Novel multifunctional initiators for anionic polymerization and polymers therefrom

a multifunctional, anionic polymerization technology, applied in the field of compounds, can solve the problems of low initiator concentration, bi-modal initiation, pre-reaction steps to synthesize,

Inactive Publication Date: 2009-12-31
BRIDGESTONE CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0024]where x is 1 or more, R3, R4 and R5 are the same or different and represent alkylene groups containing from 3 to 20 carbon atoms.

Problems solved by technology

However, this DiLi system requires polar additive triethylamine (Et3N) as solvent to prevent the aggregation of 1,3-diisopropenylbenzene, and combine with sec-butyl lithium, the major drawbacks of which are that it requires pre-reaction steps to synthesize the initiator, low initiator concentration, bi-modal initiation, and difficulty to make the low vinyl polybutadiene polymers.
Therefore, although alkali metal, mono-functional initiators such as alkyl lithium and lithium amides are known, and DiLi systems are known, multifunctional lithiated amine-containing initiators are not well known.

Method used

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  • Novel multifunctional initiators for anionic polymerization and polymers therefrom
  • Novel multifunctional initiators for anionic polymerization and polymers therefrom
  • Novel multifunctional initiators for anionic polymerization and polymers therefrom

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0089]To a dried 28-oz glass bottle was added 83.3 g of hexane, and 166.7 g of 18.0 wt % butadiene in hexane, followed 0.34 ml of 4,4′-trimethylenedipiperidine solution (1.0 M in toluene) and 0.47 ml of n-BuLi (1.60M) in hexane by hypodermic syringe. The bottle was agitated and heated at 50° C. for 1.5 hr. After polymerization, the living cement was quenched by injection with 1.5 ml of isopropanol (1-PrOH), treated with an antioxidant (3 ml of 2 wt % di-t-butyl-p-cresol in hexane), coagulated in i-PrOH, then vacuum dried. Characterizations were performed, and the result was listed in Table 1, wherein Bd means butadiene; 1,2-Bd %, cis % of 1,4-Bd and trans of 1,4-Bd are analyzed by FT-IR; Mn means number average molecular weight; Mw means weight average molecular weight; Mp means peak molecular weight; PDI means polydispersity index (Mw / Mn); Tg means glass transition temperature. The molecule weight of the polymer in the example was determined by using a Waters Model 150-C GPC.

TABLE ...

example 2

[0090]The experimental in example 1 was repeated, however, with varied amount of randomizer of 2-bis(2′-tetrahydrofuranyl)propane (OOPS) and the effect of randomizer of 2-bis(2′-tetrahydrofuranyl)propane on polymer Tg (° C.) was listed in Table 2.

TABLE 2OOPS:“Li” (molar ratio)Tg (° C.)0.00−94.230.15−46.520.25−39.240.35−33.89

example 3

[0091]To a dried 28-oz glass bottle was added 91.7 g of hexane, and 208.3 g of 21.6 wt % butadiene in hexane, followed 0.61 ml of tris[2-(methylamino)ethyl]amine solution (1.0 M in toluene), 1.4 ml of N,N,N′,N′-tetramethylethylenediamine (1.0M in hexane), and 1.15 ml of n-BuLi (1.60M) in hexane by hypodermic syringe. The bottle was agitated and heated at 50° C. for 1.5 hr. After polymerization, the living cement was quenched by injection with 1.5 ml of isopropanol (i-PrOH), treated with an antioxidant (3 ml of 2 wt % di-t-butyl-p-cresol in hexane), coagulated in i-PrOH, then vacuum dried. Characterizations were performed, and the result was listed in Table 3.

TABLE 3MnMwMpCouplingID(g / mol)(g / mol)(g / mol)PDI(%)Tg (° C.)Example 36985872166738561.0330−28.84

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Abstract

The embodiments of the invention relate to a multifunctional lithiated amine-containing compound comprising at least two molecules of lithiated amine in a molecule of the compound. In one embodiment, the compound has a formula
where x is an integer of 1 or more, Q is (a) an element selected from the group consisting of O, S, N, P and Si or (b) an alkylene group having from 1 to 20 methylene groups, and R1 and R2 are the same or different and are selected from the group consisting of alkyls, cycloalkyls and aralkyls containing from 1 to 20 carbon atoms. In another embodiment, the compound comprises cyclic lithio amines and has a formula:
    • where x is 1 or more, R3, R4 and R5 are the same or different and represent alkylene groups containing from 3 to 20 carbon atoms.

Description

RELATED APPLICATION[0001]This application claims priority from U.S. Provisional Patent Application Ser. No. 61 / 017,189, filed Dec. 28, 2007 which is incorporated herein by reference.FIELD OF INVENTION[0002]The embodiments of the invention relate to compounds that are useful as anionic polymerization initiators, and polymers therefrom.BACKGROUND[0003]Anionic polymerization techniques have been used to synthesize polymers that are useful in the manufacture of polymers, including rubbers. Certain initiators impart a functional group to the polymers, and these functional groups are believed to have a beneficial impact on the performance of polymers.[0004]One type of anionic polymerization is anionic living polymerization. This form of polymerization is called “living” or “controlled polymerization” as the ability of a growing polymer chain to terminate has been removed. The result is that the polymer chains grow at a more constant rate than seen in traditional chain polymerization and t...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C08F4/48C07F1/02C08G73/00
CPCB60C1/00C07C211/65C08C19/44C08F4/488C08F36/06C08L9/06C08G73/0213
Inventor YAN, YUAN-YONG
Owner BRIDGESTONE CORP
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