CN1376721A - Process for reducing permanent deformation of low-learity styrene type thermoplastic elastomer - Google Patents
Process for reducing permanent deformation of low-learity styrene type thermoplastic elastomer Download PDFInfo
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- CN1376721A CN1376721A CN 02114024 CN02114024A CN1376721A CN 1376721 A CN1376721 A CN 1376721A CN 02114024 CN02114024 CN 02114024 CN 02114024 A CN02114024 A CN 02114024A CN 1376721 A CN1376721 A CN 1376721A
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- styrene
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- thermoplastic elastomer
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims description 21
- 238000000034 method Methods 0.000 title claims description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 150000001993 dienes Chemical class 0.000 claims abstract description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 30
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 24
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 150000003440 styrenes Chemical class 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229920001971 elastomer Polymers 0.000 abstract 1
- 239000000806 elastomer Substances 0.000 abstract 1
- 229920001169 thermoplastic Polymers 0.000 abstract 1
- 239000004416 thermosoftening plastic Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- HASGOCLZFTZSTN-UHFFFAOYSA-N cyclohexane;hexane Chemical compound CCCCCC.C1CCCCC1 HASGOCLZFTZSTN-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A process for preparing the low-linearity thermoplastic styrene elastomer with less permanent deformation includes the stage-1 reaction of styrene monomer on n-butyl lithium or para-butyl lithium as trigger in the solvent of cyclohexane or the mixtural of cyclohexane and hexane at 40-50 deg.C for 20-50 min, adding conjugated diolefin monomer and styrene monomer, stage-2 reaction at 50-60 deg.C for 20-50 min, and stage-3 reaction at 50-60 deg.C for 20-50 min. Its advantages are correct metering and simple operating.
Description
Technical field
The present invention relates to a kind of method that reduces permanent deformation of low-learity styrene type thermoplastic elastomer, more particularly, relate to the method that reduces type SBS, SIS, m-SBM-S tension set.
Background technology
Generally speaking, the line style styrene analog thermoplastic elastomer can adopt following route synthetic: with the lithium alkylide is initiator, hexanaphthenes etc. are solvent, tetrahydrofuran (THF) is an activator, vinylbenzene or alpha-methyl styrene, divinyl or isoprene are that monomer adopts three-step approach, the segmented copolymer that forms by anionic solution polymerization.
A kind of method of the SBS of reduction set deformation volume is disclosed as Chinese patent CN85 102259B in the prior art, this patent is to adopt to add a small amount of conjugated diene in the first step polymerization process in styrene monomer, but the consumption of conjugated diene is 0.01-5.0% seldom only, is difficult to accurately metering and is difficult for realizing industrialization.Secondly, adopt the set deformation volume of this method products obtained therefrom still bigger, in 16%～44% scope,, be difficult to prepare tension set and be lower than 20% line style styrene analog thermoplastic elastomer product usually 28%～40%.The 3rd, this patent is that alpha-methyl styrene, isoprene analog thermoplastic elastomer do not relate to monomer.
Summary of the invention
The object of the invention is to overcome the defective that exists in the prior art, provide a kind of after preparation line style styrene analog thermoplastic elastomer is finished one section monomer polymerization reactions, adopt two, three sections monomer to add in the reactor simultaneously, be about to conjugated diene monomer (divinyl or isoprene) and add simultaneously with styrene monomer (vinylbenzene or alpha-methyl styrene) and carry out two sections, three sections reactions in the reactor, synthesize tension set and be lower than 25% line style styrene analog thermoplastic elastomer.
The concrete technology contents of the present invention is as follows:
With n-Butyl Lithium or s-butyl lithium is initiator (when n-Butyl Lithium is initiator, should add a small amount of activator such as tetrahydrofuran (THF) etc.), and hexanaphthene or cyclohexane hexane mixed solution etc. is a solvent.After first section vinylbenzene (or alpha-methyl styrene) has reacted, with conjugated diene (divinyl or isoprene), styrene monomer (as vinylbenzene or alpha-methyl styrene) adds together and carries out two sections, three sections reactions in the reactor, and reaction is finished after condense, make the line style styrene analog thermoplastic elastomer after the drying.This product tension set is less than 25%, and other physical and mechanical propertiess of product and former three-step approach are quite synthetic.
The styrene monomer consumption is that the corresponding with it conjugated diene consumption of 15%～40% (is benchmark with the monomer total mass) is 85%～60% in the product of the present invention.
The prepared line style styrene analog thermoplastic elastomer mean number average molecular weight of the present invention is 50,000-200, and 000 polymeric reaction temperature scope: 40 ℃～50 ℃ of one section kick off temperatures, the reaction top temperature must not be above 75 ℃.Two sections, three sections kick off temperatures are 50 ℃～60 ℃, and the reaction top temperature must not be above 110 ℃.Polymerization reaction time: one section reaction times 20min～50min.Two periods, three periods reaction times are 20min～50min.Reaction monomers concentration is 10%～20% (weight percent).
The present invention has the following advantages:
1. simple to operate, two kinds of monomer accurate measurements.
2. the products therefrom tension set is less, below 25%.
3. simple during suitability for industrialized production.
Know-why of the present invention mainly is to utilize styrene monomer and conjugated diolefin monomer to be wanting in apart from obvious at reactivity ratio, and conjugated diolefin monomer polymerization reactions speed is much larger than the polymerization rate of styrene monomer.Two, three sections monomers add fashionable simultaneously, at first reaction mainly is the conjugated diolefin monomer, carrying out along with reaction, the conjugated diolefin monomer concentration is more and more lower, having seldom this moment that weight phenylethylene class monomer and conjugated diolefin monomer generate a bit of random copolymers, is that styrene monomer reacts at last, and this segment random copolymers does not influence the two-phase separating effect of whole product, product has two second-order transition temperatures, and other physical and mechanical properties end of product is influenced.
Physical and mechanical properties according to method synthetic line style styrene analog thermoplastic elastomer provided by the present invention: 300% tensile modulus: 0.8Mpa～8.0Mpa, tensile strength: 5.0Mpa～38Mpa, tensile yield: 650%～1200%, tension set: 4%～30%, shore hardness: 40 Shao A～95 Shao A.
The preparation of specific embodiment 1. line style styrene analog thermoplastic elastomers.
Embodiment 1
Handling clean and with the 5 liter iron stills (band stirs) of nitrogen protection, (or 50m
3Polymeric kettle) in, adds solvent hexanaphthene, vinylbenzene, the tetrahydrofuran (THF) measure, add initiator n-Butyl Lithium (or s-butyl lithium) after still is warming up to 40 ℃～50 ℃.Behind the reaction 30min, vinylbenzene, the divinyl that measures added in the reactor simultaneously, the control top temperature must not surpass 110 ℃, reaction 30min.Termination reaction, discharging add 0.6% 2.6.4 (2.6 1 di-t-butyls, 4-methylphenol) of monomer gross weight, glue after cohesion white polymer, promptly get product after drying.With vinylbenzene, divinyl is that reaction monomers is carried out different vinylbenzene and divinyl proportioning test, and experimental data is listed in table 1.
Table 1
Embodiment 2
| Sequence number | ??S/B | One section vinylbenzene (g) | Two sections, three sections | |
| Divinyl (g) | Vinylbenzene (g) | |||
| ??1A | ??15/85 | ????24 | ????272 | ????24 |
| ??2A | ??20/80 | ????32 | ????256 | ????32 |
| ??3A | ??30/70 | ????48 | ????224 | ????48 |
| ??4A | ??40/60 | ????64 | ????192 | ????64 |
Substituting divinyl with isoprene tests.Reaction conditions is with embodiment 1, and experimental data is listed in table 2.
Table 2
Embodiment 3
| Sequence number | ????S/I | One section vinylbenzene (g) | Two sections, three sections | |
| Isoprene (g) | Vinylbenzene (g) | |||
| ??5A | ????15/85 | ????24 | ????272 | ????24 |
| ??6A | ????20/80 | ????32 | ????256 | ????32 |
| ??7A | ????30/70 | ????48 | ????224 | ????48 |
| ??8A | ????40/60 | ????64 | ????192 | ????64 |
Substitute vinylbenzene with alpha-methyl styrene, reaction conditions is with embodiment 1, and the experimental data example is in table 3.
Table 3
Embodiment 4
| Sequence number | ??MS/B | One section alpha-methyl styrene (g) | Two sections, three sections | |
| Divinyl (g) | Alpha-methyl styrene (g) | |||
| ?9A | ??15/85 | ????24 | ????272 | ????24 |
| ?10A | ??20/80 | ????32 | ????256 | ????32 |
| ?11A | ??30/70 | ????48 | ????224 | ????48 |
| ?12A | ??40/60 | ????64 | ????192 | ????64 |
At 50m
3In the polymeric kettle, be that monomer carries out industrial production with vinylbenzene, divinyl.Temperature of reaction, time, production data was listed in table 4 with embodiment 1.
Table 4
Embodiment 5
| Sequence number | ??S/B | One section vinylbenzene (kg) | Two sections, three sections | |
| Divinyl (kg) | Vinylbenzene (kg) | |||
| ??13A | ??15/85 | ????337.5 | ????3825 | ????337.5 |
| ??14A | ??20/80 | ????450 | ????3600 | ????450 |
| ??15A | ??30/70 | ????675 | ????3150 | ????675 |
| ??16A | ??40/60 | ????900 | ????2700 | ????900 |
At 50m
3In the polymeric kettle, be that monomer carries out commerical test with vinylbenzene, isoprene.Working condition is with embodiment 1, and production data is listed in table 5.
Table 5
2. the physical and mechanical properties of product test.
| Sequence number | ????S/B | One section vinylbenzene (kg) | Two sections, three sections | |
| Isoprene (kg) | Vinylbenzene (kg) | |||
| ??17A | ??15/85 | ????337.5 | ????3825 | ????337.5 |
| ??18A | ??20/80 | ????450 | ????3600 | ????450 |
| ??19A | ??30/70 | ????675 | ????3150 | ????675 |
| ??20A | ??40/60 | ????900 | ????2700 | ????900 |
The line style styrene analog thermoplastic elastomer that the foregoing description is prepared carries out the physical and mechanical properties test, wherein 300% tensile modulus, tensile strength, tensile yield, tension set are carried out by GB GB/T528-92, and shore hardness is carried out by GB GB/T531-92.Test result is as shown in table 6:
Table 6
Comparative example: Comparative Examples 1
| Sequence number | Tension set % | 300% tensile modulus MPa | Tensile strength MPa | Pull apart/elongation % | Shore hardness (Shao A) |
| ??1A | ????8 | ????0.8 | ????6.7 | ????1100 | ????44 |
| ??2A | ????14 | ????1.0 | ????8.4 | ????1100 | ????58 |
| ??3A | ????20 | ????2.3 | ????15.4 | ????950 | ????74 |
| ??4A | ????24 | ????2.8 | ????21.7 | ????750 | ????87 |
| ??5A | ????4 | ????1.2 | ????12.8 | ????1200 | ????43 |
| ??6A | ????14 | ????2.0 | ????18.6 | ????1200 | ????53 |
| ??7A | ????18 | ????2.1 | ????23.1 | ????1100 | ????72 |
| ??8A | ????24 | ????2.8 | ????31.7 | ????1050 | ????83 |
| ??9A | ????6 | ????1.2 | ????7.9 | ????1100 | ????41 |
| ??10A | ????12 | ????1.8 | ????10.3 | ????1050 | ????59 |
| ??11A | ????20 | ????1.7 | ????15.7 | ????9500 | ????73 |
| ??12A | ????24 | ????3.7 | ????25.6 | ????680 | ????88 |
| ??13A | ????6 | ????1.0 | ????7.3 | ????1100 | ????43 |
| ??14A | ????16 | ????1.3 | ????10.4 | ????1050 | ????56 |
| ??15A | ????20 | ????1.9 | ????18.1 | ????850 | ????75 |
| ??16A | ????23 | ????3.3 | ????27.2 | ????700 | ????87 |
| ??17A | ????8 | ????0.8 | ????15.3 | ????1200 | ????39 |
| ??18A | ????12 | ????1.9 | ????19.9 | ????1200 | ????48 |
| ??19A | ????20 | ????2.7 | ????21.3 | ????1100 | ????69 |
| ??20A | ????24 | ????2.8 | ????32.7 | ????1000 | ????86 |
The line style styrene analog thermoplastic elastomer adopts original three-step approach production technology to be first section and carries out the styrene monomer reaction, after question response is finished, adds the conjugated diene monomer reaction again, adds styrene monomer at last again and reacts.Other condition is with embodiment 1, and experimental data is listed in table 7, and the physical and mechanical properties test result is listed in table 8.
Table 7
| Sequence number | ????S/B | One section vinylbenzene (g) | Two sections divinyl (g) | Three sections vinylbenzene (g) |
| ??1B | ??15/85 | ????24 | ????272 | ????24 |
| ??2B | ??20/80 | ????32 | ????256 | ????32 |
| ??3B | ??30/70 | ????48 | ????224 | ????48 |
| ??4B | ??40/60 | ????64 | ????196 | ????64 |
Table 8
Comparative Examples 2
| Sequence number | Tension set % | 300% tensile modulus MPa | Tensile strength MPa | Pull apart/elongation % | Shore hardness (Shao A) |
| ??1B | ????28 | ????0.6 | ????5.6 | ????1100 | ????40 |
| ??2B | ????36 | ????1.2 | ????6.7 | ????1000 | ????59 |
| ??3B | ????40 | ????1.8 | ????13.7 | ????900 | ????75 |
| ??4B | ????56 | ????19.6 | ????2.3 | ????650 | ????87 |
Adopt patent CN85 102259B method, adding the conjugated diene amount in one section reaction is (0.5% weight ratio), and other condition is with embodiment 1, and experimental data is listed in table 9, the physical and mechanical properties test result is listed in table 10.
Table 9
| Sequence number | ??S/B | One section vinylbenzene (g) | Two sections divinyl (g) | Three sections vinylbenzene (g) |
| ??1C | ??15/85 | ????24 | ????272 | ????24 |
| ??2C | ??20/80 | ????32 | ????256 | ????32 |
| ??3C | ??30/70 | ????48 | ????224 | ????48 |
| ??4C | ??40/60 | ????64 | ????196 | ????64 |
Table 10
| Sequence number | Tension set % | 300% tensile modulus MPa | Tensile strength MPa | Pull apart/elongation % | Hardness (Shao Shi) |
| ??1C | ????16 | ????1.0 | ????6.0 | ????1100 | ????39 |
| ??2C | ????24 | ????1.1 | ????8.3 | ????1100 | ????57 |
| ??3C | ????30 | ????1.9 | ????14.9 | ????900 | ????73 |
| ??4C | ????40 | ????3.7 | ????20.8 | ????600 | ????89 |
Contrast table 6,8,10 as can be known, under equal conditions prepared permanent deformation of low-learity styrene type thermoplastic elastomer is lower than in addition two kinds of line style styrene analog thermoplastic elastomers that method is prepared according to the present invention.Other physical and mechanical properties is roughly suitable.
The made line style styrene analog thermoplastic elastomer of the present invention is carried out second-order transition temperature (Tg) to be measured.Data are listed in table 11
Table 11
| Sequence number | 1A | 2A | 3A | 4A | 5A | 8A | 15A | ?19A |
| ?Tg1 | -88 | -90 | -87 | -85 | -90 | -88 | -87 | ?- |
| ?Tg2 | 87 | 89 | 92 | 90 | 84 | 85 | 90 | ?87 |
As shown in Table 11, adopt the prepared line style styrene analog thermoplastic elastomer of the present invention, still have tangible two-phase separating effect.
Claims (3)
1. method that reduces permanent deformation of low-learity styrene type thermoplastic elastomer, styrene analog thermoplastic elastomer comprises with vinylbenzene, divinyl is monomer synthetic SBS, with vinylbenzene, isoprene is monomer synthetic SIS, with alpha-methyl styrene, divinyl is the m-SBS of the full one-tenth of monomer, with n-Butyl Lithium or s-butyl lithium is that initiator is (when n-Butyl Lithium is initiator, should add a small amount of activator such as tetrahydrofuran (THF) etc.), hexanaphthene or hexanaphthene, hexane mixed solution etc. is a solvent, one section kick off temperature is 40 ℃～50 ℃, the top temperature of reaction must not surpass 75 ℃, and the reaction times is 20min～50min; Two sections, three sections kick off temperatures are 50 ℃～60 ℃, and the top temperature of reaction must not surpass 110 ℃, and the reaction times is 20min～50min; Reaction monomers concentration is 10%～20% (weight percent); It is waited to levy and is after one section styrene monomer has reacted, and conjugated diolefin monomer and styrene monomer is together added carry out two sections, three sections reactions in the reactor.
2. method according to claim 1 is characterized in that styrenic content is 15%～40% (quality), and conjugated diolefin content is 85%～60%.
4. method according to claim 1 and 2 is characterized in that the molecular-weight average of line style styrene analog thermoplastic elastomer is controlled at 50000～20000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021140243A CN1182169C (en) | 2002-03-30 | 2002-03-30 | Process for reducing permanent deformation of low-learity styrene type thermoplastic elastomer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021140243A CN1182169C (en) | 2002-03-30 | 2002-03-30 | Process for reducing permanent deformation of low-learity styrene type thermoplastic elastomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1376721A true CN1376721A (en) | 2002-10-30 |
| CN1182169C CN1182169C (en) | 2004-12-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021140243A Expired - Lifetime CN1182169C (en) | 2002-03-30 | 2002-03-30 | Process for reducing permanent deformation of low-learity styrene type thermoplastic elastomer |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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) |
| CN106554474A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of low method expanded from film from film expansion rate linear hydrogenated styrene analog thermoplastic elastomer |
-
2002
- 2002-03-30 CN CNB021140243A patent/CN1182169C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554474A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of low method expanded from film from film expansion rate linear hydrogenated styrene analog thermoplastic elastomer |
| 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) |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1182169C (en) | 2004-12-29 |
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Owner name: BALING PETROCHEMICAL CO., LTD., SINOPEC Free format text: FORMER OWNER: YUEYANG PETROCHEMICAL PLANT, BALING PETROCHEMICAL CORP. Effective date: 20030103 |
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Owner name: CHINA PETROCHEMICAL CORPORATION; BALING PETROCHEM Free format text: FORMER OWNER: BALING PETROCHEMICAL CO., LTD., SINOPEC Effective date: 20070622 |
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| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20070622 Address after: 100029 No. 6, Xin Xin Street East, Beijing, Chaoyang District Co-patentee after: Baling Petrochemical Co., Ltd., SINOPEC Patentee after: China Petrochemical Group Corp. Address before: 414014 Yunxi District, Hunan, Yueyang Patentee before: Baling Petrochemical Co., Ltd., SINOPEC |
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| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20041229 |