CN100337964C - Concrete air-entrainer - Google Patents
Concrete air-entrainer Download PDFInfo
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- CN100337964C CN100337964C CNB2006100383220A CN200610038322A CN100337964C CN 100337964 C CN100337964 C CN 100337964C CN B2006100383220 A CNB2006100383220 A CN B2006100383220A CN 200610038322 A CN200610038322 A CN 200610038322A CN 100337964 C CN100337964 C CN 100337964C
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- concrete air
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- 239000004567 concrete Substances 0.000 title claims abstract description 78
- 239000000047 product Substances 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 238000005886 esterification reaction Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 230000032050 esterification Effects 0.000 claims abstract description 17
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 15
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 15
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000008130 triterpenoid saponins Chemical class 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000008399 tap water Substances 0.000 claims abstract description 4
- 235000020679 tap water Nutrition 0.000 claims abstract description 4
- -1 polyoxyethylene Polymers 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 23
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- QZXSMBBFBXPQHI-UHFFFAOYSA-N N-(dodecanoyl)ethanolamine Chemical compound CCCCCCCCCCCC(=O)NCCO QZXSMBBFBXPQHI-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 229940059574 pentaerithrityl Drugs 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 150000004054 benzoquinones Chemical class 0.000 claims description 5
- IFYDZTDBJZWEPK-UHFFFAOYSA-N alpha-hydroxyhexacosanoic acid Natural products CCCCCCCCCCCCCCCCCCCCCCCCC(O)C(O)=O IFYDZTDBJZWEPK-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 4
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- NIONDZDPPYHYKY-SNAWJCMRSA-N (2E)-hexenoic acid Chemical compound CCC\C=C\C(O)=O NIONDZDPPYHYKY-SNAWJCMRSA-N 0.000 claims description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- OXEDXHIBHVMDST-UHFFFAOYSA-N 12Z-octadecenoic acid Natural products CCCCCC=CCCCCCCCCCCC(O)=O OXEDXHIBHVMDST-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- UOQHWNPVNXSDDO-UHFFFAOYSA-N 3-bromoimidazo[1,2-a]pyridine-6-carbonitrile Chemical compound C1=CC(C#N)=CN2C(Br)=CN=C21 UOQHWNPVNXSDDO-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 235000021353 Lignoceric acid Nutrition 0.000 claims description 2
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- YIYBQIKDCADOSF-UHFFFAOYSA-N alpha-Butylen-alpha-carbonsaeure Natural products CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 claims description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- KEDPQQQNTPFUME-UHFFFAOYSA-N dodecan-1-amine;2-(2-hydroxyethylamino)ethanol Chemical compound OCCNCCO.CCCCCCCCCCCCN KEDPQQQNTPFUME-UHFFFAOYSA-N 0.000 claims description 2
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 229940099563 lactobionic acid Drugs 0.000 claims description 2
- 229960004488 linolenic acid Drugs 0.000 claims description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 235000021313 oleic acid Nutrition 0.000 claims description 2
- 229940113162 oleylamide Drugs 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 claims description 2
- 229940066675 ricinoleate Drugs 0.000 claims description 2
- PCMORTLOPMLEFB-ONEGZZNKSA-N sinapic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-ONEGZZNKSA-N 0.000 claims description 2
- PCMORTLOPMLEFB-UHFFFAOYSA-N sinapinic acid Natural products COC1=CC(C=CC(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-UHFFFAOYSA-N 0.000 claims description 2
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000010881 fly ash Substances 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 11
- 239000011382 roller-compacted concrete Substances 0.000 abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 3
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 3
- 239000006260 foam Substances 0.000 abstract 3
- 230000000087 stabilizing effect Effects 0.000 abstract 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 229920005610 lignin Polymers 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 239000003784 tall oil Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000013558 reference substance Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000004568 cement Substances 0.000 description 8
- 239000002826 coolant Substances 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000010883 coal ash Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003487 anti-permeability effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008458 response to injury Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to a concrete air-entraining agent which is prepared by the following steps: 1) rosin, tall oil, triterpenoid saponin and lignin are put in a reaction kettle according to parts by weight to be uniformly stirred after being heated and melted, and mixing resin A is manufactured; 2) maleic anhydride and benzoquinone are added in the reaction kettle, and addition resin B is manufactured after the mixing resin A is added and modified; 3) polyethylene glycol or a mixture of the polyethylene glycol and pentaerythritol is dripped, and a stem grafting esterification reaction is carried out at the temperature of 180 to 250 DEG C to generate a stem grafting esterification product C; 4) a foam stabilizing component D and a foam stabilizing component E are added after the reaction kettle is cooled to 50 to 100 DEG C; 5) the reaction kettle is continuously cooled to 20 to 95 DEG C, a reactant is neutralized by an alkali solution, tap water is simultaneously dripped, the content of an obtained solution solid matter is controlled between 29 and 31%, pH=9 to 11, and a final product is obtained. The present invention has favorable air-entraining performance and foam stabilization performance and is particularly suitable for concrete containing a flyash admixture and rolled concrete with less water consumption and difficult air entrainment.
Description
Technical field
The present invention relates to a kind of concrete air-entrainer.
Background technology
Concrete air-entrainer can effectively improve concrete and newly mix performance, improve concrete workability, reduce the bleeding performance, improved simultaneously concrete freeze proof anti-permeability performance greatly, be suitable for important engineering concrete structures such as water conservancy project, harbor work and bridge, the cryosel of concrete highway, bridge spread to(for) severe cold area are even more important.In addition, usually adopt flyash as active blending material in these concrete preparations, improving the workability of fresh concrete, and the temperature that the reduces mass concrete cracking trend that contracts.But use to find that the higher flyash of part loss on ignition usually reduces the bleed effect of air entrapment agent because of containing the unburned carbon grain.
Common air entrapment agent, for example common commercial resins class air entrapment agent, or be the air entrapment agent of main component with alkyl-sulphate and alkyl sulfate-base, to adopting the less flyash of loss on ignition is that the concrete of adulterant has bleed performance preferably, but concrete for the bigger flyash preparation of loss on ignition, owing to wherein contain more not combustion adsorptivity carbon granules, cause the initial air content of air-entraining concrete rapid, have bigger air content loss, cause the inside concrete small bubbles are fused to gradually big deterioration effect to concrete performance major diameter bubble simultaneously.Can change the concrete performance of initially newly mixing although increase the air entrapment agent volume, but because its influence to concrete over-all properties is comparatively complicated, excessive air entrapment agent volume will reduce concrete hardening strength, thick bubble structure inferior is very limited to the improvement effect of concrete endurance quality such as impervious, freeze proof, sometimes or even the effect of deterioration.
In order to improve the performance of adding coal ash concrete air-entrainer, normal fatty acid ester and the alkylaryl ester of adopting, and soap compound way improves the initial air content of concrete, but, often need to increase the volume of such concrete air-entrainer, simultaneously because the air content loss is bigger, because the rapid variation of its air content, cause that the optimum mix amount of air entrapment agent is difficult to determine in the concrete proportioning, in addition, excessive air entrapment agent will reduce concrete hardening strength.Therefore, should put forth effort to improve the bleed quality of existing air entrapment agent, make its bleed demand that is applicable to various blending concretes, simultaneously, be applicable to the bleed requirement of special concrete, as the bleed demand of the roller compacted concrete of low water usage amount, high doping quantity of fly ash.
Summary of the invention
The present invention will solve be exactly above-mentioned available coagulation soil air entrapment agent exist such as problems such as bad adaptability, the bleed not high, that can not satisfy various blending concretes and special concrete of bleed efficient require.
For solving the problems of the technologies described above, the bleed efficient that improves air entrapment agent with and and flyash between adaptability, the present invention is by multiple hybrid resin modification, introduce the nonionic structure of functional groups, and compound in conjunction with alkyl fatty acid and derivative thereof, realize air entrapment agent stable bleed performance in special concrete.
The present invention is prepared from by following step:
1) rosin, Yatall MA, triterpenoid saponin and xylogen are dropped in the reactor by 40～100: 0～40: 0～10: 0～10 ratio of weight and number, stir after being warmed up to 130～170 ℃ of fusings, make 100 parts of Resin A;
2) add maleic anhydride, benzoquinones in reactor, make addition resin B after carrying out under 160～200 ℃ that Resin A carried out addition modification, 100 parts of addition resin B are formed by the material addition modification of following weight:
Resin A: 40～95 parts
Maleic anhydride: 5～45 parts
Benzoquinones: 0～15 part
3) mixture of dropping polyoxyethylene glycol or polyoxyethylene glycol and tetramethylolmethane in reactor carries out the grafting esterification under 180～250 ℃, generates grafting esterification products C, and the weight ratio of addition resin B, tetramethylolmethane, polyoxyethylene glycol is in the grafting esterification:
Addition resin B:10～80 part
Polyoxyethylene glycol: 20～50 parts
Tetramethylolmethane: 0～40 part
4) behind the grafting esterification reef knot bundle, after reactor is cooled to 50～100 ℃, in reactor, add steady bubble component D and steady bubble component E, add 10～40 parts of steady bubble component D and 10～40 parts of steady bubble component E among 100 parts of grafting esterification reaction product C, wherein surely steeping component D is that carbonatoms is 8～30 alkyl carboxylic acid.Steady bubble component E is to be the organic alcohol amine salt of 8～24 alkyl fatty acid for carbon number;
5) continue to reduce temperature of reaction kettle to 20～95 ℃, adopt in the alkali lye and the gained reactant, drip tap water simultaneously, control gained solution solid content is 29%～31%, and pH=9～11 promptly get the finished product.
The mixing of the present invention by above resin, addition modification, grafting esterification, surely steep and five processing steps such as neutralization make.
In step 1 of the present invention, the input amount when dropping into reactant in the electric heating reacting kettle should be calculated an amount of reaction charging capacity according to the volumeter of reactor.Wherein rosin is answered the knock fragment, in order to avoid the injury response still.Energising reacting by heating still.By the time start the stirring anchor after reactant melts fully.Usually, the temperature of fusion of hybrid resin is between 130～170 ℃.
The addition modification of step 2 Resin A of the present invention mainly refers to wherein rosin composition is carried out the Diels-Alder addition reaction, and the addition modification material add-on of admixture is according to hybrid resin A total.The resin modified process is carried out under nitrogen protection, and the reaction material of input should add in batches, reacts while stir, and keeps temperature of reaction at 150～190 ℃, and the reaction times is at 0.5h～2.0h.
The present invention is to introduce wetting ability Soxylat A 25-7 segment on the acidic-group of modified resin B to the grafting esterification of modified resin B, forms the aggregate surface actives of polar resin and non-ionic type functional group.The starting material molecular weight polyethylene glycol that the grafting esterification adopts should be between 100～10000.Therefore the present invention has improved the bubble stability that air entrapment agent forms accordingly owing to owing to introduced the wetting ability polyoxyethylene segment of long-chain, increased the viscosity and the elasticity of bubble bubble wall in concrete.
The alcohols material that is dripped when the grafting esterification needs to be added dropwise in the reactor after the heating in advance, and the time that drips alcohols material is 1～3h, and the grafting esterification time that drips after finishing is 2～5h.
The carbonatoms that is adopted in the promptly steady bubble technology of step 4 of the present invention is that 8～30 alkyl carboxylic acid can be lignoceric acid, lactobionic acid, positive valeric acid, capric acid, enanthic acid, sad, hendecoic acid, lauric acid, palmitinic acid, stearic acid, palmitic acid, oleic acid, arachic acid, sinapinic acid, 19 carbonic acid, hydroxyhexacosanoic acid, octocosoic acid, triacontanoic acid, mountain Yu acid, pentenoic acid, decylenic acid, hexenoic acid, octadecenic acid, linolenic acid, ricinoleate acid etc.; The carbon number that is adopted is that the organic alcohol amine salt of 8～24 alkyl fatty acid can be February osmanthus-Semen Myristicae monoethanolamine, lauric monoethanolamide, laurylamide diethanolamine, inferior oleylamide diethanolamine and coconut monoethanolamide diethanolamine etc.
The purpose that the present invention introduces component D is to improve the bleed performance of air entrapment agent to roller compacted concrete.Introduce the E component and then can improve the concrete bleed performance of adding coal ash.
Step 5 of the present invention promptly in and alkali lye that technology adopts be to be generally 30% sodium hydroxide or potassium hydroxide solution.
Air entrapment agent of the present invention can be applied to there is not the concrete of adding coal ash or contain in the concrete preparation of by mass of cement 5～60% flyash.
Air entrapment agent of the present invention is suitable to be used for the concrete preparation with liquid form, and the volume of air entrapment agent of the present invention is 0.001～0.2% of cement or cement and a flyash gross weight.
Air entrapment agent of the present invention can with the compound use of other concrete admixture, as other gas tracting subtractive agent, high-effective concrete gas tracting subtractive agent, concrete retarder, concrete early strength agent, concrete defoamer, concrete thickening material, concrete waterproofer, concrete pump-feed agent, cement expansive material etc.
The present invention have water-soluble strong, good with any other admixture plyability, the bubble mean pore size that induces one is less, the bubble stability height, concrete strength is reduced characteristics such as less, be used for civil building, highway, railway, bridge, tunnel, hydro project and anti-concrete, the mortar air entrapment agent of freezing, be particularly useful for low slump such as roller compacted concrete, be mixed with the stable bleed of the special concrete of flyash, improve concrete and newly mix performance and sclerosis weather resistance.
Embodiment
The preparation example is as follows:
Reference substance 1:
Add entry 250g in 1000 milliliters of reactors, be warmed up to 90 ℃, add yellow soda ash 30g, dissolving, the boiling water state adds fritter rosin 100g down,
Gradation adds, and it is dissolved fully.Behind the postcooling to 50 ℃, drip the about 40g of 30% potassium hydroxide solution, regulating gained air entrapment agent strength of solution is 30 ± 1%, pH value 9～10.
Reference substance 2:
Add entry 250g in 1000 milliliters of reactors, be warmed up to 90 ℃, add yellow soda ash 25g, dissolving, the boiling water state adds fritter rosin 100g down, and gradation adds, and it is dissolved fully.After cool to 60 ℃, drip the about 40g of 30% potassium hydroxide solution, add trolamine 5g, stir 30min, at the uniform velocity drip the about 40g of water coolant, adjusting gained air entrapment agent strength of solution is 30 ± 1%, pH value 9～10.
Reference substance 3:
Add entry 250g in 1000 milliliters of reactors, be warmed up to 90 ℃, add yellow soda ash 20g, dissolving, the boiling water state adds fritter rosin 100g down, and gradation adds, and it is dissolved fully.After cool to 60 ℃, drip the about 40g of 30% potassium hydroxide solution, add trolamine 5g, Nonyl pheno (10) 5g also stirs 30min, at the uniform velocity drips the about 40g of water coolant, adjusting gained air entrapment agent strength of solution is 30 ± 1%, pH value 9～10.
Invention product 1:
With one-level rosin 100g, after breaking into pieces it is dropped in 1000 milliliters of reactors, be warmed up to 160 ℃, after the thing fusing to be mixed, start stirring, add toxilic acid 25g thereafter, be warmed up to 165 ℃, charge into nitrogen simultaneously, stirring reaction 60min.It is 2000 polyoxyethylene glycol 100g that the back adds molecular weight, is warming up to 220 ℃ and be incubated 3 hours.React and be cooled to 75 ℃ after complete, at the uniform velocity drip the about 440g of water coolant, about 30% sodium hydroxide solution 145g.Regulating gained air entrapment agent strength of solution is 30 ± 1%, pH value 9～10.
Invention product 2:
With one-level rosin 100g, after breaking into pieces it is dropped in 1000 milliliters of reactors, be warmed up to 160 ℃, after the thing fusing to be mixed, add toxilic acid 25g, be warmed up to 160～200 ℃, charge into nitrogen simultaneously, stirring reaction 60min.It is 1000 polyoxyethylene glycol 100g that the back adds molecular weight, is warming up to 220 ℃ and be incubated 3 hours.React and be cooled to 75 ℃ after complete, at the uniform velocity drip the about 440g of water coolant, about 30% sodium hydroxide solution 145g.Regulating gained air entrapment agent strength of solution is 30 ± 1%, pH value 9～10.
Invention product 3:
With superfine rosin 80g, triterpenoid saponin 20g drops into them in 1000 milliliters of reactors, is warmed up to 165 ℃, and stir thing fusing to be mixed back, adds toxilic acid 15g in the reactor, and benzoquinones 5g is warmed up to 160～200 ℃, charges into nitrogen simultaneously, stirring reaction 60min.It is 1000 polyoxyethylene glycol 100g that the back slowly adds molecular weight, is warming up to 220 ℃ and be incubated 3 hours, during inflated with nitrogen 60min.React and be cooled to 50～95 ℃ after complete, at the uniform velocity drip the about 440g of water coolant, about 30% potassium hydroxide solution 145g.Regulating gained air entrapment agent strength of solution is 30 ± 1%, pH value 9～10.
Invention product 4:
With superfine rosin 80g, Yatall MA 10g, triterpenoid saponin 10g drops into them in 1000 milliliters of reactors as hybrid resin, and the reacting by heating still makes it be warmed up to 160 ℃, start stirring after the thing fusing to be mixed, after forming homogeneous solution, in reactor, add maleic anhydride 20g, be warmed up to 160 ℃, charge into nitrogen simultaneously, stirring reaction 60min.The back adds tetramethylolmethane 50g, and molecular weight is 2000 polyoxyethylene glycol 50g, is warming up to 220 ℃ and be incubated 3 hours.React and be cooled to 65 ℃ after complete, at the uniform velocity drip the about 460g of water coolant, about 30% potassium hydroxide solution 170g.Regulating gained air entrapment agent strength of solution is 30 ± 1%, pH value 9～10.
Invention product 5:
100g one-level rosin is broken into pieces, is dropped in 1000 milliliters of reactors, after being warmed up to 165 ℃ of things to be mixed and melting, start stirring, add maleic anhydride 22.5g simultaneously, reaction 60min, during inflated with nitrogen 30min.The back slowly adds the polyoxyethylene glycol 100g of molecular weight 2000, is warming up to 205～210 ℃ and be incubated 60min, during inflated with nitrogen.React and be cooled to 80～85 ℃ after complete, add stearic acid 40g and also stir 30min.At the uniform velocity drip the about 450g of water coolant, the about 145g of 30% alkali lye.Amount of water exceeds with solid content 30 ± 1%, and the alkali lye amount is with pH value 9～10.Discharging behind the stirring 60min.
Invention product 6:
With superfine rosin 80g, Yatall MA 10g, triterpenoid saponin 10g is as hybrid resin, wherein rosin is broken into pieces, drops in 1000 milliliters of reactors with other mixture, and the reacting by heating still is to about 170 ℃ of temperature, after being melted fully, mixture starts stirring, the back slowly adds maleic anhydride 22.5g, is warmed up to 160 ± 5 ℃ of thawings, reaction 60min.In 185～191 ℃ of following insulation 2.5h, during fill nitrogen 30min.The polyoxyethylene glycol 100g of input molecule amount 1000 is warming up to 215 ℃ and be incubated 60min, during inflated with nitrogen.React and be cooled to 80～85 ℃ after complete, add stearic acid 20g, coconut monoethanolamide diethanolamine 20g stirs 30min, at the uniform velocity drips the about 490g of water coolant, the about 155g of 30% alkali lye.Amount of water exceeds with solid content 30 ± 1%, and the alkali lye amount is with pH value 9～10.Discharging behind the stirring 60min.
The application performance of air entrapment agent of the present invention compares by three kinds of concrete bleed performances of different nature.The test starting material that adopt are as follows:
Cement: the peaceful sheep P.II42.5R type cement of gold, specific surface area 310m
2/ kg, produce in cement mill, the south of the River;
Fa: Nanjing Cogeneration Power Plant first level flour coal ash;
JM-B: Jiangsu Bo Te novel material company produces naphthalene series high-efficiency water-reducing agent;
S: river, Nanjing sand, fineness modulus 2.62;
G1:10～30mm, limestone, continuous grading;
G2:30～60mm, limestone, continuous grading.
Three kinds of concrete mixs such as tables 1 that checking invention air entrapment agent performance is adopted, the air entrapment agent volume under the wherein different invention modes is listed in following each air entrapment agent performance.
Table 1: normal concrete and roller compacted concrete proportioning
| Concrete mix | C (kg/m 3) | Fa (kg/m 3) | W (kg/m 3) | S (kg/m 3) | G1 (kg/m 3) | G2 (kg/m 3) | JMB (kg/m 3) |
| Normal concrete BC | 330 | 0 | 192 | 711 | 1166 | 0 | 1.65 |
| Normal concrete BFC | 250 | 80 | 187 | 711 | 1166 | 0 | 1.60 |
| Roller compacted concrete RCC | 56 | 105 | 79 | 759 | 598 | 898 | 1.30 |
Adopt the stirrer of 70 liters of forced action types to stir, mixing the system amount of concrete is 40 liters.The concrete all material calculated to drop in the stirrer after the weighing according to proportioning stir, wherein concrete air-entrainer and the water reducer system of mixing that direct adding measures in advance after weighing is with in the tap water, make and add pre-dispersed cement and gather materials behind its homodisperse, stir 4～6min, wherein the discharging slump (SL) of proportioning BC and BFS is 8 ± 1cm, and to tie up the vigorous time (VC) be 2～4 seconds and proportioning is the discharging of RCC.
More than three kinds of concrete bleed performances see Table 2～4:
Table 2:BC concrete bleed performance
| Proportioning BC | |||||
| Volume (%) | SL(cm) | V 0(％) | V 60(％) | RV 60 (％) | |
| Reference substance 1 | 0.015 | 8.5 | 4.6 | 3.4 | 74 |
| Reference substance 2 | 0.015 | 7.8 | 4.9 | 3.7 | 76 |
| Reference substance 3 | 0.015 | 7.5 | 5.3 | 4.4 | 83 |
| Invention product 1 | 0.015 | 8.0 | 4.6 | 3.5 | 76 |
| Invention product 2 | 0.015 | 8.5 | 4.9 | 3.9 | 80 |
| Invention product 3 | 0.015 | 8.0 | 5.3 | 4.3 | 82 |
| Invention product 4 | 0.015 | 8.5 | 5.5 | 4.6 | 84 |
| Invention product 5 | 0.015 | 7.8 | 5.4 | 4.6 | 85 |
| Invention product 6 | 0.015 | 7.5 | 5.3 | 4.7 | 90 |
Table 3:BFC concrete bleed performance
| Proportioning BFC | |||||
| Volume (%) | SL(cm) | V 0(％) | V 60(％) | RV 60 (％) | |
| Reference substance 1 | 0.025 | 8.2 | 3.4 | 2.2 | 64 |
| Reference substance 2 | 0.025 | 8.3 | 3.6 | 2.4 | 68 |
| Reference substance 3 | 0.025 | 8.5 | 3.7 | 2.8 | 77 |
| Invention product 1 | 0.025 | 7.8 | 3.4 | 2.4 | 70 |
| Invention product 2 | 0.025 | 7.5 | 3.6 | 2.8 | 77 |
| Invention product 3 | 0.025 | 8.0 | 3.7 | 3.0 | 80 |
| Invention product 4 | 0.025 | 8.5 | 3.8 | 3.0 | 80 |
| Invention product 5 | 0.025 | 8.0 | 4.5 | 3.7 | 82 |
| Invention product 6 | 0.025 | 8.5 | 5.2 | 4.3 | 83 |
Table 4:RCC concrete bleed performance
| Proportioning RCC | |||||
| Volume (%) | Vc(′) | V 0(％) | V 60(％) | RV 60 (％) | |
| Reference substance 1 | 0.035 | 3 | 3.55 | 2.2 | 62 |
| Reference substance 2 | 0.035 | 3 | 3.70 | 2.6 | 72 |
| Reference substance 3 | 0.035 | 3 | 4.2 | 3.2 | 75 |
| Invention product 1 | 0.035 | 4 | 3.55 | 2.6 | 73 |
| Invention product 2 | 0.035 | 3 | 3.65 | 2.9 | 79 |
| Invention product 3 | 0.035 | 3 | 4.2 | 3.4 | 82 |
| Invention product 4 | 0.035 | 4 | 5.7 | 4.7 | 82 |
| Invention product 5 | 0.035 | 4 | 5.9 | 4.9 | 83 |
| Invention product 6 | 0.035 | 5 | 6.0 | 5.2 | 86 |
Wherein, V
0: the discharging air content, (%); V
60: air content behind the 60min, (%); RV
60: air content conservation rate behind the 60min, (%).
Because by the addition graft reaction, in the air entrapment agent surface active molecules, introduced nonionic components, simultaneously composite soap derivative of different nature, compare with the air entrapment agent that the rosined soap class and the mixture thereof of contrast are formed, use air entrapment agent of the present invention that the concrete of roller compacted concrete and doping quantity of fly ash about 25% is had higher bleed performance and bubble maintenance performance.In invention product 5, because composite stearic acid, in new breading coal ash Additive concrete, under the identical air entrapment agent volume, the initial air content of concrete is 4.5%, and the bubble conservation rate is 82%, is higher than contrast air entrapment agent sample and not composite stearic invention product 1～4; Newly mixing in the roller compacted concrete, under the identical air entrapment agent volume, the initial air content of concrete is 5.9%, and the bubble conservation rate is 83%, is higher than contrast air entrapment agent sample and not composite stearic invention product 1～4.
In invention product 6, because simultaneously composite stearic acid and coconut monoethanolamide diethanolamine, in new breading coal ash Additive concrete, under the identical air entrapment agent volume, the initial air content of concrete is 5.3%, and the bubble conservation rate is 90%, is higher than contrast air entrapment agent sample and invention product 1～5; Newly mixing in the roller compacted concrete, under the identical air entrapment agent volume, the initial air content of concrete is 6.0%, and the bubble conservation rate is 86%, is higher than contrast air entrapment agent sample and invention product 1～5.As seen, simultaneously composite stearic acid and coconut monoethanolamide diethanolamine to the effect that all is significantly improved of roller compacted concrete bleed performance and bubble maintenance performance.
Claims (8)
1, a kind of concrete air-entrainer is characterized in that it is prepared from by following step:
1) rosin, Yatall MA, triterpenoid saponin and xylogen are dropped in the reactor by 40～100: 0～40: 0～10: 0～10 ratio of weight and number, stir after the heat fused, make 100 parts of Resin A;
2) add maleic anhydride, benzoquinones in reactor, Resin A is carried out making addition resin B behind the addition modification, 100 parts of addition resin B are formed by the material addition modification of following weight:
Resin A: 40～95 parts
Maleic anhydride: 5～45 parts
Benzoquinones: 0～15 part
3) mixture of dropping polyoxyethylene glycol or polyoxyethylene glycol and tetramethylolmethane in reactor carries out the grafting esterification under 180～250 ℃, generates grafting esterification products C, and the weight ratio of addition resin B, tetramethylolmethane, polyoxyethylene glycol is in the grafting esterification:
Addition resin B:10～80 part
Polyoxyethylene glycol: 20～50 parts
Tetramethylolmethane: 0～40 part
4) behind the grafting esterification reef knot bundle, after reactor is cooled to 50～100 ℃, in reactor, add steady bubble component D and steady bubble component E, add 10～40 parts of steady bubble component D and 10～40 parts of steady bubble component E among 100 parts of grafting esterification reaction product C, wherein surely steeping component D is that carbonatoms is 8～30 alkyl carboxylic acid; Steady bubble component E is to be the organic alcohol amine salt of 8～24 alkyl fatty acid for carbon number;
5) continue to reduce temperature of reaction kettle to 20～95 ℃, adopt in the alkali lye and the gained reactant, drip tap water simultaneously, control gained solution solid content is 29%～31%, and pH=9～11 promptly get the finished product.
2, concrete air-entrainer according to claim 1 is characterized in that the grafting esterification advances the branch output of the polyoxyethylene glycol that is added between 100～10000.
3, concrete air-entrainer according to claim 1 is characterized in that described carbonatoms is that 8～30 alkyl carboxylic acid is any one in lignoceric acid, lactobionic acid, positive valeric acid, capric acid, enanthic acid, sad, hendecoic acid, lauric acid, palmitinic acid, stearic acid, palmitic acid, oleic acid, arachic acid, sinapinic acid, 19 carbonic acid, hydroxyhexacosanoic acid, octocosoic acid, triacontanoic acid, mountain Yu acid, pentenoic acid, decylenic acid, hexenoic acid, octadecenic acid, linolenic acid, the ricinoleate acid.
4, concrete air-entrainer according to claim 1 is characterized in that carbon number is that the organic alcohol amine salt of 8～24 alkyl fatty acid is any one in two bays-Semen Myristicae monoethanolamine, lauric monoethanolamide, laurylamide diethanolamine, inferior oleylamide diethanolamine and the coconut monoethanolamide diethanolamine.
5, concrete air-entrainer according to claim 1 is characterized in that the hybrid resin temperature of fusion is between 130～170 ℃ in the step 1.
6, concrete air-entrainer according to claim 1, the reaction material that drops into when it is characterized in that addition reaction should add in batches, reacts while stir, and keeps temperature of reaction at 160～200 ℃, and the reaction times is at 0.5h～2.0h.
7, concrete air-entrainer according to claim 1, the time that drips alcohols material when it is characterized in that the grafting esterification is 1～3h, the grafting esterification time that drips after finishing is 2～5h.
8, concrete air-entrainer according to claim 1 is characterized in that described alkali lye is 30% sodium hydroxide or potassium hydroxide solution.
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| CN103012511B (en) * | 2009-09-25 | 2015-01-28 | 青田中野天然植物科技有限公司 | Midbody of structure modified type tea-oil saponin and application thereof |
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| CN108439849A (en) * | 2018-05-02 | 2018-08-24 | 金陵科技学院 | A kind of concrete air-entrainer and preparation method thereof |
| CN108793814A (en) * | 2018-07-17 | 2018-11-13 | 四川银凯新材料有限公司 | A kind of preparation method of air entraining agent |
| CN109608086A (en) * | 2018-12-27 | 2019-04-12 | 山西黄腾化工有限公司 | A kind of air entraining agent and preparation method thereof for concrete |
| CN109988301B (en) * | 2019-04-04 | 2021-06-15 | 江苏苏博特新材料股份有限公司 | Concrete defoamer, preparation method and application thereof |
| CN113121148B (en) * | 2019-12-30 | 2022-06-14 | 江苏苏博特新材料股份有限公司 | Foam stabilizer and preparation method and application thereof |
| CN111116844B (en) * | 2020-01-18 | 2022-01-25 | 广东汇强外加剂有限公司 | Air-entraining type polycarboxylate superplasticizer and preparation method thereof |
| CN111170674A (en) * | 2020-02-23 | 2020-05-19 | 石旭艳 | Concrete air entraining agent with good foam stability |
| CN111484283A (en) * | 2020-03-24 | 2020-08-04 | 上海福铁龙住宅工业发展有限公司 | Moisture-absorbing concrete brick, preparation process and application of moisture-absorbing concrete brick in prefabricated wall |
| CN111825397A (en) * | 2020-08-03 | 2020-10-27 | 平凉市新世纪建材有限责任公司 | Light recycled concrete and preparation process thereof |
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| CP02 | Change in the address of a patent holder |
Address after: 210008 No. 12, Beijing West Road, Gulou District, Nanjing City, Jiangsu Province Patentee after: Jiangsu Subute New Materials Co., Ltd. Address before: No. 59, Wan An West Road, Jiangning District, Nanjing, Jiangsu Patentee before: Jiangsu Subute New Materials Co., Ltd. |
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| TR01 | Transfer of patent right |
Effective date of registration: 20201103 Address after: No.26, South Zha Road, middle Jiangtai Road, Taixing Economic Development Zone, Taizhou City, Jiangsu Province Patentee after: BOTE NEW MATERIAL TAIZHOU Co.,Ltd. Patentee after: JIANGSU SUBOTE NEW MATERIALS Co.,Ltd. Address before: 210008 No. 12 West Beijing Road, Gulou District, Jiangsu, Nanjing Patentee before: JIANGSU SUBOTE NEW MATERIALS Co.,Ltd. |
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| TR01 | Transfer of patent right |