CN103073902B - Polymer-modified asphalt and preparation method thereof - Google Patents
Polymer-modified asphalt and preparation method thereof Download PDFInfo
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- CN103073902B CN103073902B CN201310020546.9A CN201310020546A CN103073902B CN 103073902 B CN103073902 B CN 103073902B CN 201310020546 A CN201310020546 A CN 201310020546A CN 103073902 B CN103073902 B CN 103073902B
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Abstract
The invention discloses polymer-modified asphalt and a preparation method thereof. The polymer-modified asphalt is prepared from the following components in part by mass: 85-97 parts of base asphalt, 1-10 parts of polymer and 0.1-1.5 parts of auxiliary agents. The preparation method of the polymer-modified asphalt comprises the following steps: (1) mixing the base asphalt and the polymer so as to disperse the polymer into the asphalt to obtain an asphalt-polymer mixture; and (2) adding the auxiliary agent into the asphalt-polymer mixture, and performing cross-linking reaction to obtain the polymer-modified asphalt. The used auxiliary agents are composite auxiliary agents playing different roles during asphalt preparation; and thiophene sulfide as a structural sulfur is vulcanized, and compared with vulcanization of elemental sulfur, due to absence of free sulfur, heat resistance, aging resistance and tensile property of the polymer-modified asphalt are improved.
Description
Technical field
The present invention relates to a kind of polymer modified asphalt and preparation method thereof.
Background technology
Along with the widespread use of modifying asphalt, also more and more higher to the requirement of modifying asphalt, be mainly reflected in and require that modifying asphalt has good stability in storage, higher softening temperature and good low-temperature ductility.
Adopt common SBS to prepare modifying asphalt, reach and generally need higher incorporation compared with during high softening-point, the requirement of low-temperature ductility could be met simultaneously; If use higher sulfur consumption, although can improve softening temperature while reducing SBS consumption, low-temperature ductility is not up to standard, and the viscosity of 135 DEG C may be excessive simultaneously.In addition adopt low-molecular-weight SBS to prepare modifying asphalt, its low-temperature ductility is often just up to standard, if propose the requirement higher than specification in engineering, then can not reach requirement in actual production.In addition, higher SBS volume can increase the production cost of pitch, and the increase of SBS output simultaneously also can make the storage stability of pitch reduce.
US4145322 discloses a kind of method preparing SBS modifying asphalt, and heated asphalt, to 130-230 DEG C, adds the low-molecular-weight SBS of 2-20%, and using sulphur as linking agent, the shortcoming of this technology is that SBS is difficult to mix with pitch.
US5371121 discloses a kind of method preparing SBS modifying asphalt, only adds the sulphur of 0.015-0.075%, this method due to the output of sulphur too low, SBS output used is too high, and the storage stability of SBS modifying asphalt is bad.
USP6133351 discloses a kind of employing sulphur or diaryl disulfide is stablizer, and prepared a kind of modifying asphalt, in this course, the control of level of response is main influence factor.Easily cause over cure to form the problems such as colloid and operation cannot be continued, and reaction times longer increase production cost.And WO9958600 adopts the method for metal oxide or mineral acid, WO0023533 adopts the method adding polyolefins compound to solve the problem of storage stability, but effect is undesirable.
CN1239801A adopt containing high in aromatics be that by-product does compatilizer and makes polymkeric substance and pitch well be fused into homogeneous system, add linking agent and make pitch-reaction promoter-polymkeric substance generation chemical reaction, improve the stability that polymkeric substance is compatible with pitch, these reaction promoters are organic per-compounds, metal oxide, resin, sulfide, sulphur and vulcanization accelerator etc.
CN1765997A linking agent used is poly-sulfur vulcanization thing or Organo-Titanate Chelates.When linking agent uses and gathers sulfur vulcanization thing, promotor uses sulfenic acid aminated compounds to coordinate with it, and during linking agent use Organo-Titanate Chelates, promotor uses thiurams/morpholine kind compound to coordinate with it.
Existing technology is all adopt sulfocompound as linking agent, is cross-linked viscid bitumen into gilsonite, but due to cross-linking agents limited efficiency used, can not be effectively cross-linked the larger viscid bitumen of penetration degree.
Summary of the invention
The object of this invention is to provide a kind of polymer modified asphalt and preparation method thereof, the storage stability of polymer modified asphalt provided by the present invention is good, modifying asphalt softening temperature is higher than 65 DEG C, and 5 DEG C of ductilities are greater than 55cm, and the technique of preparation method provided by the present invention is simple, easy to operate.
A kind of polymer modified asphalt provided by the present invention, be made up of the component of following quality proportioning:
Basic asphalt 85 ~ 97;
Polymkeric substance 1 ~ 10; With
Auxiliary agent 0.1 ~ 1.5.
Above-mentioned polymer modified asphalt, the mass ratio of described basic asphalt, described polymkeric substance and described auxiliary agent specifically can be (93.8 ~ 96.5): (3 ~ 5.5): (0.3 ~ 1.0), 96.5:3.0:0.5,95:4.5:0.5,94.2:5.5:0.3,94.5:4.5:1.0 or 93.8:5.5:0.7.
Above-mentioned polymer modified asphalt, described basic asphalt can be residual oil, straight-run pitch, de-oiled asphalt, mediation pitch and subtracts at least one in four line wax oils, wherein said de-oiled asphalt can be the de-oiled asphalt that solvent de-asphalting process obtains, and described mediation pitch can be the mediation pitch that Blending obtains;
The penetration degree of described basic asphalt at 25 DEG C is 300 ~ 4001/10mm.
Above-mentioned polymer modified asphalt, described polymkeric substance can be the mixture of thermoplastic elastomer containing conjugated diolefine hydrocarbon structure and segmented copolymer, described is 1 ~ 10:1 ~ 10 containing the thermoplastic elastomer of conjugated diolefine hydrocarbon structure and the mass ratio of described segmented copolymer, specifically can be (5 ~ 8): 1,5:1,8:1 or 10:1.
Above-mentioned polymer modified asphalt, the described thermoplastic elastomer containing conjugated diolefine hydrocarbon structure is styrene-butadiene-styrene block copolymer (SBS) or styrene isoprene styrene block copolymer (SIS) (SIS), and its molecular weight can be 100,000.
Above-mentioned polymer modified asphalt, described segmented copolymer can be (EO)
100(PO)
70(EO)
100(F127), at least one in polyoxyethylene-poly-oxypropylene polyoxyethylene segmented copolymer (PEO-PPO-PEO), Pluronic L121 and polyoxypropylene polyoxyethylene-polyoxypropylene block copolymers, its molecular weight can be 100,000.
Above-mentioned polymer modified asphalt, described auxiliary agent can be the mixture of linking agent and promotor;
In described mixture, the mass percentage of described linking agent can be 40 ~ 100%, specifically can be 50 ~ 70%, 50%, 60% or 70%, and surplus is described promotor;
Described linking agent is thiophene-type sulfide, and described promotor can be amides.
Above-mentioned polymer modified asphalt, described thiophene-type sulfide can be thiophene, Polythiophene, dibenzothiophene, thionaphthene, 4-MDBT or 4,6-dimethyl Dibenzothiophene;
Described amides can be N-2-(3-methoxyl group-4-propargyl oxygen) phenylacetamide, N-(2-pyrimidyl) benzamide, N-arylacetamide, the fragrant thiacetamides of 4,6-dimethoxypyridins, N-substituted aryl tetrahydrochysene benzamide or β-carbonyl acid amides.
Above-mentioned polymer modified asphalt, when described auxiliary agent is only chosen as linking agent, described linking agent is metallocene-titanium metal compound or luxuriant Zr metal compound;
Described metallocene-titanium metal compound can be the luxuriant titanium of phenylbenzene hexichol, two pairs of luxuriant titaniums of phenyl two, two luxuriant titaniums of tolyl two, two methyl cyclopentadienyl phenylbenzene titanium, 1-ethyl-2, 3, 4, 5-tetramethyl-ring pentadienyl three titanium isopropylate, tetramethyl-ring pentadienyl three titanium isopropylate, cyclopentadienyl titanous chloride, cyclopentadienyl (2, 6-di-t-butyl-4-methylphenoxy) titanium dichloride, cyclopentadienyl (2-di-t-butyl-4-methoxyphenoxy) titanium dichloride, cyclopentadienyl (2, 4, 6-tri-butyl-phenoxy) titanium dichloride or cyclopentadienyl (2-di-t-butyl phenoxy group) titanium dichloride,
Described luxuriant Zr metal compound can be 1-ethyl-2,3,4,5-tetramethyl-ring pentadienyl three zirconium iso-propoxide, tetramethyl-ring pentadienyl three zirconium iso-propoxide, cyclopentadienyl tri-chlorination zirconium, cyclopentadienyl (2,6-di-t-butyl-4-methylphenoxy) zirconium dichloride, cyclopentadienyl (2-di-t-butyl-4-methoxyphenoxy) zirconium dichloride, cyclopentadienyl (2,4,6-tri-butyl-phenoxy) zirconium dichloride or cyclopentadienyl (2-di-t-butyl phenoxy group) zirconium dichloride.
Present invention also offers the preparation method of above-mentioned polymer modified asphalt, comprise the steps:
(1) by described basic asphalt and described mixed with polymers, described polymer dispersed is made to obtain bitumen-polymer mixture in described pitch;
(2) described auxiliary agent is added in described bitumen-polymer mixture, namely obtains described polymer modified asphalt through crosslinking reaction.
In above-mentioned preparation method, in step (1), the temperature of described mixing can be 110-230 DEG C, specifically can be 110-170 DEG C, 110-180 DEG C, 110 DEG C, 170 DEG C, 180 DEG C or 230 DEG C, time can be 10 ~ 60min, specifically can be 10min, 20min or 60min; And/or,
In step (2), the temperature of described crosslinking reaction can be 160 ~ 260 DEG C, and specifically can be 180 ~ 260 DEG C, 160 DEG C, 180 DEG C or 260 DEG C, the time can be 10 ~ 400min, specifically can be 50 ~ 60min, 50min or 60min.
For improving the storage stability of modifying asphalt, the auxiliary agent that the present invention adopts is the compound auxiliary agent playing not same-action in pitch preparation process, wherein thiophene-type sulfide is structure sulfur vulcanization, compared with vulcanization of elemental sulfur, owing to not having free sulphur, heat-resisting, ageing-resistant, the tensile property of its product all increase; But its sulfuration is comparatively strong, easily causes overvulcanize, the present invention adopt amides with it with the use of, would not the problems referred to above be there are.When linking agent adopts metallocene-titanium metal compound, the good asphaltic products. of storage stability can be obtained.Due to classes of compounds in the reaction role emphasize particularly on different fields, make polymkeric substance well compatible with basic asphalt, and quick and stable carry out crosslinking reaction, products obtained therefrom has satisfactory stability.
Embodiment
The experimental technique used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
The following embodiment of the present invention Polymer SBS used is the YH-791 type of Yueyang general petrochemical works, and SIS is styrene isoprene styrene block copolymer (SIS), and molecular weight is 100,000; PEO-PPO-PEO(P123 used is the product (cat. no: 435465, molecular weight is 100,000) that Aldrich company produces; (EO) used
100(PO)
70(EO)
100(F127) available from Aldrich Co.
The mensuration of the penetration degree in following embodiment adopts T0604 method to carry out measuring, and the mensuration of softening temperature adopts T0606 method to carry out measuring, and segregation experiment adopts the method for T0661 to carry out measuring.
Embodiment 1, prepare polymer modified asphalt
Be 3491/10mm by 25 DEG C of penetration degrees, softening temperature is basic asphalt (CNOOC's residual oil with subtract four line wax oils mix) (the accounting for 96.5% of total amount quality) of 29 DEG C, be heated to 170 DEG C to molten state, the SBS of the 2.5% and P123 of 0.5% is added in basic asphalt, adopts high-speed shearing machine (rotating speed 10000r/min) to mix 20min; Add the reaction promoter of 0.5% afterwards, terminate, obtain modifying asphalt at 180 DEG C after hybrid reaction 60min, its physico-chemical property is as shown in table 1.
In the present embodiment, consisting of of the reaction promoter adopted: the thiophene of 60% and N-2-(3-methoxyl group-4-propargyl oxygen) phenylacetamide of 40%, be mass percent.
Embodiment 2, prepare polymer modified asphalt
Be 3391/10mm by 25 DEG C of penetration degrees, softening temperature is basic asphalt (CNOOC's residual oil with subtract four line wax oils mix) (the accounting for 95% of total amount quality) of 31 DEG C, be heated to 180 DEG C to molten state, the SBS of the 4% and P123 of 0.5% is added in basic asphalt, adopts high-speed shearing machine (rotating speed 10000r/min) to mix 20min; Add the reaction promoter of 0.5% afterwards, terminate, obtain modifying asphalt at 180 DEG C after hybrid reaction 60min, its physico-chemical property is as shown in table 1.
In the present embodiment, the reaction promoter adopted is the luxuriant titanium of phenylbenzene two.
Embodiment 3, prepare polymer modified asphalt
Be 3141/10mm by 25 DEG C of penetration degrees, softening temperature is basic asphalt (CNOOC's residual oil with subtract four line wax oils mix) (the accounting for 94.2% of total amount quality) of 39 DEG C, be heated to 110 DEG C to molten state, the SBS of the 5% and F127 of 0.5% is added in basic asphalt, adopt high-speed shearing machine (rotating speed 10000r/min) to mix 60min, add the reaction promoter of 0.3% afterwards, terminate after hybrid reaction 50min at 160 DEG C, obtain modifying asphalt, its physico-chemical property is as shown in table 1.
In the present embodiment, consisting of of the reaction promoter adopted: the 4-MDBT of 50% and the N-substituted aryl tetrahydrochysene benzamide of 50%, be mass percent.
Embodiment 4, prepare polymer modified asphalt
Be 3541/10mm by 25 DEG C of penetration degrees, softening temperature is basic asphalt (CNOOC's residual oil with subtract four line wax oils mix) (the accounting for 94.5% of total amount) of 28 DEG C, be heated to 230 DEG C to molten state, the SIS of the 4% and P123 of 0.5% is added in basic asphalt, adopt high-speed shearing machine (rotating speed 10000r/min) to mix 10min, add the reaction promoter of 1.0% afterwards, terminate after hybrid reaction 60min at 260 DEG C, obtain modifying asphalt, its physico-chemical property is as shown in table 1.
In the present embodiment, consisting of of the reaction promoter adopted: the dibenzothiophene of 70% and N-(2-pyrimidyl) benzamide of 30%, be mass percent.
Embodiment 5, prepare polymer modified asphalt
Be 3651/10mm by 25 DEG C of penetration degrees, softening temperature is basic asphalt (CNOOC's residual oil with subtract four line wax oils mix) (the accounting for 93.8% of total amount quality) of 27 DEG C, be heated to 180 DEG C to molten state, the SBS of the 5% and F127 of 0.5% is added in basic asphalt, adopt high-speed shearing machine (rotating speed 10000r/min) to mix 20min, add the reaction promoter of 0.7% afterwards, terminate after hybrid reaction 60min at 180 DEG C, obtain modifying asphalt, its physico-chemical property is as shown in table 1.
In the present embodiment, the reaction promoter adopted is two methyl cyclopentadienyl phenylbenzene titanium.
The character of table 1 embodiment medium pitch product
Table 2SBS class Technical Requirement of Modified Asphalt (JTG F40-2004)
Table 2 is the technical requirements of SBS class modifying asphalt, and the data in contrast table 1 and table 2 are known, and asphaltic products. prepared by this invention, meets the requirement of the C level pitch of national regulations.
Claims (2)
1. a polymer modified asphalt, is characterized in that: described modifying asphalt is made up of the component of following quality proportioning:
Basic asphalt 85 ~ 97;
Polymkeric substance 1 ~ 10;
Auxiliary agent 0.1 ~ 1.5;
Described basic asphalt is residual oil, straight-run pitch, de-oiled asphalt, mediation pitch and subtract at least one in four line wax oils;
The penetration degree of described basic asphalt at 25 DEG C is 300 ~ 400 1/10 mm;
Described polymkeric substance is the mixture of thermoplastic elastomer containing conjugated diolefine hydrocarbon structure and segmented copolymer;
The described thermoplastic elastomer containing conjugated diolefine hydrocarbon structure is styrene-butadiene-styrene or styrene-isoprene-styrene copolymer-; Described is 1 ~ 10:1 ~ 10 containing the thermoplastic elastomer of conjugated diolefine hydrocarbon structure and the mass ratio of described segmented copolymer;
Described segmented copolymer is (EO)
100(PO)
70(EO)
100, polyoxyethylene-poly-oxypropylene polyoxyethylene segmented copolymer, at least one in Pluronic L121 and polyoxypropylene polyoxyethylene-polyoxypropylene block copolymers;
Described auxiliary agent is the mixture of linking agent and promotor;
In described mixture, the mass percentage of described linking agent is 50 ~ 70%, and surplus is described promotor;
Described linking agent is thiophene-type sulfide, and described promotor is amides;
Described thiophene-type sulfide is thiophene, Polythiophene, dibenzothiophene, thionaphthene, 4-MDBT or 4,6-dimethyl Dibenzothiophene;
Described amides is N-2-(3-methoxyl group-4-propargyl oxygen) phenylacetamide, N-(2-pyrimidyl) benzamide, N-arylacetamide, the fragrant thiacetamides of 4,6-dimethoxypyridins, N-substituted aryl tetrahydrochysene benzamide or β-carbonyl acid amides;
Described modifying asphalt is prepared by following method:
(1) by described basic asphalt and described mixed with polymers, described polymer dispersed is made to obtain bitumen-polymer mixture in described pitch;
(2) described auxiliary agent is added in described bitumen-polymer mixture, namely obtains described polymer modified asphalt through crosslinking reaction.
2. the preparation method of polymer modified asphalt described in claim 1, comprises the steps:
(1) by described basic asphalt and described mixed with polymers, described polymer dispersed is made to obtain bitumen-polymer mixture in described pitch;
(2) described auxiliary agent is added in described bitumen-polymer mixture, namely obtains described polymer modified asphalt through crosslinking reaction.
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| CN103936927B (en) * | 2014-04-25 | 2016-09-28 | 交通运输部公路科学研究所 | Response type asphalt mixture additive and compound, its preparation method and application |
| CN112110680B (en) * | 2020-09-14 | 2022-09-06 | 山东高速交通建设集团股份有限公司 | Asphalt reducing agent, cold-mixed pavement finish coat material and finish coat paving method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1649965A (en) * | 2002-04-24 | 2005-08-03 | 旭化成化学株式会社 | Asphalt composition |
| CN1765997A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Polymer modified asphalt with storage stability and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1649965A (en) * | 2002-04-24 | 2005-08-03 | 旭化成化学株式会社 | Asphalt composition |
| CN1765997A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Polymer modified asphalt with storage stability and its preparation method |
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Effective date of registration: 20170224 Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: China National Offshore Oil Corporation Patentee after: China National Offshore Oil Corporation Patentee after: CNOOC Refining & Chemical Research Institute (Beijing) Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: China National Offshore Oil Corporation Patentee before: China National Offshore Oil and Gas Development and Utilization Co., Ltd. |
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Address after: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee after: China National Offshore Oil Corporation Patentee after: China Offshore Oil Group Co., Ltd. Co-patentee after: CNOOC Refining & Chemical Research Institute (Beijing) Co., Ltd. Address before: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee before: China National Offshore Oil Corporation Patentee before: China National Offshore Oil Corporation Co-patentee before: CNOOC Refining & Chemical Research Institute (Beijing) Co., Ltd. |
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