CN1175595A - Preparation method of styrene-isoprene block copolymer - Google Patents
Preparation method of styrene-isoprene block copolymer Download PDFInfo
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- CN1175595A CN1175595A CN 96118322 CN96118322A CN1175595A CN 1175595 A CN1175595 A CN 1175595A CN 96118322 CN96118322 CN 96118322 CN 96118322 A CN96118322 A CN 96118322A CN 1175595 A CN1175595 A CN 1175595A
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- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 55
- 238000010168 coupling process Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000005859 coupling reaction Methods 0.000 claims abstract description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000007822 coupling agent Substances 0.000 claims abstract description 18
- 239000012190 activator Substances 0.000 claims abstract description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 55
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 38
- 239000003999 initiator Substances 0.000 claims description 30
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 29
- 230000000977 initiatory effect Effects 0.000 claims description 20
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 13
- 230000003213 activating effect Effects 0.000 claims description 13
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000002516 radical scavenger Substances 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 230000008878 coupling Effects 0.000 abstract description 25
- 239000000126 substance Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003292 glue Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 229910003910 SiCl4 Inorganic materials 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 229920005684 linear copolymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 239000012629 purifying agent Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
The invention relates to a preparation method of a styrene-isoprene block copolymer, in particular to a three-step feeding process and a two-step feeding coupling process. In the three-step charging process, the reaction temperature is controlled, and the activator tetrahydrofuran is added before the third-stage polymerization, in the two-step coupling process, the first two steps are the same as the three-step method, and a method of adding the coupling agent step by step is adopted in the coupling step. The invention realizes the synthesis of the styrene-isoprene segmented copolymer on a ten-thousand-ton device by improving the prior art, and the synthesized copolymer has good physical and chemical properties.
Description
The invention relates to a preparation method of a styrene-isoprene block copolymer, in particular to a three-step feeding process and a two-step feeding coupling process.
The styrene-isoprene block copolymer is a sister product of SBS, and the synthesis method is the same as SBS, and there can be several ways: a bifunctional initiator process, a three-step feeding process and a coupling process.
The three-step charging process adopts a monofunctional initiator and cyclohexane as a solvent. Firstly, the initiator reacts with one molecule of the styrene monomer, namely the initiation reaction,
this product then undergoes a propagation reaction with styrene, namely:
(PSn-Li+) After addition of isoprene, PSnLi can further initiate the polymerization:
finally, styrene is added to obtain SIS.
This reaction is difficult and easily results in the formation of two blocks of PSI.
In the coupling process, the first two-step polymerization is the same as the three-step method, and the last step is to add a bifunctional or polyfunctional coupling agent, wherein the reaction formula is as follows:
the star-shaped block copolymer can be obtained by adopting a polyfunctional group coupling agent. However, due to the steric effect of the polyisoprene block, the coupling degree and the coupling efficiency of the copolymer are low, the content of the PSI two blocks is high, and the product performance is influenced.
In addition, with pure cyclohexane as the solvent, difficulties arise in solvent transport at ambient temperatures below 5 ℃. A mixed solution of cyclohexane and benzene is used as a solvent, but the solvent is not a good solvent in consideration of the environmental hazard caused by the toxicity of benzene.
The invention aims to provide a process method for synthesizing a styrene-isoprene block copolymer with good physical and chemical properties in a ten-thousand-ton device.
Typically, the styrene-isoprene block copolymers of both structures have molecular weights between 60000 and 300000, with a weight percent of styrene monomer of 10-30% and an isoprene monomer of 70-90%.
To prepare the copolymers described above on a ten-thousand-ton scale, the present invention was prepared as follows. The preparation method is improved on the basis of the existing three-step feeding process and two-step feeding coupling process, so that the preparation method is suitable for ten-thousand-ton-grade industrial device production, and the first two steps of the two preparation methods are the same.
Preparation of a Linear copolymer (SIS):
the invention adopts cyclohexane as solvent, n-butyllithium or sec-butyllithium as initiator and tetrahydrofuran as activator, and the copolymer is prepared by three-step charging process, namely
(1) Adding a solvent and styrene into a polymerization kettle, initiating a first block polymerization reaction at 45-55 ℃ in the presence of an initiator and an activator, controlling the reaction temperature to be 50-80 ℃, and controlling the reaction time to be 20-30 min;
(2) after the first block is polymerized, adding an isoprene monomer into a polymerization kettle, initiating the polymerization of the second block at 40-60 ℃ for 5-20min, and then controlling the reaction temperature at 70-120 ℃ and the reaction time for 30-45 min;
(3) after the second block polymerization is finished, adding tetrahydrofuran serving as an activating agent into a polymerization kettle, controlling the molar ratio of the addition amount of the tetrahydrofuran to the addition amount of an initiator to be 1.0-2.0, controlling the initiation temperature to be not lower than 70 ℃, adding a styrene monomer, carrying out third block polymerization, and controlling the reaction time to be 20-25min so as to discharge.
The temperature has a certain influence on each step of the preparation method.
FIG. 1 is a graph of first stage conversion versus time at various temperatures;
FIG. 2 is a graph of second stage conversion versus time at different temperatures.
It can be seen from FIG. 1 that increasing the temperature, although it is advantageous for increasing the reaction rate, is not very sensitive to temperature effects since the polymerization rate is already high under the selected conditions.
As can be seen from FIG. 2, the growth rate of active polystyrene based lithium system initiated isoprene polymerization process is much slower than that of butyl lithium initiated styrene polymerization, and meanwhile, the temperature change has a significant effect on the reaction rate; the second stage reaction adopts low temperature initiation, and after a period of time, the reaction temperature is increased, the reaction rate is adjusted, and the reaction time is shortened.
Although the third stage is the same as the first stage in the polymerization of styrene, the reaction speed of the third stage is reduced due to the change of the polymerization "active species" and the difference of the system viscosity, and an induction period occurs at a low temperature. The activator tetrahydrofuran is added in the third step, and the initiation temperature of the third section is controlled to be not lower than 70 ℃, so that the generation of two-block PSI can be effectively reduced.
The optimal ratio of the mole number of the added activator tetrahydrofuran to the mole number of the initiator is 1.05-1.35; the optimum value of the initiation temperature is 80-85 ℃.
Preparation of the two Star-shaped copolymer (SI) nR:
cyclohexane is used as a solvent, n-butyllithium or sec-butyllithium is used as an initiator, tetrahydrofuran is used as an activating agent, and the copolymer is prepared by a two-step charging coupling method process, namely
(1) Adding a solvent and styrene into a polymerization kettle, initiating a first block polymerization reaction at 45-55 ℃ in the presence of an initiator and an activator, controlling the reaction temperature to be 50-80 ℃, and controlling the reaction time to be 20-30 min;
(2) after the first block is polymerized, adding an isoprene monomer into a polymerization kettle, initiating the polymerization of the second block at 40-60 ℃ for 5-20min, and then controlling the reaction temperature at 70-120 ℃ and the reaction time for 30-45 min;
(3) adding a coupling agent SiCl after the second block polymerization is finished4Coupling is carried out, the total mole number of the added coupling agent is 0.25-0.30 times of the mole number of the initiator, the coupling agent is added in two times, and the total amount of the first addition is70% of (1), after 10min, adding for the second timeAnd finishing the coupling reaction after 20-25min after adding the rest amount.
The first two steps of the above preparation process are the same as those of the linear copolymer preparation process. And the third step is different. In the third step of the preparation method, the coupling agent is added step by step, which is beneficial to improving the coupling degree and the coupling efficiency of the final product. In order to improve the coupling degree and coupling efficiency of the final product, purified butadiene can be added into the reaction liquid after the second stage polymerization is completed, wherein the mole number of the added butadiene is 1-14 times that of the initiator. The addition of butadiene makes the reactant S-IB-Li+In the formula, Mn (B) of the B section is more than 54, and then a coupling agent is added for coupling reaction to ensure that the final product achieves high coupling degree and high coupling efficiency, wherein the coupling degree is more than 3.5, and the coupling efficiency is more than 90%.
In order to solve the problem that when pure cyclohexane is used as a solvent, the transportation is inconvenient when the environmental temperature is lower than 5 ℃, the invention adopts a mixed solution of cyclohexane and raffinate oil as the solvent. Wherein the raffinate oil is 1-50 wt%, preferably 1-20 wt% in solvent, the raffinate oil is gasoline fraction obtained by extracting aromatic hydrocarbon from refinery platinum reforming, the boiling range is 60-140 deg.C, preferably cutting, and collecting 65-90 deg.C fraction.
The purity of the raw materials involved in the reaction is in accordance with the requirements of the polymerization reaction, and the following requirements are particularly preferably achieved:
the purity of isoprene is more than or equal to 99.5 percent, the water content is less than or equal to 20ppm, the cyclopentadiene is less than or equal to 2ppm, the alkyne is less than or equal to 20ppm, the carbonyl compound is less than or equal to 10ppm, and the piperylene is less than or equal to 80 ppm;
the purity of the styrene is more than or equal to 99.5 percent, the water content is less than or equal to 20ppm, the benzaldehyde content is less than or equal to 50ppm, and the autopolymer content is less than or equal to 300 ppm.
In order to meet the purity requirements of the raw materials, various methods are adopted in the prior art. The present invention is based on the following method.
Isoprene monomer is passed through atmospheric rectification in high-effective silk screen corrugated packed tower and adsorption treatment in 3 Å, 4 Å and 5 Å molecular sieve drying tower, the isoprene is refined according to the molecular sieve proportion of 1: 2: 3 and its order, and the harmful impurity is removed, and styrene monomer is passed through high-effective silk screen corrugated packed towerReduced pressure rectification in a packed column with striated packing, side stream discharge, and Al2O33 Å molecular sieve drying tower for adsorption treatment to remove harmful impurities, the method can obtain raw material meeting the requirements
Before the first polymerization step, butyl lithium as a chemical purifying agent was added to the polymerization vessel to chemically purify the solvent and styrene. The amount of the scavenger is equivalent to the amount of impurities in the solvent and the styrene, and then the required amount of the initiator is added into the polymerization kettle for reaction.
After the reaction is finished, the required product can be obtained by adopting the post-treatment processes of elutriation and coagulation, extrusion dehydration and expansion drying. The invention further adopts a hot air drying process to dry the product, so that the content of volatile matters in the product is lower than 0.5 percent. The temperature of the hot air used was 50-105 ℃.
The copolymer prepared by the preparation method provided by the invention is analyzed by a gel chromatograph (taking THF as a solvent), the molecular weight distribution is very narrow, the D value is between 1.02 and 1.06, and the copolymer does not contain homopolymer and SI two-block products basically; the microstructure of the midblock is mainly cis-1, trans-4 structure and about 90 percent, and is assisted by 3 and 4 structure through nuclear magnetic resonance spectrometer analysis, and the midblock has good physicochemical property.
Examples 1 to 10
Preparation of linear SIS
With a volume of 30m3The polymerization kettle is heated and baked, and is repeatedly replaced by high-purity nitrogen until the polymerization kettle is anhydrous and oxygen-free. Then cooling to normal temperature under the protection of high-purity nitrogen. Pumping preheated refined solvent (pure cyclohexane or mixture of cyclohexane and raffinate oil) and refined styrene with temperature of 0-10 deg.C into polymerization kettle according to required dosage (see table 1), stirring uniformly and heating to 30-35 deg.C, adding appropriate amount of chemical purifying agent-butyl lithium into polymerization kettle at one time, and chemically purifying solvent and styrene, wherein dosage of the purifying agent depends on harmful impurity content in solvent and styrene. After the purification operation is finished, the required amount of initiator butyl lithium and activator tetrahydrofuran (shown in table 1) are quickly added into a polymerization kettle, and the temperature is raised to 45 ℃ for initiationThe first block polymerization reaction is completed after the first stage reaction is carried out for 30min under the condition that the reaction temperature is controlled to be 50-80 ℃. Adding the required amount of isoprene monomer into a polymerization kettle by a pump, initiating at 50-60 ℃ for 5-10min, then carrying out polymerization of the second block, controlling the highest reaction temperature below 100 ℃, reacting for 45min, and finishing the polymerization of the second block. Adding tetrahydrofuran as an activator into reaction liquid in a polymerization kettle, wherein the mole number of the tetrahydrofuran as the activator is 1.05-1.35 times of that of an initiator, and controlling the temperature of the reaction liquid in the kettle to be 80-85 ℃; adding purified styrene monomer in required amount for the third block polymerization, and finishing the SIS polymerization reaction 25min later. And (3) conveying the materials from the polymerization kettle to a glue solution tank by using a glue solution pump, stopping the reaction by adopting a method of adding water in the discharging process, adding 2.6.4 percent of anti-aging agent which is 0.6 percent of the weight of the polymer into the glue solution, condensing the glue solution by a elutriation method, extruding and dehydrating the glue solution, and performing expansion drying and hot air drying to obtain the cylindrical small particle product.
The physical and mechanical properties of the linear SIS prepared according to examples 1 to 10 are shown in Table 2. Wherein the stretching strength is GB 528-82; tensile strength was measured according to GB 528-82; permanent set was determined according to GB 528-82; hardness (Shore A) was determined according to GB 531-75; melt flow rate according to GB 3682-83.
As is clear from Table 2, the linear SIS products prepared by the preparation process provided by the present invention have superior physical and mechanical properties.
Examples 11 to 18
Preparation of Star-Shaped (SI) nR
The two-step polymerization reaction before the preparation process of Star (SI) nR is the same as that of the linear SIS, the feeding formula is shown in table 3, and after the two-step polymerization is completed, a coupling agent SiCl is added4A coupling reaction is carried out. Adding coupling agent twice, adding 70% of total amount for the first time, adding the rest for the second time after coupling for 10min, adding purified butadiene monomer (the amount is shown in table 3) into the reaction solution after finishing the second stage polymerization if the coupling degree and coupling efficiency of (SI) nR are to be improved, and continuing to react for 5min to make the reactant become S-I-B-Li+Then adding SiCl as a coupling agent in the method4The coupling reaction is carried out, so that the final product can achieve high coupling efficiency and obtain ideal physical and mechanical properties.
The physical and mechanical properties of (SI) nR prepared in examples 11-18 are shown in Table 4, wherein the degree of coupling and coupling efficiency are the results of GPC analysis, and the other indices are determined by the same method as that of the linear SIS.
As can be seen from Table 4, the star-Shaped (SI) nR prepared by the preparation process provided by the invention has excellent physical and mechanical properties.
Examples 19 to 24
The preparation method of the linear SIS is basically the same as that of the examples 1 to 10, and the difference is that the initiation temperature adopted by the second block (polyisoprene block) is lower, the initiation temperature is 45 to 50 ℃, after initiation, the temperature of a polymerization reaction system is rapidly raised to 70 ℃, the heat supply is stopped, the reaction temperature is controlled to be not higher than 100 ℃, the polymerization reaction time is 35 to 38min, the total reaction time is less than 100min, the feeding formula is shown in a table 5, the physical property test is shown in a table 6, the data in the table show that the physical properties of all products are better, and the production capacity can be improved.
Examples 25 to 30
The preparation method of Star (SI) nR is the same as that of examples 19-24 in the first two steps, the rest is the same as that of examples 11-18, the total reaction time of a single kettle is within 100min, the feeding formula is shown in Table 7, and the physical property test result is shown in Table 8.
Examples 31 to 36
The preparation of Star (SI) nR is essentially identical to that of examples 11 to 18, with the difference that the coupling agent SiCl is present4The addition of (A) is a one-time addition. The feed formulation is shown in Table 9, and the results of the physical property tests are shown in Table 10. As can be seen from Table 10, the physical properties, coupling degree and coupling efficiency of the product obtained by adding the coupling agent in one step are inferior to those of the coupling method in which the coupling agent is added in two steps.
TABLE 1 examples of Linear SIS dosing formulations
| Fitting for mixing Square block Number (C) | S/I (Wt) | Design of Mn (Wan) | Monomer Concentration of (Wt％) | Monomer Total amount of (kg) | A section | Two sections | Three sections | In a solvent Raffinate oil Percentage of (％) | |||||
| Solvent(s) (l) | Styrene (meth) acrylic acid ester (kg) | Activating agent (mol) | Initiator (mol) | Isoprene (I) (kg) | Activating agent (mol) | Solvent(s) (l) | Styrene (meth) acrylic acid ester (kg) | ||||||
| 1 | 15/85 | 10 | 10.3 | 1883 | 19635 | 143 | 26.4 | 18.9 | 1600 | 19.9 | 509 | 140 | 20 |
| 2 | 15/85 | 12 | 13.8 | 2601 | 19651 | 196 | 34.8 | 21.7 | 2211 | 25.5 | 309 | 194 | 20 |
| 3 | 15/85 | 10 | 17.0 | 3090 | 19641 | 233 | 61.8 | 30.9 | 2627 | 45.4 | 509 | 230 | 20 |
| 4 | 15/85 | 12 | 16.4 | 3028 | 19665 | 228 | 68.4 | 25.3 | 2574 | 0 | 549 | 226 | 20 |
| 5 | 20/80 | 12 | 13.8 | 2536 | 19661 | 255 | 51.0 | 21.2 | 2029 | 0 | 514 | 252 | 20 |
| 6 | 20/80 | 10 | 16.2 | 3057 | 19640 | 307 | 61.0 | 30.6 | 2445 | 40.7 | 504 | 305 | 20 |
| 7 | 20/80 | 12 | 17.1 | 3271 | 19658 | 328 | 54.0 | 27.5 | 2617 | 29.6 | 540 | 326 | 20 |
| 8 | 24/76 | 10 | 11.4 | 2092 | 19642 | 252 | 39.4 | 20.9 | 1590 | 22.1 | 544 | 250 | 20 |
| 9 | 24/76 | 12 | 13.8 | 2582 | 19639 | 313 | 34.6 | 21.6 | 1963 | 27.6 | 300 | 306 | 0 |
| 10 | 20/80 | 10 | 11.3 | 1966 | 19655 | 198 | 27.6 | 19.7 | 1573 | 26.9 | 309 | 195 | 0 |
TABLE 2 Properties of Linear SIS products
| Fitting for mixing Square block Number (C) | 300% definite elongation Strength of (MPa) | Tensile strength Strength of (MPa) | Elongation at break Length of growth (％) | Permanent deformation (％) | Hardness of (Shao) | Melt flow Dynamic rate (g/10min) |
| 1 | 0.6 | 24.4 | 1300 | 12 | 48 | 10.5 |
| 2 | 0.7 | 25.0 | 1250 | 20 | 45 | 8.7 |
| 3 | 0.6 | 24.1 | 1300 | 24 | 45 | 9.6 |
| 4 | 0.6 | 17.8 | 1150 | 32 | 57 | 2.8 |
| 5 | 0.6 | 17.1 | 1200 | 24 | 51 | 2.4 |
| 6 | 0.7 | 22.0 | 1300 | 24 | 38 | 7.3 |
| 7 | 0.9 | 19.9 | 1270 | 24 | 44 | 6.5 |
| 8 | 1.3 | 19.5 | 1200 | 28 | 59 | 5.6 |
| 9 | 1.6 | 24.0 | 1300 | 20 | 54 | 8.4 |
| 10 | 0.7 | 20.1 | 1300 | 24 | 42 | 6.2 |
TABLE 3 Star (SI) nR dosing formulation examples
| Fitting for mixing Square block Number (C) | S/I (Wt) | Design of Mn (Wan) | Monomer Concentration of (Wt％) | Monomer Total amount of (Wt) | A section | Two sections | Three sections | In a solvent Raffinate oil (％) | ||||
| Solvent(s) (l) | Styrene (meth) acrylic acid ester (kg) | Activating agent (mol) | Initiator (mol) | Isoprene (I) (kg) | Butadiene (kg) | SiCl4 (mol) | ||||||
| 11 | 15/85 | 16 | 11.4 | 2035 | 20150 | 305 | 145.8 | 50.9 | 1730 | 0 | 14.0 | 0 |
| 12 | 20/85 | 16 | 15.0 | 2773 | 20014 | 555 | 169.0 | 69.4 | 2218 | 33.3 | 19.1 | 0 |
| 13 | 15/85 | 16 | 13.5 | 2467 | 20135 | 370 | 150 | 61.7 | 2097 | 0 | 17.0 | 10 |
| 14 | 15/85 | 20 | 15.3 | 2849 | 20087 | 427 | 142.5 | 57.0 | 2422 | 39.5 | 15.7 | 10 |
| 15 | 15/85 | 28 | 16.8 | 3179 | 20054 | 477 | 112.5 | 45.5 | 2702 | 32.2 | 12.6 | 10 |
| 16 | 20/80 | 16 | 12.0 | 2164 | 20215 | 433 | 108.2 | 54.2 | 1731 | 0 | 15.0 | 10 |
| 17 | 20/80 | 20 | 14.6 | 2701 | 20125 | 540 | 121.5 | 54.1 | 2161 | 26.0 | 15.0 | 10 |
| 18 | 20/80 | 28 | 17.0 | 3222 | 20038 | 644 | 115 | 46.1 | 2578 | 42.4 | 12.7 | 10 |
TABLE 4 physical Properties of Star-Shaped (SI) nR products
| Fitting for mixing Square block Number (C) | 300% definite elongation Strength of (MPa) | Tensile strength Strength of (MPa) | Elongation at break Length of growth (％) | Permanent deformation (％) | Hardness of (Shao) | Melt flow Speed of rotation (g/10 min) | Degree of coupling f | Coupling of Efficiency of (％) |
| 11 | 0.6 | 13.7 | 1196 | 18 | 52 | 7.6 | 2.4 | 59.4 |
| 12 | 0.8 | 19.4 | 1200 | 24 | 38 | 9.0 | 3.5 | 91.0 |
| 13 | 0.7 | 13.2 | 980 | 28 | 48 | 6.7 | 2.3 | 70.9 |
| 14 | 0.7 | 20.6 | 1300 | 29 | 42 | 9.3 | 3.6 | 93.2 |
| 15 | 0.9 | 19.9 | 1250 | 26 | 43 | 8.9 | 3.5 | 91.5 |
| 16 | 0.7 | 12.6 | 1150 | 20 | 42 | 6.5 | 2.5 | 65.3 |
| 17 | 0.7 | 20.8 | 1300 | 20 | 43 | 9.1 | 3.7 | 94.3 |
| 18 | 0.7 | 19.7 | 1250 | 30 | 45 | 8.5 | 3.5 | 92.0 |
TABLE 5 example Linear SIS dosing formulations
| Fitting for mixing Square block Number (C) | S/I (Wt) | Design of Mn (Wan) | Monomer Concentration of (Wt％) | Monomer Total amount of (Wt) | A section | Two sections | Three sections | In a solvent Raffinate oil Percentage of (％) | |||||
| Solvent(s) (l) | Styrene (meth) acrylic acid ester (kg) | Activating agent (mol) | Initiator (mol) | Isoprene (I) (kg) | Activating agent (mol) | Solvent(s) (l) | Styrene (meth) acrylic acid ester (kg) | ||||||
| 19 | 15/85 | 10 | 8.5 | 1469 | 19640 | 111 | 26.4 | 14.7 | 1248 | 14.5 | 510 | 110 | 30 |
| 20 | 15/85 | 12 | 12.0 | 2159 | 19663 | 162 | 36.0 | 18.0 | 1835 | 15.4 | 509 | 162 | 40 |
| 21 | 20/80 | 10 | 10.2 | 1798 | 19652 | 180 | 33.0 | 18.0 | 1438 | 15.4 | 514 | 180 | 30 |
| 22 | 20/80 | 12 | 13.5 | 2469 | 19642 | 247 | 37.0 | 20.6 | 1975 | 26.2 | 508 | 247 | 40 |
| 23 | 25/75 | 10 | 11.3 | 2019 | 19648 | 253 | 40.0 | 20.2 | 1514 | 26.1 | 540 | 252 | 30 |
| 24 | 25/75 | 12 | 9.6 | 1684 | 19655 | 211 | 28.0 | 14.0 | 1263 | 14.5 | 545 | 210 | 40 |
TABLE 6 SIS product Properties
| Fitting for mixing Square block Number (C) | 300% definite elongation Strength of (MPa) | Tensile strength Strength of (MPa) | Elongation at break Length of growth (％) | Permanent deformation (％) | Hardness of (Shao's A) |
| 19 | 0.7 | 19.9 | 1300 | 16 | 40 |
| 20 | 0.9 | 23.5 | 1250 | 20 | 42 |
| 21 | 0.9 | 21.4 | 1300 | 17 | 38 |
| 22 | 1.0 | 22.5 | 1300 | 20 | 36 |
| 23 | 0.8 | 24.0 | 1250 | 21 | 45 |
| 24 | 1.0 | 20.9 | 1300 | 19 | 38 |
TABLE 7 Star (SI) nR dosing formulation examples
| Fitting for mixing Square block Number (C) | S/I (Wt) | Design of Mn (Wan) | Monomer Concentration of (Wt％) | Monomer Total amount of (Wt) | A section | Two sections | Three sections | In a solvent Raffinate oil (％) | ||||
| Solvent(s) (l) | Styrene (meth) acrylic acid ester (kg) | Activating agent (mol) | Initiator (mol) | Isoprene (I) (kg) | Butadiene (kg) | SiCl4 (mol) | ||||||
| 25 | 15/85 | 18 | 15.2 | 2837 | 20160 | 426 | 170.1 | 63.1 | 2411 | 26.5 | 15.8 | 20 |
| 26 | 15/85 | 24 | 12.6 | 2288 | 20215 | 343 | 114.0 | 38.1 | 1945 | 18.2 | 10.5 | 30 |
| 27 | 15/85 | 26 | 10.5 | 1865 | 20250 | 280 | 86.1 | 28.7 | 1585 | 19.7 | 8.6 | 30 |
| 28 | 20/80 | 18 | 14.5 | 2688 | 20190 | 538 | 177.0 | 59.8 | 2150 | 0 | 16.5 | 30 |
| 29 | 20/80 | 24 | 13.2 | 2415 | 20230 | 483 | 120.0 | 40.3 | 1932 | 28.7 | 10.5 | 20 |
| 30 | 20/80 | 26 | 11.0 | 1965 | 20243 | 393 | 90.0 | 30.3 | 1572 | 0 | 8.5 | 20 |
TABLE 8 (SI) nR product Properties
| Fitting for mixing Square block Number (C) | 300% definite elongation Strength of (MPa) | Tensile strength Strength of (MPa) | Elongation at break Length of growth (％) | Permanent deformation (％) | Hardness of (Shao's A) | Degree of coupling f | Coupling of Efficiency of (％) |
| 25 | 0.9 | 19.4 | 1250 | 20 | 42 | 3.5 | 92.0 |
| 26 | 0.8 | 20.3 | 1300 | 21 | 43 | 3.6 | 91.5 |
| 27 | 1.0 | 19.8 | 1250 | 19 | 45 | 3.5 | 91.0 |
| 28 | 0.6 | 13.5 | 1200 | 18 | 42 | 2.5 | 70.6 |
| 29 | 0.9 | 20.5 | 1250 | 20 | 42 | 3.5 | 91.0 |
| 30 | 0.7 | 14.4 | 1150 | 20 | 44 | 2.6 | 69.8 |
TABLE 9 Star (SI) nR dosing formulation examples
| Fitting for mixing Square block Number (C) | S/I (Wt) | Design of Mn (Wan) | Monomer Concentration of (Wt％) | Monomer Total amount of (Wt) | A section | Two sections | Three sections | In a solvent Raffinate oil (％) | ||||
| Solvent(s) (l) | Styrene (meth) acrylic acid ester (kg) | Activating agent (mol) | Initiator (mol) | Isoprene (I) (kg) | Butadiene (kg) | SiCl4 (mol) | ||||||
| 31 | 15/85 | 16 | 14.3 | 2648 | 20216 | 398 | 180.0 | 66.2 | 2250 | 26.8 | 18.2 | 0 |
| 32 | 15/85 | 20 | 13.8 | 2546 | 20255 | 382 | 150.0 | 50.9 | 2164 | 23.8 | 14.8 | 20 |
| 33 | 15/85 | 28 | 12.3 | 2236 | 20305 | 336 | 96.0 | 32.0 | 1900 | 0 | 9.0 | 30 |
| 34 | 20/80 | 16 | 16.5 | 3138 | 20226 | 628 | 211.8 | 78.5 | 2510 | 0 | 20.0 | 20 |
| 35 | 20/80 | 20 | 13.5 | 2474 | 20196 | 495 | 133.5 | 49.5 | 1979 | 28.0 | 13.7 | 30 |
| 36 | 20/80 | 28 | 11.4 | 2046 | 20260 | 410 | 69.0 | 29.3 | 1636 | 20.5 | 8.2 | 0 |
TABLE 10 (SI) nR product Properties
| Fitting for mixing Square block Number (C) | 300% definite elongation Strength of (MPa) | Tensile strength Strength of (MPa) | Elongation at break Length of growth (％) | Permanent deformation (％) | Hardness of (Shao's A) | Degree of coupling f | Coupling of Efficiency of (％) |
| 31 | 0.7 | 18.5 | 1250 | 21 | 45 | 3.2 | 90.0 |
| 32 | 0.6 | 19.0 | 1200 | 22 | 44 | 3.1 | 89.5 |
| 33 | 0.5 | 11.5 | 1150 | 20 | 48 | 2.1 | 57.2 |
| 34 | 0.5 | 10.8 | 1150 | 18 | 42 | 2.2 | 58.0 |
| 35 | 0.6 | 17.9 | 1200 | 20 | 43 | 3.0 | 88.3 |
| 36 | 0.7 | 18.0 | 1250 | 19 | 50 | 3.1 | 89.0 |
Claims (13)
1. The preparation method of styrene-isoprene block copolymer with linear SIS structure adopts cyclohexane as solvent, n-butyllithium or sec-butyllithium as initiator and tetrahydrofuran as activating agent, and adopts three-step charging process to prepare the described copolymer, i.e. it is made up by using cyclohexane as solvent, n-butyllithium or sec-butyllithium as activating agent and adopting three-step charging process
(1) Adding a solvent and styrene into a polymerization kettle, initiating a first block polymerization reaction at 45-55 ℃ in the presence of an initiator and an activator, controlling the reaction temperature to be 50-80 ℃, and the reaction time to be 20-30 min, wherein the mole number of the activator is 2-6 times that of the initiator;
(2) after the first block is polymerized, adding an isoprene monomer into a polymerization kettle, initiating the polymerization of the second block at 40-60 ℃ for 5-20min, and then controlling the reaction temperature at 70-120 ℃ and the reaction time for 30-45 min;
(3) after the second block polymerization is finished, adding tetrahydrofuran serving as an activating agent into a polymerization kettle, controlling the molar ratio of the addition amount of the tetrahydrofuran to the addition amount of an initiator to be 1.0-2.0, controlling the initiation temperature to be not lower than 70 ℃, adding a styrene monomer, carrying out third block polymerization, and controlling the reaction time to be 20-25min so as to discharge.
2. The preparation of styrene-isoprene block copolymer according to claim 1, wherein the ratio of the number of moles of the activator to the number of moles of the initiator added in the third step is 1.05-1.35.
3. The preparation of styrene-isoprene block copolymer according to claim 1, wherein the initiation temperature of the third segment is 80-85 ℃.
4. The preparation method of styrene-isoprene block copolymer with Star (SI) nR structure adopts cyclohexane as solvent, n-butyllithium or sec-butyllithium as initiator and tetrahydrofuran as activating agent, and adopts two-step charging coupling process to prepare the invented copolymer
(1) Adding a solvent and styrene into a polymerization kettle, initiating a first block polymerization reaction at 45-55 ℃ in the presence of an initiator and an activator, controlling the reaction temperature to be 50-80 ℃, and controlling the reaction time to be 20-30 min;
(2) after the first block is polymerized, adding an isoprene monomer into a polymerization kettle, initiating the polymerization of the second block at 40-60 ℃ for 5-20min, and then controlling the reaction temperature at 70-120 ℃ and the reaction time for 30-45 min;
(3) adding a coupling agent SiCl after the second block polymerization is finished4Coupling is carried out, the total mole number of the added coupling agent is 0.25-0.30 time of the mole number of the initiator, the coupling agent is added in two times, 70 percent of the total amount is added for the first time, the residual amount is added for the second time after 10min, and the coupling reaction is finished after 20-25 min.
5. The method of preparing styrene-isoprene block copolymer according to claim 4, wherein butadiene is added before the addition of the coupling agent in the third step, and the number of moles of butadiene added is 1 to 14 times that of the initiator.
6. The preparation of styrene-isoprene block copolymer according to claim 5, wherein the molar number of butadiene added is 2 to 3 times that of the initiator.
7. The preparation of styrene-isoprene block copolymers according to claim 1 or 4, characterized in that the initiation temperature of the second stage is 40-50 ℃.
8. The process for producing a styrene-isoprene block copolymer according to claim 1 or 4, wherein a mixed solution of cyclohexane and raffinate oil is used as the solvent, wherein the raffinate oil is 1 to 50% in percentage, and the raffinate oil is a gasoline fraction remaining after the aromatic hydrocarbons are extracted from a refinery by platinum reforming and has a boiling range of 60 to 140 ℃.
9. The process for producing a styrene-isoprene block copolymer according to claim 8, wherein the raffinate oil used is a fraction obtained by cutting and having a boiling range of 65 to 90 ℃.
10. A process for producing a styrene-isoprene block copolymer according to claim 1 or 4, characterized in that
(1) The used isoprene monomer is refined, wherein the purity of isoprene is more than or equal to 99.5 percent, the water content is less than or equal to 20ppm, cyclopentadiene is less than or equal to 2ppm, alkyne is less than or equal to 20ppm, carbonyl compound is less than or equal to 10ppm, and piperylene is less than or equal to 80 ppm;
(2) the styrene monomer is refined, wherein the purity of the styrene is more than or equal to 99.5 percent, the water content is less than or equal to 20ppm, the benzaldehyde content is less than or equal to 50ppm, and the content of the self-polymer is less than or equal to 300 ppm.
11. The method of claim 10, wherein the isoprene is purified by atmospheric distillation using a high-efficiency wire-mesh corrugated packed column and adsorption-removal of 3 Å, 4 Å, 5 Å molecular sieves in the order of 1: 2: 3.
12. The method of claim 10, wherein the styrene is refined by vacuum distillation of side stream and Al in a high efficiency wire mesh corrugated packed column2O3The 3A molecular sieve is matched according to the proportion of 1: 1, and is adsorbed and removed according to the sequence.
13. The method of preparing styrene-isoprene block copolymer according to claim 1 or 4, wherein n-butyllithium or sec-butyllithium as a scavenger is added before the initiator and the activator in the first step, depending on the content of harmful impurities in the solvent and styrene.
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|---|---|---|---|
| CN 96118322 CN1175595A (en) | 1996-09-02 | 1996-09-02 | Preparation method of styrene-isoprene block copolymer |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833945A (en) * | 2012-11-27 | 2014-06-04 | 中国石油天然气股份有限公司 | Star-shaped isoprene-styrene block copolymer and preparation method thereof |
| CN105218766A (en) * | 2015-11-10 | 2016-01-06 | 宁波科元特种橡胶有限公司 | A kind of synthetic method of styrene isoprene styrene block copolymer (SIS) |
| CN106866905A (en) * | 2017-03-31 | 2017-06-20 | 安徽同心化工有限公司 | A kind of isoprene is modified dicyclopentadiene petroleum resin and preparation method |
-
1996
- 1996-09-02 CN CN 96118322 patent/CN1175595A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833945A (en) * | 2012-11-27 | 2014-06-04 | 中国石油天然气股份有限公司 | Star-shaped isoprene-styrene block copolymer and preparation method thereof |
| CN103833945B (en) * | 2012-11-27 | 2016-12-21 | 中国石油天然气股份有限公司 | Star-shaped isoprene-styrene block copolymer and preparation method thereof |
| CN105218766A (en) * | 2015-11-10 | 2016-01-06 | 宁波科元特种橡胶有限公司 | A kind of synthetic method of styrene isoprene styrene block copolymer (SIS) |
| CN106866905A (en) * | 2017-03-31 | 2017-06-20 | 安徽同心化工有限公司 | A kind of isoprene is modified dicyclopentadiene petroleum resin and preparation method |
| CN106866905B (en) * | 2017-03-31 | 2019-08-30 | 安徽同心化工有限公司 | A kind of modified dicyclopentadiene petroleum resin of isoprene and preparation method |
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