that insolubles on 125 μm of strainers is gel, then press SH/T1050-91 mensuration; The molecular weight gel permeation chromatograph external standard method of polymkeric substance is tested.
Embodiment 1 ~ 5 is adopted alcohols and is made terminator.Embodiment 6 ~ 9 adopts phenols to make terminator, and embodiment 10 ~ 15 adopts carboxylic-acid to make terminator.Embodiment 16 adopts alcohol and phenol to combine and makes terminator, and embodiment 17 adopts phenol and carboxylic acid composition to make terminator, and embodiment 18 adopts alcohol and carboxylic acid composition to make terminator.
Embodiment 1
In the polymeric kettle of clean band magnetic agitation, use cyclohexane give polymer solvent, adopt Multistep feeding method synthesizing styrene-isoprene styrene reactive polymer (Multistep feeding method is that the those of ordinary skill in anionoid polymerization field is known), observe active polymers solution in yellow, polyreaction completes and adds terminator termination living chain immediately, terminator methyl alcohol: active chain end=1.05:1(mol ratio, following ratio is mol ratio), maintain the temperature at 10 ~ 80 DEG C, stir 0.1 ~ 20min, polymers soln water white transparency is observed after stopping, illustrate and stopped.It is 10.9 ten thousand that the number-average molecular weight of polymkeric substance is surveyed in sampling, with design molecular weight 10.7 ten thousand closely.Released from polymeric kettle by glue, add oxidation inhibitor and stir, desolventizing dehydration obtains the finished product.Drop into lower batch solvent and monomer and other material again, after repeating above-mentioned process of the test 100 times, sample survey gel content wherein when plastic emitting, because gel content is too low, inspection does not measure.Polymeric kettle is opened and observes still wall, stir shaft and agitating vane, all do not find gel.
Embodiment 2 ~ 4
Change terminator into isooctyl alcohol respectively, 2-methyl-2-propanol, 3,7-dimethyl-3-octanols, repeat the step synthesizing styrene-butadiene-styrene reactive polymer of embodiment 1.The number-average molecular weight of polymkeric substance is about 11.0 ten thousand, with design molecular weight 10.7 ten thousand closely.After testing 100 times, do not detect gel.Polymeric kettle is opened and observes still wall, stir shaft and agitating vane, all do not find gel.
Embodiment 5
Terminator adopts methyl alcohol and 3,7-dimethyl-3-octanol combines, wherein methyl alcohol: 3,7-dimethyl-3-octanol=1:1, add-on is total hydroxyl of the hydroxyl in methyl alcohol and the hydroxyl sum in 3,7-dimethyl-3-octanol: active chain end=1.1:1(mol ratio) repeat the step of embodiment 1.The number-average molecular weight of polymkeric substance is 11.0 ten thousand, with design molecular weight 10.7 ten thousand closely.After testing 100 times, do not detect gel.Polymeric kettle is opened and observes still wall, stir shaft and agitating vane, all do not find gel.
Embodiment 6 ~ 9
Terminator adopts 2,6-bis--t-butyl-4-methylphenol respectively, and 2,4,6-tri-butyl-phenol, 1,3,5-trimethylammonium-2,4,6-(3,5-di-t-butyl-4-hydroxyphenylmethyl) benzene, 2,6-bis--t-butyl-4-methylphenol and 1,3,5-trimethylammonium-2,4,6-(3,5-di-t-butyl-4-hydroxyphenylmethyl) benzene combines, and add-on is total phenolic group: active chain end=1.2:1(mol ratio) repeat the step of embodiment 1.The number-average molecular weight of polymkeric substance all about 10.7 ten thousand, with design molecular weight 10.7 ten thousand closely.After testing 100 times, do not detect gel.Polymeric kettle is opened and observes still wall, stir shaft and agitating vane, all do not find gel.
Embodiment 10 ~ 15
Terminator adopts formic acid respectively, tertiary capric acid, formic acid and isocaprylic acid combine (wherein formic acid: isocaprylic acid=1:1), phenylformic acid, phthalic acid, formic acid and phenylformic acid combine (formic acid: phenylformic acid=1:1), and add-on is total carboxyl: active chain end=1.3:1(mol ratio) repeat the step of embodiment 1.The number-average molecular weight of polymkeric substance all about 10.7 ten thousand, with design molecular weight 10.7 ten thousand closely.After testing 100 times, do not detect gel.Polymeric kettle is opened and observes still wall, stir shaft and agitating vane, all do not find gel.
Embodiment 16
Adopt methyl alcohol and 2,4,6-tri-butyl-phenol to combine and make terminator, wherein methyl alcohol: 2,4,6-tri-butyl-phenol=1:1, hydroxyl+phenolic group is 1.3:1 with the ratio of active chain end, repeats the step of embodiment 1.The number-average molecular weight of polymkeric substance all about 10.7 ten thousand, with design molecular weight 10.7 ten thousand closely.After testing 100 times, do not detect gel.Polymeric kettle is opened and observes still wall, stir shaft and agitating vane, all do not find gel.
Embodiment 17
Adopt 1,3,5-trimethylammonium-2,4,6-(3,5-di-t-butyl-4-hydroxyphenylmethyl) benzene and tertiary capric acid combine makes terminator, wherein 1,3,5-trimethylammonium-2,4,6-(3,5-di-t-butyl-4-hydroxyphenylmethyl) benzene: tertiary capric acid=1:1, phenolic group+carboxyl is 1.2:1 with the ratio of active chain end, repeats the step of embodiment 1.The number-average molecular weight of polymkeric substance all about 10.7 ten thousand, with design molecular weight 10.7 ten thousand closely.After testing 100 times, do not detect gel.Polymeric kettle is opened and observes still wall, stir shaft and agitating vane, all do not find gel.
Embodiment 18
Adopt methyl alcohol and tertiary capric acid to combine and make terminator, wherein methyl alcohol; Tertiary capric acid=1:1, hydroxyl+carboxyl is 1.2:1 with the ratio of active chain end, repeats the step of embodiment 1.The number-average molecular weight of polymkeric substance all about 10.7 ten thousand, with design molecular weight 10.7 ten thousand closely.After testing 100 times, do not detect gel.Polymeric kettle is opened and observes still wall, stir shaft and agitating vane, all do not find gel.
Comparative example 1
In the polymeric kettle of clean band magnetic agitation, use cyclohexane give polymer solvent, adopt Multistep feeding method synthesizing styrene-isoprene styrene reactive polymer (Multistep feeding method is that the those of ordinary skill in anionoid polymerization field is known), after having reacted, glue is released from polymeric kettle, add deionized water and stop living chain outward at still, add oxidation inhibitor again to stir, desolventizing dehydration obtains the finished product, the number-average molecular weight that polymkeric substance is surveyed in sampling is 11.9 ten thousand, bigger than normal than design molecular weight 10.7 ten thousand.Drop into lower batch solvent and monomer and other material again, after repeating above-mentioned process of the test 100 times, sample survey gel content wherein when plastic emitting, gel content is 0.2g/100g product.Polymeric kettle opened observation, finds on stir shaft, enter material mouth be all stained with gel on agitating vane and in still, gel is harder small-particle.
Comparative example 2
In the polymeric kettle of clean band magnetic agitation, use cyclohexane give polymer solvent, add isoprene and THF, butyllithium, at 40 ~ 120 DEG C, react 30 ~ 40min, after having reacted, glue is released from polymeric kettle, add deionized water and stop living chain outward at still, then add oxidation inhibitor and stir, desolventizing dehydration obtains the finished product, the number-average molecular weight that polymkeric substance is surveyed in sampling is 11.8 ten thousand, more higher than design molecular weight 10.7 ten thousand.Drop into lower batch solvent and monomer and other material again, after repeating above-mentioned process of the test 100 times, sample survey gel content wherein when plastic emitting, gel content is 0.1g/100g product.Opened by polymeric kettle and observe still wall, stir shaft and agitating vane, find on stir shaft, enter material mouth be all stained with gel on agitating vane and in still, gel is transparent jelly sample.
Claims (5)
1. one kind prevents terminating method in the interior reactive polymer still producing gel of still, it is characterized in that, one or more are added in alcohols, phenols or carboxylic-acid as terminator in the reactor that active anionic polymerization completes, at 10 ~ 80 DEG C, termination reaction 0.1 ~ 20min;
When alcohols selected separately by described terminator, the mol ratio of the living chain terminal in alcohol and reactive polymer is 0.1 ~ 2.0:1; During independent selection phenols, the mol ratio of phenolic hydroxyl group and active chain end is 0.5 ~ 2.0:1; During independent selection carboxylic-acid, the mol ratio of carboxyl and active chain end is 0.5 ~ 2.0:1; When selecting two or more mixing terminator in alcohols, phenols or carboxylic-acid, hydroxyl+phenolic group+carboxyl in terminator: the mol ratio of active chain end is 0.5 ~ 2.0:1;
Described alcohols is for comprising C
1~ C
8primary alconol, 2-methyl-2-propanol, in 2-methyl-2-butanols or 3,7-dimethyl-3-octanol one or more;
Described phenols comprises one or more in 2,6-bis--t-butyl-4-methylphenol, 2,4,6-tri-butyl-phenols or 1,3,5-trimethylammonium-2,4,6-(3,5-di-t-butyl-4-hydroxyphenylmethyl) benzene;
Described acids comprises formic acid, branched C
5~ C
20one or more in carboxylic acid, phenylformic acid or phthalic acid;
The solvent that polymerization adopts comprises one or more in hexane, hexanaphthene or C6 oil.
2. the method for claim 1, is characterized in that, described terminator comprises: C
1~ C
8primary alconol, 2-methyl-2-propanol, 2-methyl-2-butanols, 3,7-dimethyl-3-octanols, 2,6-bis--t-butyl-4-methylphenols, 2,4,6-tri-butyl-phenol, 1,3,5-trimethylammonium-2,4,6-(3,5-di-t-butyl-4-hydroxyphenylmethyl) benzene, formic acid, branched C
5~ C
20one or both or three kinds in carboxylic acid, phenylformic acid or phthalic acid.
3. method as claimed in claim 2, is characterized in that, described C
1~ C
8primary alconol comprise methyl alcohol, ethanol, n-propyl alcohol, n-butanols, n-amylalcohol, isooctyl alcohol, 2-propyl group-1-amylalcohol and 2,2-dimethyl-1-propyl alcohol.
4. the method for claim 1, is characterized in that, described branched C
5~ C
20carboxylic acid comprises isocaprylic acid and tertiary capric acid.
5. the method for claim 1, is characterized in that, when alcohols selected separately by described terminator, the mol ratio of the living chain terminal in alcohol and reactive polymer is 0.95 ~ 1.10:1; During independent selection phenols, the mol ratio of phenolic hydroxyl group and active chain end is 0.9 ~ 1.1:1; During independent selection carboxylic-acid, the mol ratio of carboxyl and active chain end is 1.1 ~ 1.3:1; When selecting two or more mixing in alcohols, phenols or carboxylic-acid, hydroxyl+phenolic group+carboxyl in terminator: the mol ratio of active chain end is 0.9 ~ 1.3:1.
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| CN101255203A (en) * | 2007-03-01 | 2008-09-03 | 中国石油化工股份有限公司 | Method for restraining gelatin during preparation of conjugated diolefin and monovinyl aromatic hydrocarbons random polymers |
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| JP2005060536A (en) * | 2003-08-13 | 2005-03-10 | Denki Kagaku Kogyo Kk | Manufacturing process of block copolymer |
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| CN101362808A (en) * | 2007-08-07 | 2009-02-11 | 株式会社普利司通 | Polyhydroxy compounds as polymerization quenching agents |
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