CN107793542B - Method for synthesizing hydrogenated styrene/isoprene block copolymer - Google Patents
Method for synthesizing hydrogenated styrene/isoprene block copolymer Download PDFInfo
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Abstract
The invention discloses a method for synthesizing hydrogenated styrene/isoprene block copolymer; synthesizing a diblock copolymer or a multiblock copolymer containing a styrene block and an isoprene block in an anionic polymerization system using nonpolar alkane and toluene as polymerization solvents, and hydrogenating the diblock copolymer or the multiblock copolymer to obtain a hydrogenated styrene/isoprene block copolymer; the method adopts a mixed solvent of nonpolar alkane and toluene, so that the reaction probability of an active PS-Li end group and isoprene can be effectively increased, the content of micromolecule polystyrene in the hydrogenated styrene/isoprene block copolymer is reduced or eliminated, the dropping point of the two-block or multi-block hydrogenated styrene/isoprene block copolymer when being applied to optical fibers and optical cables for filling factice is improved, or the comprehensive physical and mechanical properties of the multi-block hydrogenated styrene/isoprene block copolymer are improved.
Description
Technical Field
The invention relates to a method for synthesizing hydrogenated styrene/isoprene block copolymer, in particular to a basic solvent system for synthesizing hydrogenated styrene/isoprene block copolymer, more specifically, styrene/isoprene block copolymer with styrene block molecular weight of 2-5 ten thousand and hydrogenated polymer thereof are synthesized by adopting special mixed solvent consisting of nonpolar alkane and toluene, belonging to the technical field of styrene thermoplastic elastomer synthesis.
Background
The styrene thermoplastic elastomer (SDC) adopts a lithium initiator anion solution polymerization process industrially, the used solvent is a hydrocarbon solvent, and cyclohexane is generally adopted as a polymerization solution in China.
There is no relevant patent and literature in the solvent system for synthesizing hydrogenated styrene/isoprene polymer at home and abroad. At present, no industrial product exists in the domestic hydrogenated styrene/isoprene polymer, and the synthesis research on the hydrogenated styrene/isoprene polymer just starts. Some studies have shown that: when the two-block hydrogenated styrene-isoprene polymer is synthesized, cyclohexane is used as a polymerization solvent, and the synthesized hydrogenated styrene-isoprene polymer has high content of small molecular polymer Polystyrene (PS), thereby seriously influencing the dropping point of the polymer when the polymer is applied to optical fibers and optical cable filling factice. It was found that in the anionic polymerization of the PS block, after the polymerization reaction was completed, the PS still had the living character, but part of the PS-Li did not react with the isoprene added in stages. The main reason is that when the molecular weight of PS is increased, the obtained PS block can be curled and wound, the active end group can be easily embedded in the polymer and can not be in contact reaction with isoprene added at the second section, the coated active lithium stays in a pseudo-active state, and a small molecular polymer is formed after artificial termination reaction is finished. At present, no report on the method is well solved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for effectively increasing the reaction probability of active PS-Li end groups and isoprene so as to reduce or eliminate the content of small-molecular polystyrene in a hydrogenated styrene/isoprene block copolymer.
In order to achieve the above technical objects, the present invention provides a method for synthesizing a hydrogenated styrene/isoprene block copolymer, comprising synthesizing a di-block copolymer or a multi-block copolymer comprising a styrene block and an isoprene block in an anionic polymerization system, and hydrogenating the di-block copolymer or the multi-block copolymer to obtain a hydrogenated styrene/isoprene block copolymer,
in the preferable scheme, the weight ratio of the nonpolar alkane to the toluene in the mixed solvent is (90-50) to (10-50); more preferably (85-60) and (15-40); most preferably (85-70) and (15-30).
Preferably, the nonpolar hydrocarbon solvent is cyclohexane.
In a preferred embodiment, the anionic polymer system comprises a lithium-based initiator, an activator, and a structure modifier. The initiator, activator and structure modifier are conventional in the art.
In a preferred scheme, the molecular weight of a single styrene block in the diblock copolymer or the multiblock copolymer containing the styrene block and the isoprene block is 2-5 ten thousand.
The key point of the technical scheme of the invention is that a mixed solvent consisting of nonpolar alkane and toluene is adopted. The conventional polymerization solvent adopted by the conventional anionic polymerization is single nonpolar alkane, the nonpolar alkane has good solubility to micromolecular polystyrene in the polymerization process of styrene, the solubility of the nonpolar alkane in the nonpolar alkane is reduced along with the increase of the molecular weight of the polystyrene, a polymerization chain cannot be well stretched, the twisting and winding occur, the active PS-Li end group is embedded, the pseudo activity occurs, the polymerization reaction with isoprene cannot be further carried out, and the micromolecular polystyrene remains in a final polymer to influence the performance of a final product. The mixed solvent of nonpolar alkane and toluene adopted by the invention enables PS with relatively large molecular weight to be completely stretched in the mixed solvent, avoids the pseudo-activity phenomenon of active PS-Li end groups, increases the reaction probability of the active PS-Li end groups and isoprene, thereby achieving the purposes of reducing or eliminating the existence of micromolecule PS, improving the dropping point of the two-block hydrogenated styrene/isoprene block copolymer when being applied to optical fibers and optical cables for filling factice, or improving the comprehensive physical and mechanical properties of the multi-block hydrogenated styrene/isoprene block copolymer.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1. the technical scheme of the invention can effectively reduce or eliminate the content of micromolecule polystyrene in the diblock or multiblock hydrogenated styrene/isoprene copolymer, greatly improve the dropping point of the diblock copolymer when the diblock copolymer is applied to optical fibers and optical cables for filling factice, and improve the comprehensive physical and mechanical properties of the multiblock hydrogenated styrene/isoprene block copolymer.
2. Compared with the prior art, the technical scheme of the invention only needs to add a proper amount of toluene, does not need to change the prior mature process, has simple operation and low cost, and is beneficial to popularization and application.
3. The technical scheme of the invention is suitable for synthesizing the styrene/isoprene block copolymer and the hydrogenated polymer thereof by using a lithium-series initiator anion solution polymerization process, is particularly suitable for synthesizing the hydrogenated styrene/isoprene copolymer with the molecular weight of a single styrene block more than 2 ten thousand, and is most suitable for synthesizing the hydrogenated styrene/isoprene polymer with the molecular weight of the single styrene block between 2 and 5 ten thousand.
Detailed Description
In order to describe the present invention in more detail, the following examples are further illustrated, but the present invention is not limited to the scope of the examples.
The synthesis process and hydrogenation process of the styrene-isoprene polymer or the three-block hydrogenated styrene-isoprene-styrene polymer are conventional methods. The technical scheme of the invention is characterized in that a solvent system adopted by the technical scheme of the invention consists of cyclohexane and toluene, wherein the weight ratio of the cyclohexane to the toluene is 90-50: 10-50. Other auxiliary agents such as an activator, a structure regulator and the like may be added as required in synthesizing the hydrogenated styrene/isoprene polymer.
The molecular weights, coupling efficiencies, and degrees of coupling of the polymers in the examples were determined by gel permeation chromatography using GPC measurements according to Q/SH019.05.P.003(05) -1998;
the degree of hydrogenation was determined by iodometry.
The preparation method of the factice for filling the optical fiber and the optical cable comprises the following steps: 16g of diblock hydrogenated styrene-isoprene and 184g of a type II base oil were put into a 500mL beaker, heated in a heating mantle and stirred at a temperature of 100 ℃ and 120 ℃ until a homogeneous viscous ointment was obtained.
The dropping point of the optical fiber and optical cable filling ointment is measured according to the GB 4929-85 standard.
300% tensile strength at definite elongation, tensile strength at break, elongation at break, permanent set test standard: measured according to GB/T528-92 standard;
hardness test standard: measuring according to GB/T531-99 standard;
example 1
Synthesizing a two-block hydrogenated styrene/isoprene polymer by adopting a lithium initiator anion solution polymerization process, wherein the mass ratio of cyclohexane to toluene in a solvent is 90: 10, the adding amount of tetrahydrofuran as an activator is 100mg/Kg of solvent, the total molecular weight of the two-block hydrogenated styrene-isoprene polymer is 12.4 ten thousand, and the molecular weight of a single styrene block is 2.4 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The oil is added into base oil II according to the proportion of 8 percent, and the dropping point of the oil is tested.
Comparative example 1
The method adopts a lithium-series initiator anion solution polymerization process to synthesize the two-block hydrogenated styrene-isoprene polymer, wherein the solvent is cyclohexane, the addition amount of an activating agent tetrahydrofuran is 100mg/Kg solvent, the total molecular weight of the two-block hydrogenated styrene-isoprene polymer is 12.2 ten thousand, and the molecular weight of a single styrene block is 2.3 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The oil is added into base oil II according to the proportion of 8 percent, and the dropping point of the oil is tested.
Example 2
Synthesizing a two-block hydrogenated styrene-isoprene polymer by adopting a lithium initiator anion solution polymerization process, wherein the mass ratio of cyclohexane to toluene in a solvent is 80: 20, the adding amount of the regulator tetrahydrofuran is 100mg/Kg solvent, the total molecular weight of the two-block hydrogenated styrene-isoprene polymer is 12.2 ten thousand, and the molecular weight of a single styrene block is 2.2 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The oil is added into base oil II according to the proportion of 8 percent, and the dropping point of the oil is tested.
Example 3
Synthesizing a two-block hydrogenated styrene-isoprene polymer by adopting a lithium initiator anion solution polymerization process, wherein the mass ratio of cyclohexane to toluene in a solvent is 70: 30, the adding amount of the regulator tetrahydrofuran is 100mg/Kg solvent, the total molecular weight of the two-block hydrogenated styrene-isoprene polymer is 12.4 ten thousand, and the molecular weight of a single styrene block is 2.4 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The oil is added into base oil II according to the proportion of 8 percent, and the dropping point of the oil is tested.
Example 4
Synthesizing a two-block hydrogenated styrene-isoprene polymer by adopting a lithium initiator anion solution polymerization process, wherein the mass ratio of cyclohexane to toluene in a solvent is 60: 40, the addition of the regulator tetrahydrofuran is 100mg/Kg of solvent, the total molecular weight of the two-block hydrogenated styrene-isoprene polymer is 12.2 ten thousand, and the molecular weight of a single styrene block is 2.3 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The oil is added into base oil II according to the proportion of 8 percent, and the dropping point of the oil is tested.
Example 5
Synthesizing a two-block hydrogenated styrene-isoprene polymer by adopting a lithium initiator anion solution polymerization process, wherein the mass ratio of cyclohexane to toluene in a solvent is 50: 50, the adding amount of regulator tetrahydrofuran is 100mg/Kg solvent, the total molecular weight of the two-block hydrogenated styrene-isoprene polymer is 12.5 ten thousand, and the molecular weight of a single styrene block is 2.5 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The oil is added into base oil II according to the proportion of 8 percent, and the dropping point of the oil is tested.
Example 6
Synthesizing a two-block hydrogenated styrene-isoprene polymer by adopting a lithium initiator anion solution polymerization process, wherein the mass ratio of cyclohexane to toluene in a solvent is 70: 30, the adding amount of the regulator tetrahydrofuran is 100mg/Kg solvent, the total molecular weight of the two-block hydrogenated styrene-isoprene polymer is 13.4 ten thousand, and the molecular weight of a single styrene block is 3.5 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The oil is added into base oil II according to the proportion of 8 percent, and the dropping point of the oil is tested.
Example 7
Synthesizing a two-block hydrogenated styrene-isoprene polymer by adopting a lithium initiator anion solution polymerization process, wherein the mass ratio of cyclohexane to toluene in a solvent is 70: 30, the adding amount of the regulator tetrahydrofuran is 100mg/Kg solvent, the total molecular weight of the two-block hydrogenated styrene-isoprene polymer is 13.6 ten thousand, and the molecular weight of a single styrene block is 4.8 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The oil is added into base oil II according to the proportion of 8 percent, and the dropping point of the oil is tested.
Comparative example 2
The method adopts a lithium-series initiator anion solution polymerization process to synthesize the two-block hydrogenated styrene-isoprene polymer, wherein the solvent is cyclohexane, the addition amount of an activating agent tetrahydrofuran is 100mg/Kg solvent, the total molecular weight of the two-block hydrogenated styrene-isoprene polymer is 13.2 ten thousand, and the molecular weight of a single styrene block is 4.7 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The oil is added into base oil II according to the proportion of 8 percent, and the dropping point of the oil is tested.
TABLE 1 comparison of the Properties of the different base solvents for the synthesis of two-block styrene-isoprene
Example 8
Synthesizing a triblock hydrogenated styrene-isoprene-styrene polymer by adopting a lithium initiator anionic solution polymerization process, wherein the mass ratio of cyclohexane to toluene in a solvent is 90: 10, the addition amount of tetrahydrofuran as an activator is 100mg/Kg of solvent, the total molecular weight of the triblock hydrogenated styrene-isoprene-styrene polymer is 16.3 ten thousand, and the molecular weight of a single styrene block is 2.1 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The polymer was tested for various physical properties.
Comparative example 3
The triblock hydrogenated styrene-isoprene-styrene polymer is synthesized by adopting a lithium initiator anion solution polymerization process, wherein the solvent is cyclohexane, the addition amount of an activating agent tetrahydrofuran is 100mg/Kg, the total molecular weight of the diblock hydrogenated styrene-isoprene-styrene polymer is 16.6 ten thousand, and the molecular weight of a single styrene block is 2.2 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The polymer was tested for various physical properties.
Example 9
Synthesizing a triblock hydrogenated styrene-isoprene-styrene polymer by adopting a lithium initiator anionic solution polymerization process, wherein the mass ratio of cyclohexane to toluene in a solvent is 80: 20, the adding amount of tetrahydrofuran as an activating agent is 100mg/Kg of solvent, the total molecular weight of the triblock hydrogenated styrene-isoprene-styrene polymer is 16.5 ten thousand, and the molecular weight of a single styrene block is 2.2 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The polymer was tested for various physical properties.
Example 10
Synthesizing a triblock hydrogenated styrene-isoprene-styrene polymer by adopting a lithium initiator anionic solution polymerization process, wherein the mass ratio of cyclohexane to toluene in a solvent is 70: 30, the addition amount of tetrahydrofuran as an activator is 100mg/Kg of solvent, the total molecular weight of the triblock hydrogenated styrene-isoprene-styrene polymer is 16.2 ten thousand, and the molecular weight of a single styrene block is 2.1 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The polymer was tested for various physical properties.
Example 11
Synthesizing a triblock hydrogenated styrene-isoprene-styrene polymer by adopting a lithium initiator anionic solution polymerization process, wherein the mass ratio of cyclohexane to toluene in a solvent is 60: 40, the addition of the activator tetrahydrofuran is 100mg/Kg of solvent, the total molecular weight of the triblock hydrogenated styrene-isoprene-styrene polymer is 16.7 ten thousand, and the molecular weight of a single styrene block is 2.3 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The polymer was tested for various physical properties.
Example 12
Synthesizing a triblock hydrogenated styrene-isoprene-styrene polymer by adopting a lithium initiator anionic solution polymerization process, wherein the mass ratio of cyclohexane to toluene in a solvent is 50: 50, the adding amount of activator tetrahydrofuran is 100mg/Kg solvent, the total molecular weight of the triblock hydrogenated styrene-isoprene-styrene polymer is 16.0 ten thousand, and the molecular weight of a single styrene block is 2.0 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The polymer was tested for various physical properties.
Example 13
Synthesizing a triblock hydrogenated styrene-isoprene-styrene polymer by adopting a lithium initiator anionic solution polymerization process, wherein the mass ratio of cyclohexane to toluene in a solvent is 70: 30, the addition amount of tetrahydrofuran as an activator is 100mg/Kg of solvent, the total molecular weight of the triblock hydrogenated styrene-isoprene-styrene polymer is 18.0 ten thousand, and the molecular weight of a single styrene block is 3.3 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The polymer was tested for various physical properties.
Comparative example 4
The triblock hydrogenated styrene-isoprene-styrene polymer is synthesized by adopting a lithium initiator anion solution polymerization process, wherein the solvent is cyclohexane, the addition amount of an activating agent tetrahydrofuran is 100mg/Kg, the total molecular weight of the diblock hydrogenated styrene-isoprene-styrene polymer is 18.6 ten thousand, and the molecular weight of a single styrene block is 3.4 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The polymer was tested for various physical properties.
Example 14
Synthesizing a triblock hydrogenated styrene-isoprene-styrene polymer by adopting a lithium initiator anionic solution polymerization process, wherein the mass ratio of cyclohexane to toluene in a solvent is 70: 30, the adding amount of tetrahydrofuran as an activating agent is 100mg/Kg of solvent, the total molecular weight of the triblock hydrogenated styrene-isoprene-styrene polymer is 18.8 ten thousand, and the molecular weight of a single styrene block is 4.4 ten thousand. The polymer is selectively hydrogenated, and the hydrogenation degree is more than or equal to 98 percent. And (3) condensing the polymer by water vapor, and drying to obtain the copolymer. The polymer was tested for various physical properties.
TABLE 2 comparison of the Properties of the different base solvents for the synthesis of triblock styrene-isoprene-styrene
Claims (3)
1. A method for synthesizing hydrogenated styrene/isoprene block copolymer, in an anionic polymerization system, synthesizing diblock copolymer or multiblock copolymer containing styrene block and isoprene block, and hydrogenating the diblock copolymer or multiblock copolymer to obtain hydrogenated styrene/isoprene block copolymer, characterized in that: the anion polymerization system adopts a mixed solvent consisting of nonpolar alkane and toluene;
the weight ratio of the nonpolar alkane to the toluene in the mixed solvent is (85-70) to (15-30);
the nonpolar alkane is cyclohexane.
2. The method of synthesizing a hydrogenated styrene/isoprene block copolymer according to claim 1, wherein: the anionic polymer system comprises a lithium-based initiator, an activator and a structure regulator.
3. The method of synthesizing a hydrogenated styrene/isoprene block copolymer according to claim 1, wherein: the molecular weight of a single styrene block in the diblock copolymer or the multiblock copolymer containing the styrene block and the isoprene block is 2-5 ten thousand.
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| JPH069935A (en) * | 1992-05-14 | 1994-01-18 | Nippon Zeon Co Ltd | Self-adhesive composition |
| CN1149061A (en) * | 1996-10-04 | 1997-05-07 | 北京燕山石油化工公司研究院 | Block polymer of isoprene and styrene and preparation thereof |
| US5990236A (en) * | 1993-10-18 | 1999-11-23 | Basf Aktiengesellschaft | Preparation of impact-resistant polystyrene |
| CN102485762A (en) * | 2009-11-03 | 2012-06-06 | 中国石油化工股份有限公司 | Colourless butylbenzene segmented copolymer with low gel content and preparation method thereof |
| CN105754055A (en) * | 2014-12-16 | 2016-07-13 | 中国石油天然气股份有限公司 | Star-shaped hydrogenated styrene diene copolymer and preparation method thereof |
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|---|---|---|---|---|
| JPH069935A (en) * | 1992-05-14 | 1994-01-18 | Nippon Zeon Co Ltd | Self-adhesive composition |
| US5990236A (en) * | 1993-10-18 | 1999-11-23 | Basf Aktiengesellschaft | Preparation of impact-resistant polystyrene |
| CN1149061A (en) * | 1996-10-04 | 1997-05-07 | 北京燕山石油化工公司研究院 | Block polymer of isoprene and styrene and preparation thereof |
| CN102485762A (en) * | 2009-11-03 | 2012-06-06 | 中国石油化工股份有限公司 | Colourless butylbenzene segmented copolymer with low gel content and preparation method thereof |
| CN105754055A (en) * | 2014-12-16 | 2016-07-13 | 中国石油天然气股份有限公司 | Star-shaped hydrogenated styrene diene copolymer and preparation method thereof |
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