CN102212172A - Resin special for anchoring agent and preparation method thereof - Google Patents
Resin special for anchoring agent and preparation method thereof Download PDFInfo
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- CN102212172A CN102212172A CN 201110039826 CN201110039826A CN102212172A CN 102212172 A CN102212172 A CN 102212172A CN 201110039826 CN201110039826 CN 201110039826 CN 201110039826 A CN201110039826 A CN 201110039826A CN 102212172 A CN102212172 A CN 102212172A
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- resin
- acid
- anchoring agent
- acid number
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- 238000004873 anchoring Methods 0.000 title claims abstract description 32
- 229920005989 resin Polymers 0.000 title claims abstract description 32
- 239000011347 resin Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 18
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001530 fumaric acid Substances 0.000 claims abstract description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 6
- 239000003112 inhibitor Substances 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000006641 stabilisation Effects 0.000 claims description 5
- 238000011105 stabilization Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- HAVACXTVLQTJNR-UHFFFAOYSA-N CCCC[Se]=O Chemical group CCCC[Se]=O HAVACXTVLQTJNR-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000010288 sodium nitrite Nutrition 0.000 claims description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 abstract 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 abstract 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- 239000004575 stone Substances 0.000 description 6
- 239000004927 clay Substances 0.000 description 4
- 229920006305 unsaturated polyester Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- -1 promotor Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a resin special for an anchoring agent and a preparation method thereof. The resin is mainly prepared from terephthalic acid, fumaric acid, abietic acid, maleic anhydride, oxalic acid, glycerol, diglycol, a catalyst, a polymerization inhibitor, a stabilizing additive and styrene according to a certain proportion. A special resin which is most suitable to serve as an anchoring agent product is provided through means such as the adoption of a reasonable production process design formula, the adding of some chemical additives and the like. The gel time of the resin is short and is slightly affected by the temperature, the final curing strength is high, the early strength is quickly developed, the storage stability is high, the resin has high adhesion to mountain flour and has high adaptability to the mountain flour, and the doping amount of the mountain flour is large; and the cost is low, and each ton of the resin is 10 to 20 percent cheaper than each ton of an ordinary unsaturated resin.
Description
Technical field
The invention belongs to the unsaturated polyester resin technical field, be specifically related to unsaturated polyester resin of anchoring agent use and preparation method thereof.
Background technology
The anchoring agent is a modern Application bond-anchorage material the most widely, and it is by high-performance unsaturated polyester resin and solidifying agent, promotor, compositions such as filler and other chemical assistant.Resin anchoring agent is in the history in existing more than 50 year of application of China's coal-mine, along with country to the great attention of mine safety and the continuous increase of anchoring agent consumption, range of application constantly enlarges, anchoring agent performance has also been proposed more and more higher requirement, do anchoring agent product with traditional universal unsaturated polyester and exist a lot of problems: be short as the anchoring developing agent storage phase, at room temperature can only preserve 3-6 month, the clay part that also do not reach anchoring agent in 2 months in the storage period that has summer is with regard to hardening especially; Anchoring agent gel time is slow; The gel time temperature influence is bigger; It is low to solidify the back final strength, and the early strength development is also slow, and resin is to the bad adaptability of stone flour, and adhesivity is also poor, and stone powder mixing quantity is low, and resistance to elevated temperatures is poor, the also more high a series of problems of resin price.
Summary of the invention
The present invention does the deficiency of anchoring agent in order to solve above-mentioned universal unsaturated polyester, provides a kind of anchoring agent resin dedicated and preparation method thereof.
The present invention adopts following scheme to achieve these goals:
A kind of anchoring agent is resin dedicated, and the weight ratio of its constitutive material is: terephthalic acid 200-250, fumaric acid 100-150, sylvic acid 50-100, cis-butenedioic anhydride 145-200, oxalic acid 70-100, glycerine 30-80, glycol ether 250-400, catalyzer 0.5-1, stopper 0.3-1, stabilization aid 10-15, vinylbenzene 300-350.
Described anchoring agent is resin dedicated, described catalyzer is a monobutyl selenium oxide, stopper is the mixture of Resorcinol, pentanoic, Sodium Nitrite, toluhydroquinone, its mass ratio is 1: 1: 0.3: 0.2, stabilization aid is the mixture of vinylbenzene volatilization inhibitor, oxidation inhibitor-3026, gas-phase silica, whiteruss, and its mass ratio is 1: 0.2: 0.2: 1.
The resin dedicated preparation method of described anchoring agent may further comprise the steps:
(1) presses raw material weight than terephthalic acid, sylvic acid, oxalic acid, glycerine, glycol ether, catalyzer are dropped in the reactor, stir, heating makes material dissolution, be heated to 150-160 ℃ of insulation 1-1.5 hour, continue to heat up, temperature rise rate is controlled at and per hour is not more than 15 ℃, column temperature is no more than 105 ℃, when material rises to 230 ℃, column temperature is surveyed acid number in the time of 70-80 ℃, if acid number≤10mgKOH/g carries out next step;
(2) be cooled to 200 ℃, drop into cis-butenedioic anhydride and fumaric acid by weight in reactor, slowly heat up, temperature rise rate is controlled at and per hour is not more than 15 ℃, column temperature is no more than 105 ℃, when material rises to 220 ℃, column temperature is surveyed acid number in the time of 75-80 ℃, if survey acid number≤50mgKOH/g, vacuum-pumping underpressure distillation 10-20 minute so that remove remaining water, vacuumizes the back acid number and is controlled at 30-45mgKOH/g;
(3) be cooled to 180 ℃ and add stopper and stable helping and slowly cooling, behind near 140 ℃ of temperature of charge, add vinylbenzene, stirred 20-30 minute, cold gradually going carried out the packing of product to 40-50 ℃.
Beneficial effect of the present invention:
Replace phthalic anhydride with crude terephthalic acid and sylvic acid, fumaric acid replaces cis-butenedioic anhydride and adds stopper and the stabilization method auxiliary agent, the resin dedicated cost that reduces resin of the anchoring agent of producing, can reduce 10%-20% than common anchoring agent with the resin cost, the anchoring agent made from the resin of this invention can reach 70-85Mpa in 24 hours, the early strength development is fast, solidify and to reach 55-60Mpa in back 1 hour, the clay Heat stability is good of making, can reach 6-10 month storage period in the time of 25 ℃, and this resin is big to stone powder mixing quantity simultaneously, generally can reach quality: stone flour=1: 6～7 (mass ratio), to the stone flour wide adaptability, make big advantages such as anchoring agent clay good stability.
The resin that the present invention goes out reached the resin dedicated requirement of desirable anchoring agent, remedied the shortcoming that resins for universal use is done the anchoring agent effectively, solved resins for universal use: price height, shortcoming such as curing speed is slow, and storage period is short, and package stability is poor, and stone powder mixing quantity is low.Make anchoring agent that this resin of inventing out makes satisfy the requirement of MT146-2002 fully through the practical application of colliery and Hydraulic and Hydro-Power Engineering, research level reaches leading domestic.
Embodiment
Embodiment 1
The resin dedicated preparation method of a kind of anchoring agent may further comprise the steps:
(1) presses raw material weight than terephthalic acid, sylvic acid, oxalic acid, glycerine, glycol ether, catalyzer are dropped in the reactor, stir, electrically heated makes material dissolution, be heated to 160 ℃ of insulations 1 hour, continue to heat up, temperature rise rate is controlled at and per hour is not more than 15 ℃, column temperature is no more than 105 ℃, when material rises to 230 ℃, column temperature is surveyed acid number in the time of 70-80 ℃, if acid number≤10mgKOH/g carries out next step;
(2) be cooled to 200 ℃, drop into cis-butenedioic anhydride and fumaric acid by weight in reactor, slowly heat up, temperature rise rate is controlled at and per hour is not more than 15 ℃, column temperature is no more than 105 ℃, when material rises to 220 ℃, column temperature is surveyed acid number in the time of 75-80 ℃, if survey acid number≤50mgKOH/g, vacuum-pumping underpressure distillation 10-20 minute so that remove remaining water, vacuumizes the back acid number and is controlled at 30-45mgKOH/g;
(3) be cooled to 180 ℃ and add stopper and stable helping and slowly cooling, behind near 140 ℃ of temperature of charge, add vinylbenzene, stirred 20-30 minute, cold gradually going carried out the packing of product to 40-50 ℃.
General unsaturated polyester of table 1 and the resin dedicated performance comparison of anchoring agent (25 ± 1 ℃ of temperature)
The resin dedicated anchoring agent clay salient features contrast of making of general unsaturated polyester of table 2 and anchoring agent
(25 ± 1 ℃ of temperature)
Claims (3)
1. an anchoring agent is resin dedicated, it is characterized in that the weight ratio of its constitutive material is: terephthalic acid 200-250, fumaric acid 100-150, sylvic acid 50-100, cis-butenedioic anhydride 145-200, oxalic acid 70-100, glycerine 30-80, glycol ether 250-400, catalyzer 0.5-1, stopper 0.3-1, stabilization aid 10-15, vinylbenzene 300-350.
2. anchoring agent according to claim 1 is resin dedicated, it is characterized in that: described catalyzer is a monobutyl selenium oxide, stopper is the mixture of Resorcinol, pentanoic, Sodium Nitrite, toluhydroquinone, its mass ratio is 1: 1: 0.3: 0.2, stabilization aid is the mixture of vinylbenzene volatilization inhibitor, oxidation inhibitor-3026, gas-phase silica, whiteruss, and its mass ratio is 1: 0.2: 0.2: 1.
3. resin dedicated preparation method of anchoring agent as claimed in claim 1 is characterized in that: may further comprise the steps:
(1) presses raw material weight than terephthalic acid, sylvic acid, oxalic acid, glycerine, glycol ether, catalyzer are dropped in the reactor, stir, heating makes material dissolution, be heated to 150-160 ℃ of insulation 1-1.5 hour, continue to heat up, temperature rise rate is controlled at and per hour is not more than 15 ℃, column temperature is no more than 105 ℃, when material rises to 230 ℃, column temperature is surveyed acid number in the time of 70-80 ℃, if acid number≤10mgKOH/g carries out next step;
(2) be cooled to 200 ℃, drop into cis-butenedioic anhydride and fumaric acid by weight in reactor, slowly heat up, temperature rise rate is controlled at and per hour is not more than 15 ℃, column temperature is no more than 105 ℃, when material rises to 220 ℃, column temperature is surveyed acid number in the time of 75-80 ℃, if survey acid number≤50mgKOH/g, vacuum-pumping underpressure distillation 10-20 minute so that remove remaining water, vacuumizes the back acid number and is controlled at 30-45mgKOH/g;
(3) be cooled to 180 ℃ and add stopper and stable helping and slowly cooling, behind near 140 ℃ of temperature of charge, add vinylbenzene, stirred 20-30 minute, cold gradually going carried out the packing of product to 40-50 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110039826 CN102212172B (en) | 2011-02-17 | 2011-02-17 | Resin special for anchoring agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110039826 CN102212172B (en) | 2011-02-17 | 2011-02-17 | Resin special for anchoring agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102212172A true CN102212172A (en) | 2011-10-12 |
| CN102212172B CN102212172B (en) | 2013-07-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 201110039826 Active CN102212172B (en) | 2011-02-17 | 2011-02-17 | Resin special for anchoring agent and preparation method thereof |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585104A (en) * | 2012-02-16 | 2012-07-18 | 淮南市顺辉锚固有限公司 | Water repellent resin and preparation method and application thereof in preparation of anchoring agent |
| CN102584110A (en) * | 2011-12-29 | 2012-07-18 | 安徽淮河化工股份有限公司 | Method for dispersing thixotropic agent in resin anchoring agent |
| CN102690081A (en) * | 2012-06-11 | 2012-09-26 | 安徽省煤炭科学研究院 | Preparation method of delayed coagulation type resin bolting anchoring agent |
| CN102993976A (en) * | 2012-12-21 | 2013-03-27 | 广西梧州日成林产化工股份有限公司 | Preparation method of anti-crystallization stable rosin |
| CN103058576A (en) * | 2012-12-07 | 2013-04-24 | 安徽淮河化工股份有限公司 | Composite dispersant for resin anchoring agent |
| CN103058580A (en) * | 2012-12-07 | 2013-04-24 | 安徽淮河化工股份有限公司 | High-temperature-resistant resin anchoring agent and preparation method thereof |
| CN103772622A (en) * | 2014-01-22 | 2014-05-07 | 宜兴市兴合树脂有限公司 | Resin capable of being thickened at room temperature for sheet molding compound and preparation method thereof |
| CN105626110A (en) * | 2016-01-25 | 2016-06-01 | 唐永志 | Full-sized anchoring construction method |
| CN106280196A (en) * | 2016-08-27 | 2017-01-04 | 安徽省新力复合材料有限公司 | A kind of heat resistant unsaturated polyester resin |
| CN106366301A (en) * | 2016-08-27 | 2017-02-01 | 安徽省新力复合材料有限公司 | Low-shrinkage-rate unsaturated polyester resin for anchoring agent |
| CN106366251A (en) * | 2016-08-27 | 2017-02-01 | 安徽省新力复合材料有限公司 | Antibacterial low-viscosity unsaturated polyester resin for anchoring agent |
| CN106366601A (en) * | 2016-08-27 | 2017-02-01 | 安徽省新力复合材料有限公司 | Unsaturated polyester resin for anchoring agents |
| CN106366542A (en) * | 2016-08-27 | 2017-02-01 | 安徽省新力复合材料有限公司 | Antibacterial aging resistant unsaturated polyester resin |
| CN106366250A (en) * | 2016-08-27 | 2017-02-01 | 安徽省新力复合材料有限公司 | Anti-corrosion unsaturated polyester resin for anchoring agent and preparation method thereof |
| CN106397680A (en) * | 2016-08-27 | 2017-02-15 | 安徽省新力复合材料有限公司 | High-toughness unsaturated polyester resin used for anchoring agent, and preparation method thereof |
| CN106432701A (en) * | 2016-09-14 | 2017-02-22 | 中国科学院宁波材料技术与工程研究所 | Bio-based unsaturated polyester as well as preparation method and application thereof |
| CN106589749A (en) * | 2016-12-03 | 2017-04-26 | 安徽富丽华化工有限公司 | Modified unsaturated polyester resin having excellent acid and alkali resistance, and preparation method thereof |
| WO2018011226A1 (en) * | 2016-07-12 | 2018-01-18 | Centre National De La Recherche Scientifique (Cnrs) | Organogels allowing reduction and control of the evaporation of volatile organic liquids |
| CN111138604A (en) * | 2020-01-07 | 2020-05-12 | 美亚高新材料股份有限公司 | Preparation method of unequal-length double-speed anchoring agent |
| CN117736689A (en) * | 2023-12-18 | 2024-03-22 | 研墨化工(上海)有限公司 | Solvent-free modified polyurethane adhesive and preparation method thereof |
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| CN101412603A (en) * | 2008-11-07 | 2009-04-22 | 安徽淮河化工股份有限公司 | Ultra-slow resin anchoring agent |
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| CN101412603A (en) * | 2008-11-07 | 2009-04-22 | 安徽淮河化工股份有限公司 | Ultra-slow resin anchoring agent |
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| CN102584110A (en) * | 2011-12-29 | 2012-07-18 | 安徽淮河化工股份有限公司 | Method for dispersing thixotropic agent in resin anchoring agent |
| CN102585104A (en) * | 2012-02-16 | 2012-07-18 | 淮南市顺辉锚固有限公司 | Water repellent resin and preparation method and application thereof in preparation of anchoring agent |
| CN102585104B (en) * | 2012-02-16 | 2013-11-13 | 淮南市顺辉锚固有限公司 | Water repellent resin and preparation method and application thereof in preparation of anchoring agent |
| CN102690081A (en) * | 2012-06-11 | 2012-09-26 | 安徽省煤炭科学研究院 | Preparation method of delayed coagulation type resin bolting anchoring agent |
| CN102690081B (en) * | 2012-06-11 | 2013-06-19 | 安徽省煤炭科学研究院 | Preparation method of delayed coagulation type resin bolting anchoring agent |
| CN103058576A (en) * | 2012-12-07 | 2013-04-24 | 安徽淮河化工股份有限公司 | Composite dispersant for resin anchoring agent |
| CN103058580A (en) * | 2012-12-07 | 2013-04-24 | 安徽淮河化工股份有限公司 | High-temperature-resistant resin anchoring agent and preparation method thereof |
| CN103058576B (en) * | 2012-12-07 | 2014-06-04 | 安徽淮河化工股份有限公司 | Composite dispersant for resin anchoring agent |
| CN103058580B (en) * | 2012-12-07 | 2014-08-20 | 安徽淮河化工股份有限公司 | High-temperature-resistant resin anchoring agent and preparation method thereof |
| CN102993976A (en) * | 2012-12-21 | 2013-03-27 | 广西梧州日成林产化工股份有限公司 | Preparation method of anti-crystallization stable rosin |
| CN103772622A (en) * | 2014-01-22 | 2014-05-07 | 宜兴市兴合树脂有限公司 | Resin capable of being thickened at room temperature for sheet molding compound and preparation method thereof |
| CN103772622B (en) * | 2014-01-22 | 2016-04-27 | 宜兴市兴合树脂有限公司 | Can the sheet molding compound resin and preparation method thereof of normal temperature thickening |
| CN105626110A (en) * | 2016-01-25 | 2016-06-01 | 唐永志 | Full-sized anchoring construction method |
| WO2018011226A1 (en) * | 2016-07-12 | 2018-01-18 | Centre National De La Recherche Scientifique (Cnrs) | Organogels allowing reduction and control of the evaporation of volatile organic liquids |
| FR3053967A1 (en) * | 2016-07-12 | 2018-01-19 | Centre National De La Recherche Scientifique (Cnrs) | ORGANOGELS FOR REDUCING AND CONTROLLING THE EVAPORATION OF VOLATILE ORGANIC LIQUIDS |
| CN106366601A (en) * | 2016-08-27 | 2017-02-01 | 安徽省新力复合材料有限公司 | Unsaturated polyester resin for anchoring agents |
| CN106280196A (en) * | 2016-08-27 | 2017-01-04 | 安徽省新力复合材料有限公司 | A kind of heat resistant unsaturated polyester resin |
| CN106366542A (en) * | 2016-08-27 | 2017-02-01 | 安徽省新力复合材料有限公司 | Antibacterial aging resistant unsaturated polyester resin |
| CN106366250A (en) * | 2016-08-27 | 2017-02-01 | 安徽省新力复合材料有限公司 | Anti-corrosion unsaturated polyester resin for anchoring agent and preparation method thereof |
| CN106397680A (en) * | 2016-08-27 | 2017-02-15 | 安徽省新力复合材料有限公司 | High-toughness unsaturated polyester resin used for anchoring agent, and preparation method thereof |
| CN106366251A (en) * | 2016-08-27 | 2017-02-01 | 安徽省新力复合材料有限公司 | Antibacterial low-viscosity unsaturated polyester resin for anchoring agent |
| CN106366301A (en) * | 2016-08-27 | 2017-02-01 | 安徽省新力复合材料有限公司 | Low-shrinkage-rate unsaturated polyester resin for anchoring agent |
| CN106432701A (en) * | 2016-09-14 | 2017-02-22 | 中国科学院宁波材料技术与工程研究所 | Bio-based unsaturated polyester as well as preparation method and application thereof |
| CN106589749A (en) * | 2016-12-03 | 2017-04-26 | 安徽富丽华化工有限公司 | Modified unsaturated polyester resin having excellent acid and alkali resistance, and preparation method thereof |
| CN111138604A (en) * | 2020-01-07 | 2020-05-12 | 美亚高新材料股份有限公司 | Preparation method of unequal-length double-speed anchoring agent |
| CN117736689A (en) * | 2023-12-18 | 2024-03-22 | 研墨化工(上海)有限公司 | Solvent-free modified polyurethane adhesive and preparation method thereof |
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| CN102212172B (en) | 2013-07-03 |
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