阅读说明：本技术 仿生合成橡胶 (Bionic synthetic rubber ) 是由 U.温德勒 M.马尔克 L-G-B.米勒 C.舒尔泽格罗诺弗 D.普鲁弗 J.沃特泽尔 于 2018-08-27 设计创作，主要内容包括：本发明涉及一种组合物,包含：(i)可交联的合成的顺式-1,4-聚二烯,其具有至少95％的顺式含量并且在末端位置具有官能团；和(ii)两亲性化合物。(The present invention relates to a composition comprising: (i) a crosslinkable synthetic cis-1, 4-polydiene having a cis content of at least 95% and having a functional group at a terminal position; and (ii) an amphiphilic compound.)

1. Composition of comprising

-a crosslinkable synthetic cis-1, 4-polydiene having a cis content of at least 95% and having a functional group in a terminal position,

-an amphiphilic compound.

2. The composition of claim 1, wherein the cis-1, 4-polydiene is cis-1, 4-polyisoprene or cis-1, 4-polybutadiene or a mixture of the two polymers; and/or wherein the synthetic cis-1, 4-polydiene is obtainable by polymerization in the presence of a coordination catalyst comprising a transition metal or a rare earth metal.

3. The composition according to claim 1 or 2, wherein the terminal functional group is a carboxyl or carboxylate group, a hydroxyl, an amine or ammonium group, an ester group or a cyano group.

4. Composition according to one of the preceding claims, in which the amphiphilic compound is a polar lipid; a protein; a fatty acid or fatty acid salt; a fatty acid derivative; surfactants or mixtures of at least two of these compounds.

5. Composition according to one of the preceding claims, in which the amphiphilic compound is present in the composition in an amount of up to 30% by weight.

6. Composition according to one of the preceding claims, in which the amphiphilic compound is not covalently bonded to the cis-1, 4-polydiene.

7. Composition according to one of the preceding claims, further comprising a crosslinking agent, in particular sulfur or a peroxide.

8. Process for manufacturing a composition according to one of claims 1 to 7, comprising the following process steps:

-preparing a cis-form having a cis-content of at least 95% by polymerization in the presence of a coordination catalyst

-a 1, 4-polydiene,

-attaching a functional group in a terminal position of said cis-1, 4-polydiene,

-mixing said cis-1, 4-polydiene with said amphiphilic compound.

9. The method of claim 8 wherein the cis-1, 4-polydiene is reacted with a modifier compound and thereby functional groups are introduced at terminal positions of the cis-1, 4-polydiene.

10. Elastomeric composition obtainable by crosslinking of the cis-1, 4-polydiene in a composition according to any one of claims 1 to 7.

11. A molded body comprising the elastomer composition according to claim 10.

12. The molded body according to claim 11, wherein the molded body is a tire, a medical article or an industrial rubber article.

13. Use of a composition according to one of claims 1 to 7 for producing shaped bodies, preferably tires or hoses.

Examples

Comparative example 1:

cis-1, 4-polyisoprene having a cis content of 98% was prepared by coordination polymerization in the presence of a neodymium-containing catalyst as follows:

unstable isoprene was first charged into dry cyclohexane (10 wt%), the system temperature was controlled at 50 ℃, a Nd-containing catalyst (sold by combar Chemicals) was dissolved in n-hexane (1.0 vol%, based on monomer), and the isothermal reaction time was 3 hours. The resulting polymer solution was terminated with isopropanol, stabilized with butylhydroxytoluene, and the solvent was removed by coagulation/stripping.

The prepared cis-1, 4-polyisoprene was dissolved in chloroform (10 wt%). To the solution was additionally added 1% by weight of dicumyl peroxide (crosslinker), based on the polymer.

After stirring well, the solvent was evaporated. The film having a thickness of 1mm was subjected to a heat treatment at 160 ℃ to initiate crosslinking of polyisoprene.

Strain crystallization was then determined for the crosslinked composition in the following manner:

relative crystallinity was determined in the static stretch range of 0% to 650% based on uniaxially stretched rubber strips. The method employed here is based on the analysis of one-dimensional X-ray scatter data detected perpendicular to the direction of stretching. After quantification of the intensity (area evaluation) of the amorphous (Halo) and crystalline scattering contributions ((200) and (120) reflections), epsilon was determined as the static stretching_{Static state}Relative crystallinity D of a function of_{c, relative to}＝(I₂₀₀+I₁₂₀)/(I_{Halo (halo)}+I₂₀₀+I₁₂₀)＝I_Crystal/I_{Total of}. The relative crystallinity was calculated for 10-15 static stretches and graphically represented. Determination of the elongation or stretching value epsilon by linear extrapolation based on the graphical representation_{Start of}At this value strain induced crystallization starts.

At 600% static draw, a relative crystallinity D was observed_c,600％Is about 28%. At a value of elongation ε_{Start of}The onset of crystallization was detected at about 350%.

Comparative example 2:

cis-1, 4-polyisoprene was prepared under the same polymerization conditions as in comparative example 1. The cis content of cis-1, 4-polyisoprene was 98%. After the polymerization has proceeded, but before it has stopped, the CO is further introduced₂As modifier compound, for end-group functionalization of the polyisoprene.Cis-1, 4-polyisoprene having a terminal carboxyl group is thus obtained. The polymer solution obtained is quenched with isopropanol, stabilized with butylhydroxytoluene, and the solvent is removed in the conventional manner by coagulation/stripping.

The prepared cis-1, 4-polyisoprene was dissolved in chloroform (10 wt%). Then, 1% by weight of dicumyl peroxide (crosslinker), based on the polymer, was added to the solution. After stirring well, the solvent was evaporated. The film having a thickness of 1mm was subjected to a heat treatment at 160 ℃ to initiate crosslinking of polyisoprene.

Then, for the crosslinked composition, the strain crystallinity was determined according to the method described in comparative example 1.

At 600% static draw, a relative crystallinity D was observed_c,600％About 32.9%. At a value of elongation ε_{Start of}The onset of crystallization was detected at about 350%.

Example 1 according to the invention:

first, cis-1, 4-polyisoprene was prepared under the same polymerization conditions as in comparative example 1. After the polymerization has proceeded, but before it has stopped, the CO is further introduced₂As modifier compound, for end-group functionalization of the polyisoprene. Cis-1, 4-polyisoprene having a terminal carboxyl group is thus obtained. The cis content of the cis-1, 4-polyisoprene was 98%. The polymer solution obtained is stabilized with butylhydroxytoluene and the solvent is removed in a conventional manner by coagulation/stripping.

The prepared cis-1, 4-polyisoprene was dissolved in chloroform (10 wt%). Then, 0.4% by weight of L- α -lecithin (phospholipid functioning as amphiphilic compound) and 1% by weight of dicumyl peroxide (crosslinking agent) based on the polymer were added to the solution.

After stirring well, the solvent was evaporated. The film having a thickness of 1mm was subjected to a heat treatment at 160 ℃ to initiate crosslinking of polyisoprene.

Then, for the crosslinked composition, the strain crystallinity was determined according to the method described in comparative example 1.

At a static extension of 600% the tensile strength,relative crystallinity D was observed_c,600％Is about 46.9%. At a value of elongation ε_{Start of}The onset of crystallization was detected at about 300%.

Comparative example 3:

for comparison, strain crystallinity was also determined for the same vulcanized natural rubber sample.

At 600% static draw, a relative crystallinity D is observed here_c,600％About 42.4%. At a value of elongation ε_{Start of}The onset of crystallization was detected at about 200%.

With the composition according to the invention comprising an end-functionalized cis-1, 4-polydiene and an amphiphilic compound, it is possible to achieve a strain crystallinity after crosslinking that is almost equivalent to that of natural rubber. Stretching D at 600%_C,600％The relative crystallinity of (a) below exceeds that of the natural rubber Sample (SRV) with the same degree of crosslinking studied as a reference.