CS231023B1 - Method of selective polymerization of butadiene from c4 fraction - Google Patents
Method of selective polymerization of butadiene from c4 fraction Download PDFInfo
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- CS231023B1 CS231023B1 CS573482A CS573482A CS231023B1 CS 231023 B1 CS231023 B1 CS 231023B1 CS 573482 A CS573482 A CS 573482A CS 573482 A CS573482 A CS 573482A CS 231023 B1 CS231023 B1 CS 231023B1
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- CS
- Czechoslovakia
- Prior art keywords
- polymerization
- butadiene
- fraction
- alpha
- methylstyrene
- Prior art date
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims description 17
- 238000006116 polymerization reaction Methods 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- PNHIJJOZOUVMNU-UHFFFAOYSA-N prop-1-en-2-ylbenzene;sodium Chemical compound [Na].[Na].CC(=C)C1=CC=CC=C1 PNHIJJOZOUVMNU-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- -1 e.g. Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920006250 telechelic polymer Polymers 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
hmotností v rozsahu od 1 000 do 250 000 v homogenní kapalné fázi v přítomnosti alkalokovových organických iniciátorů» zejména na bázi sodíku, podle vynálezu, který spočívá v tom, Že se jako iniciátor použije dinatrium-alfa-metylstyrenový tetramer. Polymeraci lze s výhodou provádět v kapalné fázi v rozsahu teplot 198 až 303 K, zejména pak při 223 až 273 K. Polymeraci lze rovněž provádět v přítomnosti aniontové kopolymerovatelného monomeru, s výhodou akrylonitrilu, styrenu, alfa-metylstyrenu, izoprenu, nebo metylmetakrylátu. V tomto případě kopolymerace lze získávat blokové kopolymery butadienu typu A-B-A, jakož i kopolymery se statistickým rozdělením monomerů. Telechelické homopolymery a kopolymery butadienu mají funkcionalitu blížící se Číslu 2. Molekulární hmotnost polymeru lze nastavit v potřebném rozsahu. Polymerace může probíhat buí ve hmotě a/nebo s přídavkem nepolárních rozpouštědel, zejména benzenu, toluenu, n-hexanu, n-heptanu, cyklohexanu nebo benzinových frakcí. Výhodnějěí vSak je pracovat bez přídavku těchto rozpouštědel, přičemž jako ředidla působí pouze ostatní uhlovodíky z frakce. V důsledku požadavku, aby polymerace probíhala v kapalné fázi, je možno pracovat bud za atmosférického nebo zvýšeného tlaku. Doba polymerace je zpravidla 1 až 3 h. Jelikož se jedná o stechiometrickou polymeraci, určuje obsah iniciátoru požadovanou molekulovou hmotnost.% by weight in the range from 1,000 to 250,000 in a homogeneous liquid phase in the presence of alkali metal organic initiators, in particular sodium-based, according to the invention, characterized in that disodium-alpha-methylstyrene tetramer is used as initiator. The polymerization can advantageously be carried out in the liquid phase at temperatures of from 198 to 303 K, in particular at 223 to 273 K. The polymerization can also be carried out in the presence of an anionic copolymerizable monomer, preferably acrylonitrile, styrene, alpha-methylstyrene, isoprene, or methyl methacrylate. In this case of copolymerization, butadiene block copolymers of type A-B-A can be obtained, as well as copolymers with a random monomer distribution. Telechelic homopolymers and copolymers of butadiene have a functionality close to that of Number 2. The molecular weight of the polymer can be adjusted to the desired extent. The polymerization can be carried out either in bulk and / or with the addition of non-polar solvents, in particular benzene, toluene, n-hexane, n-heptane, cyclohexane or gasoline fractions. However, it is preferable to work without the addition of these solvents, with only other hydrocarbons from the fraction acting as diluents. Due to the requirement that the polymerization be carried out in the liquid phase, either atmospheric or elevated pressure can be used. The polymerization time is generally 1 to 3 hours. Since it is a stoichiometric polymerization, the initiator content determines the desired molecular weight.
Aktivní konce řetězců výsledného živého polymeru lze funkcionalizovat známým způsobem elektrofilními činidly pro vytváření funkčních skupin, např. oxidem uhličitým, alkylenoxidy, nebo epichlorhydrinem. Vznikají tak telechelické polymery.The active chain ends of the resulting living polymer can be functionalized in a known manner by electrophilic functional grouping agents, e.g., carbon dioxide, alkylene oxides, or epichlorohydrin. Telechelic polymers are formed.
Produkty získané způsobem podle vynálezu mají stejné vlastnosti jako polymery získané při polymeraci čistého butadienu. Je proto výhodou způsobu podle vynálezu, že se tyto polymery dají připravit, aniž je třeba předem provádět izolaci butadienu z frakce, čímž se uspoří výrobní náklady. Ostatní uhlovodíky v frakci zůstanou po polymeraci к dispozici pro dalěí využití.The products obtained by the process according to the invention have the same properties as the polymers obtained in the polymerization of pure butadiene. It is therefore an advantage of the process according to the invention that these polymers can be prepared without the need to pre-isolate butadiene from the fraction, thereby saving production costs. The other hydrocarbons in the fraction will remain available for further use after polymerization.
U způsobu podle vynálezu lze dosáhnout vysokého podílu struktury 1,2,polymeruje-li se v přítomnosti polárních sloučenin jako donorů elektronů.In the process according to the invention, a high proportion of structure 1,2 can be achieved when polymerized in the presence of polar compounds as electron donors.
Dále uváděné příklady objasňují způsob provedení vynálezu.The following examples illustrate the method of carrying out the invention.
Přikladl mmol dinatrium-alfa-metylstyrenového tetrameru, rozpuštěného v 355 ml tetrahydrofuranu, bylo vloženo do skleněného autoklávu a po dobu 1 hodiny se к němu přidávalo 172 g frakce, která obsahovala 43,6 hmotnostních % 1,3-butadienu. Polymerace probíhala za teploty 243 K. Potom se reakční směs míchala ještě 1 hodinu, načež se polymerace přerušila metanolem. Separovaly se nezřeagované uhlovodíky a vytvořený polybutadien se separoval oo odstranění vody na vakuové rotační odparce při 323 K. Při 100 % výtěžku se získal kapalný polybutadien o střední molekulové hmotnosti 2 050. Polymer měl mikrbstrukturu 81 molárních %Example 1 mmol of disodium-alpha-methylstyrene tetramer, dissolved in 355 ml of tetrahydrofuran, was placed in a glass autoclave and 172 g of a fraction containing 43.6% by weight of 1,3-butadiene was added over 1 hour. The polymerization was carried out at a temperature of 243 K. Thereafter, the reaction mixture was stirred for 1 hour, after which the polymerization was interrupted with methanol. Unreacted hydrocarbons separated and the polybutadiene formed was separated to remove water on a vacuum rotary evaporator at 323 K. At 100% yield, liquid polybutadiene with an average molecular weight of 2050 was obtained. The polymer had a microstructure of 81 molar%
1,2 a 19 molárních % 1,4 jednotek..1.2 and 19 mole% 1.4 units.
Příklad 2Example 2
К 50 mmol dinatrium-alfa-metylstyrenového tetrameru, rozpuštěného v 237 ml tetrahydrofuranu, se za obdobných podmínek jako v příkladu 1 přidávalo v průběhu 2 hodin 114.5 a frakce, která obsahovala 43,6 hmotnostních % 1,3 butadienu, který se přidával kontinuálně při 223 K. Po skončení polymerace se к homogennímu roztoku přidalo 6,6 g etylenoxidu, načež se provedla hydrolýze vodou. Získalo se 49 g kapalného polybutadienu, který měl na každém konci řetězce primární skupinu -OH. Relativní střední molekulová hmotnost, stanovená osmometricky byla 2 090, vypočtená 2 000. Produkt měl obsah hydroxylů 1,47%, z čehož vyplývá funkcionalita 1,81.50 50 mmol of disodium-alpha-methylstyrene tetramer dissolved in 237 ml of tetrahydrofuran was added over 2 hours to 114.5 and a fraction containing 43.6% by weight of 1,3 butadiene, which was added continuously at 223 K. At the end of the polymerization, 6.6 g of ethylene oxide were added to the homogeneous solution, followed by hydrolysis with water. 49 g of liquid polybutadiene having primary -OH group at each end of the chain was obtained. The relative average molecular weight, determined osmometrically was 2,090, calculated as 2,000. The product had a hydroxyl content of 1.47%, resulting in a functionality of 1.81.
P . ř í k 1 a d 3P. 1 and d 3
Polymerace probíhala stejně jako v příkladu 2, s tím rozdílem, že se současně s Сд frakcí přidávalo i 16,7 g styrenu, rozpuštěného v 200 ml toluenu. Po stejném zpracování sa získal kopolymer butadienu se . styrenem se 100% výtěžkem, přičemž produkt měl obsah styrenu 35 %.The polymerization was carried out as in Example 2, except that 16.7 g of styrene dissolved in 200 ml of toluene were added simultaneously with the Cd fraction. After the same treatment, butadiene copolymer was obtained. styrene in 100% yield, the product having a styrene content of 35%.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD23271481A DD200326A1 (en) | 1981-08-21 | 1981-08-21 | METHOD FOR SELECTIVE BUTADIA POLYMERIZATION FROM C LOW 4 FRACTIONS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS231023B1 true CS231023B1 (en) | 1984-09-17 |
Family
ID=5533073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS573482A CS231023B1 (en) | 1981-08-21 | 1982-07-30 | Method of selective polymerization of butadiene from c4 fraction |
Country Status (2)
| Country | Link |
|---|---|
| CS (1) | CS231023B1 (en) |
| DD (1) | DD200326A1 (en) |
-
1981
- 1981-08-21 DD DD23271481A patent/DD200326A1/en not_active IP Right Cessation
-
1982
- 1982-07-30 CS CS573482A patent/CS231023B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DD200326A1 (en) | 1983-04-13 |
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