CN1048257C - Synthesis of homotrans-1,4-polyisoprene - Google Patents
Synthesis of homotrans-1,4-polyisoprene Download PDFInfo
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- CN1048257C CN1048257C CN95110352A CN95110352A CN1048257C CN 1048257 C CN1048257 C CN 1048257C CN 95110352 A CN95110352 A CN 95110352A CN 95110352 A CN95110352 A CN 95110352A CN 1048257 C CN1048257 C CN 1048257C
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Abstract
The present invention relates to a method for synthesizing high trans-1, 4-polyisoprene, which adopts a load type titanium catalyst and body slurry polymerization (namely, precipitation polymerization) technology. Polymerization is carried out under the protection of refined N2. isoprene and catalysts are added in sequence and are stirred and polymerized by segments until all monomers are converted into polymer particles. The catalytic efficiency is larger than 50kg of polymer/g Ti. A product can be directly used, and post treatment and a monomer solvent recovery process step are not needed. The present invention has the advantages of simple technical process, high productive efficiency, low cost and no pollution of three wastes. The trans-1, 4-structure content of the product is larger than 98%. the indexes of physical properties conform to the requirements of specified indexes.
Description
The present invention relates to a kind of synthetic macromolecular material, i.e. high trans-1, the synthetic method of 4-polyisoprene.High trans-1,4-polyisoprene (being called for short TPI) is a kind of tacticity polymer, and the monomer whose chain link is regular anti-form-1 in molecular chain, and 4-arranges, and therefore is easy to crystallization, crystalline melt point Tm=60-65 ℃.This just structure is given the excellent properties of the many uniquenesses of TPI, has extensive use, as shape memory functional material, and medical splint and orthotic material, plastics and rubber material modified etc.
Human use TPI is from big right guttapercha (Balata Rubber) and gutta-percha (Gutta-percha) the earliest, and it is skin, the leaf of gutta-percha tree, the extract of seed.Because content is limited, and extracting method is numerous and diverse, so the cost height, costs an arm and a leg, and range of application is severely limited.
After the Zieler-Natta catalyzer tactic polymerization discovery fifties, synthetic TPI becomes possibility.Be the synthetic TPI of catalyst system that halogenide, oxyhalogenation thing and trialkylaluminium with vanadium are formed at first, its anti-form-1, the 4-structural content can reach 99%, but catalytic efficiency is very low, only is 50-100gTPI/gVCl
3, improvement effect afterwards is also not obvious.With the synthetic TPI of vanadium-titanium mixed catalyst system, polymerization activity is significantly improved, and catalytic efficiency reaches 1000-2000gTPI/gV-Ti, but still belongs to the low activity catalyst system, and anti-form-1,4-structural content decrease (generally being no more than 97%).It is to be noted, before this patent invention, the synthetic solution polymerization process that all adopts in hydro carbons or aromatic solvents of TPI, the polymeric gel power viscosity of surging is very high, brought a series of difficulty for the mixing of polymeric kettle, heat transfer and aftertreatment, also limit simultaneously the concentration (generally only 5-6%) of still interpolymer, thereby reduced throughput, increased cost.
The objective of the invention is to overcome the difficulty that above-mentioned traditional TPI runs in synthetic, the one, adopt load-type Titanium series catalyst as Primary Catalysts, not only catalytic activity increases substantially, and catalytic efficiency is greater than 5 * 10
4GTPI/gTi, and keep anti-form-1, the 4-structural content is more than 98%; The 2nd, adopt the slurry polymerization new process of (or claiming precipitation polymerization), bulk slurry polymeric method particularly, not only can solve many difficult problems that high kinetic viscosity is brought in the solution method polymerization, and can cut off aftertreatment and solvent, MONOMER RECOVERY operation, thereby simplify technical process greatly, enhance productivity, reduce production costs, also do not have the environmental problem of three-waste pollution.
Basic fundamental of the present invention design is, TPI is the crystal polymer thing, under the normal temperature in monomer whose and general varsol indissoluble.Therefore, how to regulate processing condition and prescription, the formation and the growth of control catalyst-polymkeric substance crystal grain, making the polymer particles intergranular that bonding not take place is key of the present invention.Secondly, the particle diameter of controlling polymers is also very important.
This invention is coordinated anionic polymerization.Adopt load-type Titanium series catalyst, under the condition of impurity such as anoxybiotic, exhausted water, carry out, earlier the container there-necked flask is cleaned, dries, vacuumized, use smart N
2After the displacement for several times, add isoprene monomer, add quantitative AlR more successively
3With the Ti catalyzer, under fully stirring, earlier be lower than 10 ℃ of following prepolymerization 0.5-2 hours, form homodisperse polymer beads, in the water-bath under 10-60 ℃ polymerization 15-72 hour again, all change into polymer beads until monomer, transformation efficiency stops polymerization with the ethanolic soln of being furnished with conventional stablizer at last greater than 95%.The resulting polymers particle is dried to constant weight in vacuum drying oven, weigh and calculate transformation efficiency, catalytic efficiency gets final product.Polymerizing condition is: Ti/Ip＜5 * 10
-5(mol ratio), Al/Ti=30-150 (mol ratio).
Analytical results shows, does not have cis-1 basically among the synthetic TPI of present method, the 4-structure, and 1,2 chain link content also can be ignored, and 3,4-chain link content is about 0.62%, and all the other are anti-form-1, the 4-chain link.Test result shows that the performance index of the synthetic TPI of present method can reach and surpass the performance index of international like product fully.Because the science of present technique is simplified production technique, the production efficiency height is expected to reduce cost significantly, obtains considerable industrial value.
Embodiment 1
The 500ml there-necked flask is cleaned, dries, vacuumized, use high-purity N
2Displacement adds the 200ml isoprene monomer, for several times with Ti/Ip=5 * 10
-5, Al/Ti=70 adds the Al (i-Bu) of calculated amount successively
3And load-type Titanium series catalyst, pre-polymerization 1 hour in 0 ℃ of ice-water-bath earlier under fully stirring, move to again and continue polymerization 20 hours in 13 ℃ of water-baths, stop polymerization with few stable agent-ethanolic soln, through vacuum-drying must loosen, no bonded particulate 135g, monomer conversion is 96.4%, catalytic efficiency is 27kgTPI/gTi, the product anti-form-1, the 4-structural content is greater than 98%.
Embodiment 2
Polymerization process is with embodiment 1, and polymerizing condition is: Ti/Ip=2.5 * 10
-5, Al/Ti=90 is earlier 0 ℃ of following pre-polymerization 1 hour, again 20 ℃ of following polymerase 17s 2 hours.Monomer conversion is near 100%, and catalytic efficiency is 56kgTPI/gTi, and anti-form-1,4-structural content do not have bonding greater than 98% between the polymer beads.
Embodiment 3
Polymerization process adds 350ml isoprene/hexane solution, monomer concentration 300mlIp/L with embodiment 1 in the 500ml there-necked flask, prescription and step be with embodiment 1, stop after leach solvent, drying, granulated polymer 58.8g, monomer conversion 85%, catalytic efficiency 24kgTPI/gTi.Solution slurry polymerization helps controlled polymerization composition granule and Stirring heat transfer, but catalytic efficiency and throughput decreases, and also has the solvent recuperation problem.
Embodiment 4
Adopt the 2000ml there-necked flask, polymerization process and condition are with embodiment 2, and the result is also approaching with embodiment 2, illustrate that the poly-unit capacity amplifies, and does not have influence to product structure and performance.
The Main physical mechanical property contrast of the synthetic TPI of present method is as follows:
| Content measurement | Literature value | This law measured value |
| Color and luster | Brown or shallow milk yellow | White or shallow milk yellow |
| Relative density | 0.950 | 0.956 |
| Fusing point (℃) | 60 | 59-62 |
| Mooney viscosity (ML 1+4 100℃) | 35-25 | 30 |
| Hardness (Shao A) | 95 | 95 |
| Degree of crystallinity (%) | 30 | 34 |
| Ash content (%) | ＜0.3 | |
| Tensile strength at yield (Mpa) | 35.2 | 36.7 |
| 300% tensile modulus (Mpa) | 17.6 | 22.5 |
| Pull apart extensibility (%) | 460-500 | 400 |
Claims (1)
1, a kind of synthetic high trans-1, the novel method of 4-polyisoprene is characterized in that adopting load-type Titanium series catalyst, carries out under the condition of anoxybiotic, exhausted water, earlier aggregation container is cleaned, dries, is vacuumized, and uses smart N
2After the displacement for several times, add isoprene monomer, add load-type Titanium series catalyst more successively, under fully stirring,, form homodisperse polymer beads earlier being lower than 10 ℃ of following prepolymerization 0.5-2 hours, in the water-bath under 10-60 ℃ polymerization 15-72 hour again, all change into polymer beads until monomer, stop polymerization with the ethanolic soln of being furnished with conventional stablizer at last, polymerizing condition is: Ti/Ip＜5 * 10
-5(mol ratio), Al/Ti=30-150 (mol ratio).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95110352A CN1048257C (en) | 1995-02-17 | 1995-02-17 | Synthesis of homotrans-1,4-polyisoprene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95110352A CN1048257C (en) | 1995-02-17 | 1995-02-17 | Synthesis of homotrans-1,4-polyisoprene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1117501A CN1117501A (en) | 1996-02-28 |
| CN1048257C true CN1048257C (en) | 2000-01-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN95110352A Expired - Fee Related CN1048257C (en) | 1995-02-17 | 1995-02-17 | Synthesis of homotrans-1,4-polyisoprene |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100494229C (en) * | 2006-04-11 | 2009-06-03 | 青岛科大方泰材料工程有限公司 | Industrial synthesis process of high trans-1, 4-iroprene polymer |
| CN105601814B (en) | 2016-03-24 | 2020-11-27 | 青岛科技大学 | Industrial production method of trans-butadiene-isoprene copolymer rubber and device for implementing method |
| CN112707985B (en) * | 2020-12-23 | 2022-05-10 | 青岛竣翔科技有限公司 | Homogeneous catalyst for preparing trans-1, 4-polyisoprene polymer, preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60190407A (en) * | 1984-03-12 | 1985-09-27 | Toyo Soda Mfg Co Ltd | Production of trans-1,4-polyisoprene |
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- 1995-02-17 CN CN95110352A patent/CN1048257C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60190407A (en) * | 1984-03-12 | 1985-09-27 | Toyo Soda Mfg Co Ltd | Production of trans-1,4-polyisoprene |
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