CN106397680A - High-toughness unsaturated polyester resin used for anchoring agent, and preparation method thereof - Google Patents
High-toughness unsaturated polyester resin used for anchoring agent, and preparation method thereof Download PDFInfo
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- CN106397680A CN106397680A CN201610737495.5A CN201610737495A CN106397680A CN 106397680 A CN106397680 A CN 106397680A CN 201610737495 A CN201610737495 A CN 201610737495A CN 106397680 A CN106397680 A CN 106397680A
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- polyester resin
- unsaturated polyester
- tenacity
- anchor agent
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 40
- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004873 anchoring Methods 0.000 title abstract 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 61
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229960000892 attapulgite Drugs 0.000 claims abstract description 49
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 49
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002113 nanodiamond Substances 0.000 claims abstract description 22
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 21
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims abstract description 20
- LNYYKKTXWBNIOO-UHFFFAOYSA-N 3-oxabicyclo[3.3.1]nona-1(9),5,7-triene-2,4-dione Chemical compound C1=CC(C(=O)OC2=O)=CC2=C1 LNYYKKTXWBNIOO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 20
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- XMVQWNRDPAAMJB-UHFFFAOYSA-N (+)-13-Cyclopent-2-enyl-tridecansaeure Natural products OC(=O)CCCCCCCCCCCCC1CCC=C1 XMVQWNRDPAAMJB-UHFFFAOYSA-N 0.000 claims description 20
- XMVQWNRDPAAMJB-QGZVFWFLSA-N (S)-chaulmoogric acid Chemical compound OC(=O)CCCCCCCCCCCC[C@H]1CCC=C1 XMVQWNRDPAAMJB-QGZVFWFLSA-N 0.000 claims description 20
- 239000010941 cobalt Substances 0.000 claims description 20
- 229910017052 cobalt Inorganic materials 0.000 claims description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 20
- 229910019142 PO4 Inorganic materials 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 239000010452 phosphate Substances 0.000 claims description 19
- -1 phosphate ester Chemical class 0.000 claims description 19
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 14
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 abstract 2
- ILGKHPUEWOKEGV-UHFFFAOYSA-N C1(CCCC1)C(=O)O.[Co] Chemical compound C1(CCCC1)C(=O)O.[Co] ILGKHPUEWOKEGV-UHFFFAOYSA-N 0.000 abstract 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 abstract 1
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229920006305 unsaturated polyester Polymers 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21D—SHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
- E21D20/00—Setting anchoring-bolts
- E21D20/02—Setting anchoring-bolts with provisions for grouting
- E21D20/025—Grouting with organic components, e.g. resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Dispersion Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a high-toughness unsaturated polyester resin used for an anchoring agent, and a preparation method thereof. The high-toughness unsaturated polyester resin comprises maleic anhydride, isophthalic acid anhydride, propylene glycol, D-33 monomer, hydroxyhydroquinone, hydroquinone, styrene, melamine phosphate, methyl ethyl ketone peroxide, cobalt cyclopentanecarboxylic acid, aluminium hydroxide, nanosilicon dioxide, nano diamond, modified attapulgite, and ethanediol. The high-toughness unsaturated polyester resin is used for producing the anchoring agent, possesses excellent toughness, and is capable of satisfying requirements on toughness in anchoring agent production process, and improving the toughness of the anchoring agent effectively.
Description
Technical field
The invention belongs to unsaturated polyester resin technical field, more particularly, to a kind of Anchor Agent high tenacity unsaturated polyester (UP)
Resin and preparation method thereof.
Background technology
Unsaturated polyester resin, usually by unsaturated dibasic acid dihydroxylic alcohols or monounsaturated dicarboxylic acid unsaturation dihydroxylic alcohols contracting
The poly- chain macromolecule compound with ester bond and unsaturated double-bond.Generally, polyesterification polycondensation reaction is in 190-220
DEG C carry out, until it reaches expected acid number, after polyesterification contracting reaction terminates, add a certain amount of vinyl monomer while hot, join
Become sticky liquid, such polymer solution is referred to as unsaturated polyester resin.
The processing performance of unsaturated polyester resin is excellent, and this is the maximum advantage of unsaturated polyester resin.Can be in room temperature
Lower solidification, molding under normal pressure, processing performance flexibly, is particularly suitable for large-scale and making in site glass fiber reinforced plastics product.Mechanical performance index
Slightly below epoxy resin, but it is better than phenolic resin.Corrosion resistance, electrical property and anti-flammability can be by selecting the tree of the suitable trade mark
Fat is shallow to meet requirement, color of resin, can make transparent article.Wide in variety, adapt to extensively, price is relatively low.
Unsaturated polyester resin used in Anchor Agent preparation process of the prior art, its toughness cannot meet Anchor Agent
Demand, therefore need badly design a kind of Anchor Agent solve the problems of the prior art with high-tenacity unsaturated polyester resin.
Content of the invention
For solving technical problem present in background technology, the present invention proposes a kind of Anchor Agent high tenacity unsaturated polyester (UP)
Resin and preparation method thereof, the unsaturated polyester resin toughness preparing is high, disclosure satisfy that in Anchor Agent production process to tough
The demand of property.
A kind of Anchor Agent high-tenacity unsaturated polyester resin proposed by the present invention, its raw material includes by weight：Along fourth
Enedioic acid acid anhydride 25-35 part, isophthalic anhydride 2-5 part, propylene glycol 4-8 part, D-33 monomer 1-5 part, benzenetriol 2-6 part, to benzene
Diphenol 3-5 part, styrene 1-4 part, phosphate ester tripolycyanamide 4-8 part, methyl ethyl ketone peroxide 3-6 part, chaulmoogric acid cobalt 1-4 part, hydrogen
Aluminium oxide 2-5 part, nano silicon 1-6 part, Nano diamond 3-5 part, attapulgite modified 4-8 part, ethylene glycol 5-15 part.
Preferably, attapulgite modified it is prepared by following technique：By dehydrated alcohol, silane coupler KH-560 and steaming
Distilled water mix homogeneously, is then placed in heating 25-35min in water-bath, is subsequently added into attapulgite, ultrasonic disperse 10-20min, connects
Regulation pH to 2.5-3.5, be then placed in heating 25-35min in water-bath, then carry out solid-liquid separation, by the solid after separation
With distilled water wash 2-4 time, it is subsequently adding n-butyl alcohol and carries out distillation dehydration, then the powder after dehydration is put into 100-120 DEG C
1-3h is dried in baking oven, be cooled to room temperature obtain attapulgite modified.
Preferably, in attapulgite modified preparation process, the mol ratio of attapulgite and silane coupler KH-560 is
3-6：1-3.
Preferably, aluminium hydroxide, nano silicon, Nano diamond and attapulgite modified weight are than for 3-4：2-
5：3.5-4.5：5-7.
Preferably, its raw material includes by weight：Maleic anhydride 28-32 part, isophthalic anhydride 3-4 part, the third two
Alcohol 5-7 part, D-33 monomer 2-4 part, benzenetriol 3-5 part, hydroquinone 3.5-4.5 part, styrene 2-3 part, phosphate ester melamine
Amine 5-7 part, methyl ethyl ketone peroxide 4-5 part, chaulmoogric acid cobalt 2-3 part, aluminium hydroxide 3-4 part, nano silicon 2-5 part, nanometer
Diamond 3.5-4.5 part, attapulgite modified 5-7 part, ethylene glycol 8-12 part.
Preferably, its raw material includes by weight：30 parts of maleic anhydride, 3.5 parts of isophthalic anhydride, propylene glycol 6
Part, 3 parts of D-33 monomer, 4 parts of benzenetriol, 4 parts of hydroquinone, 2.5 parts of styrene, 6 parts of phosphate ester tripolycyanamide, peroxidating first and second
4.5 parts of ketone, 2.5 parts of chaulmoogric acid cobalt, 3.5 parts of aluminium hydroxide, 3.5 parts of nano silicon, 4 parts of Nano diamond, modification are concavo-convex
Rod soil 6 parts, 10 parts of ethylene glycol.
A kind of preparation method of Anchor Agent high-tenacity unsaturated polyester resin of the present invention, comprises the steps：
S1, by ethylene glycol, propylene glycol and isophthalic anhydride mix homogeneously, be warming up to 180-220 DEG C insulation 1-3h, then
It is cooled to 150-160 DEG C, adds maleic anhydride and D-33 monomer mix homogeneously, then heat to 180-190 DEG C, be incubated 2-
4h, is cooled to room temperature and obtains material a；
S2, in material a add benzenetriol, be warming up to 195-205 DEG C, be incubated 1-3h, controls vacuum be 0.1-
0.2Gpa continuous evacuation 1-3h controls acid number to stop evacuation after 20-30mgKOH/g and start to be cooled to 175-185 DEG C of throwing
Enter hydroquinone mix homogeneously, cold go to obtain material b to room temperature；
S3, in material b add styrene, be warming up to 125-145 DEG C, be incubated 0.5-1.5h, then in 400-600r/
Min stirs 30-50min, is then cooled to 60-80 DEG C, is incubated 0.5-1.5h, is subsequently added into phosphate ester tripolycyanamide, in 250-
350r/min stirs 15-25min, is cooled to room temperature and obtains material c；
S4, in material c add aluminium hydroxide, nano silicon, Nano diamond and attapulgite modified mixing equal
Even, stir 30-50min in 1500-2500r/min, be subsequently added into methyl ethyl ketone peroxide and chaulmoogric acid cobalt mix homogeneously, ultrasonic point
Scattered 10-20min obtains Anchor Agent high-tenacity unsaturated polyester resin.
A kind of Anchor Agent high-tenacity unsaturated polyester resin of the present invention, its raw material includes maleic anhydride, isophthalic
Dicarboxylic acid anhydride, propylene glycol, D-33 monomer, benzenetriol, hydroquinone, styrene, phosphate ester tripolycyanamide, methyl ethyl ketone peroxide,
Chaulmoogric acid cobalt, aluminium hydroxide, nano silicon, Nano diamond, attapulgite modified and ethylene glycol.Wherein with maleic two
Anhydride and isophthalic anhydride as anhydride reaction thing, using propylene glycol and ethylene glycol as alcohol reactant, with benzenetriol with to benzene
Diphenol, as phenol reactant, using styrene as cross-linking agent, is used as initiator by adding methyl ethyl ketone peroxide, chaulmoogric acid cobalt is made
For accelerator, and add aluminium hydroxide, nano silicon, Nano diamond and attapulgite modified as filler, using filling out
Hydroxyl on material, by styrene and alcohol reactant, is effectively combined, and the unsaturated polyester resin preparing has
Excellent toughness.Wherein interpolation attapulgite modified with attapulgite and silane coupler KH-560 as raw material, through silane
The graft modification of coupling agent, effectively imparts the excellent toughness of unsaturated polyester resin of the present invention.The present invention prepares not
Saturated polyester resin is used for producing Anchor Agent, has excellent toughness, disclosure satisfy that the toughness requirements in Anchor Agent production process,
The toughness of Anchor Agent can be effectively improved.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail it should be appreciated that embodiment is served only for this is described
Bright, rather than be used for limiting the invention, any modification made on the basis of the present invention, equivalent etc. are all at this
In bright protection domain.
In specific embodiment, the weight portion of maleic anhydride can for 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30
Part, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts；The weight portion of isophthalic anhydride can for 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4
Part, 4.5 parts, 5 parts；The weight portion of propylene glycol can be 4 parts, 5 parts, 6 parts, 7 parts, 8 parts；The weight portion of D-33 monomer can be 1
Part, 2 parts, 3 parts, 4 parts, 5 parts；The weight portion of benzenetriol can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts；The weight portion of hydroquinone can
Think 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；Cinnamic weight portion can for 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5
Part, 4 parts；The weight portion of phosphate ester tripolycyanamide can be 4 parts, 5 parts, 6 parts, 7 parts, 8 parts；The weight portion of methyl ethyl ketone peroxide can
Think 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；The weight portion of chaulmoogric acid cobalt can for 1 part, 1.5 parts, 2 parts, 2.5
Part, 3 parts, 3.5 parts, 4 parts；The weight portion of aluminium hydroxide can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；Nanometer
The weight portion of silicon dioxide can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；
The weight portion of Nano diamond can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；Attapulgite modified weight portion can be 4
Part, 5 parts, 6 parts, 7 parts, 8 parts；The weight portion of ethylene glycol can for 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13
Part, 14 parts, 15 parts.
Embodiment 1
A kind of Anchor Agent high-tenacity unsaturated polyester resin proposed by the present invention, its raw material includes by weight：Along fourth
30 parts of enedioic acid acid anhydride, 3.5 parts of isophthalic anhydride, 6 parts of propylene glycol, 3 parts of D-33 monomer, 4 parts of benzenetriol, 4 parts of hydroquinone, benzene
2.5 parts of ethylene, 6 parts of phosphate ester tripolycyanamide, 4.5 parts of methyl ethyl ketone peroxide, 2.5 parts of chaulmoogric acid cobalt, 3.5 parts of aluminium hydroxide, receive
3.5 parts of silicon dioxide of rice, 4 parts of Nano diamond, attapulgite modified 6 parts, 10 parts of ethylene glycol.
Embodiment 2
A kind of Anchor Agent high-tenacity unsaturated polyester resin proposed by the present invention, its raw material includes by weight：Along fourth
25 parts of enedioic acid acid anhydride, 5 parts of isophthalic anhydride, 4 parts of propylene glycol, 5 parts of D-33 monomer, 2 parts of benzenetriol, 5 parts of hydroquinone, benzene second
1 part of alkene, 8 parts of phosphate ester tripolycyanamide, 3 parts of methyl ethyl ketone peroxide, 4 parts of chaulmoogric acid cobalt, 2 parts of aluminium hydroxide, nano silicon 6
Part, 3 parts of Nano diamond, attapulgite modified 8 parts, 5 parts of ethylene glycol.
Attapulgite modified it is prepared by following technique：Dehydrated alcohol, silane coupler KH-560 and distilled water are mixed
Close uniformly, be then placed in heating 25min in water-bath, be subsequently added into attapulgite, ultrasonic disperse 20min, then adjust pH to
2.5, it is then placed in heating 35min in water-bath, then carries out solid-liquid separation, by the distilled water wash 2 times of the solid after separation, so
Add n-butyl alcohol to carry out distillation dehydration afterwards, then put into the powder after dehydration in 120 DEG C of baking ovens and 1h is dried, be cooled to room temperature and obtain
To attapulgite modified.Wherein, the mol ratio of attapulgite and silane coupler KH-560 is 3：3.
A kind of preparation method of Anchor Agent high-tenacity unsaturated polyester resin of the present invention, comprises the steps：
S1, by ethylene glycol, propylene glycol and isophthalic anhydride mix homogeneously, be warming up to 180 DEG C insulation 3h, be then cooled to
150 DEG C, add maleic anhydride and D-33 monomer mix homogeneously, then heat to 190 DEG C, be incubated 2h, be cooled to room temperature and obtain
To material a；
S2, in material a add benzenetriol, be warming up to 205 DEG C, be incubated 1h, control vacuum continuously take out very for 0.2Gpa
Empty 1h controls acid number to stop evacuation starting after 30mgKOH/g and be cooled to 175 DEG C putting into hydroquinone mix homogeneously, cold goes
Obtain material b to room temperature；
S3, in material b add styrene, be warming up to 145 DEG C, be incubated 0.5h, then in 600r/min stir 30min,
Then it is cooled to 80 DEG C, is incubated 0.5h, is subsequently added into phosphate ester tripolycyanamide, stir 15min in 350r/min, be cooled to room temperature
Obtain material c；
S4, in material c add aluminium hydroxide, nano silicon, Nano diamond and attapulgite modified mixing equal
Even, stir 30min in 2500r/min, be subsequently added into methyl ethyl ketone peroxide and chaulmoogric acid cobalt mix homogeneously, ultrasonic disperse 20min
Obtain Anchor Agent high-tenacity unsaturated polyester resin.
Embodiment 3
A kind of Anchor Agent high-tenacity unsaturated polyester resin proposed by the present invention, its raw material includes by weight：Along fourth
35 parts of enedioic acid acid anhydride, 2 parts of isophthalic anhydride, 8 parts of propylene glycol, 1 part of D-33 monomer, 6 parts of benzenetriol, 3 parts of hydroquinone, benzene second
4 parts of alkene, 4 parts of phosphate ester tripolycyanamide, 6 parts of methyl ethyl ketone peroxide, 1 part of chaulmoogric acid cobalt, 5 parts of aluminium hydroxide, nano silicon 1
Part, 5 parts of Nano diamond, attapulgite modified 4 parts, 15 parts of ethylene glycol.
Attapulgite modified it is prepared by following technique：Dehydrated alcohol, silane coupler KH-560 and distilled water are mixed
Close uniformly, be then placed in heating 35min in water-bath, be subsequently added into attapulgite, ultrasonic disperse 10min, then adjust pH to
3.5, it is then placed in heating 25min in water-bath, then carries out solid-liquid separation, by the distilled water wash 4 times of the solid after separation, so
Add n-butyl alcohol to carry out distillation dehydration afterwards, then put into the powder after dehydration in 100 DEG C of baking ovens and 3h is dried, be cooled to room temperature and obtain
To attapulgite modified.Wherein, the mol ratio of attapulgite and silane coupler KH-560 is 6：1.
A kind of preparation method of Anchor Agent high-tenacity unsaturated polyester resin of the present invention, comprises the steps：
S1, by ethylene glycol, propylene glycol and isophthalic anhydride mix homogeneously, be warming up to 220 DEG C insulation 1h, be then cooled to
160 DEG C, add maleic anhydride and D-33 monomer mix homogeneously, then heat to 180 DEG C, be incubated 4h, be cooled to room temperature and obtain
To material a；
S2, in material a add benzenetriol, be warming up to 195 DEG C, be incubated 3h, control vacuum continuously take out very for 0.1Gpa
Empty 3h controls acid number to stop evacuation starting after 20mgKOH/g and be cooled to 185 DEG C putting into hydroquinone mix homogeneously, cold goes
Obtain material b to room temperature；
S3, in material b add styrene, be warming up to 125 DEG C, be incubated 1.5h, then in 400r/min stir 50min,
Then it is cooled to 60 DEG C, is incubated 1.5h, is subsequently added into phosphate ester tripolycyanamide, stir 25min in 250r/min, be cooled to room temperature
Obtain material c；
S4, in material c add aluminium hydroxide, nano silicon, Nano diamond and attapulgite modified mixing equal
Even, stir 50min in 1500r/min, be subsequently added into methyl ethyl ketone peroxide and chaulmoogric acid cobalt mix homogeneously, ultrasonic disperse 10min
Obtain Anchor Agent high-tenacity unsaturated polyester resin.
Embodiment 4
A kind of Anchor Agent high-tenacity unsaturated polyester resin proposed by the present invention, its raw material includes by weight：Along fourth
28 parts of enedioic acid acid anhydride, 4 parts of isophthalic anhydride, 5 parts of propylene glycol, 4 parts of D-33 monomer, 3 parts of benzenetriol, 4.5 parts of hydroquinone, benzene
2 parts of ethylene, 7 parts of phosphate ester tripolycyanamide, 4 parts of methyl ethyl ketone peroxide, 3 parts of chaulmoogric acid cobalt, 3 parts of aluminium hydroxide, nanometer titanium dioxide
5 parts of silicon, 3.5 parts of Nano diamond, attapulgite modified 7 parts, 8 parts of ethylene glycol.
Attapulgite modified it is prepared by following technique：Dehydrated alcohol, silane coupler KH-560 and distilled water are mixed
Close uniformly, be then placed in heating 28min in water-bath, be subsequently added into attapulgite, ultrasonic disperse 18min, then adjust pH to
2.8, it is then placed in heating 32min in water-bath, then carries out solid-liquid separation, by the distilled water wash 2 times of the solid after separation, so
Add n-butyl alcohol to carry out distillation dehydration afterwards, then put into the powder after dehydration in 115 DEG C of baking ovens and 1.5h is dried, be cooled to room temperature
Obtain attapulgite modified.Wherein, the mol ratio of attapulgite and silane coupler KH-560 is 4：2.5.
A kind of preparation method of Anchor Agent high-tenacity unsaturated polyester resin of the present invention, comprises the steps：
S1, by ethylene glycol, propylene glycol and isophthalic anhydride mix homogeneously, be warming up to 185 DEG C insulation 2.5h, then lower the temperature
To 152 DEG C, add maleic anhydride and D-33 monomer mix homogeneously, then heat to 188 DEG C, be incubated 2.5h, be cooled to room
Temperature obtains material a；
S2, in material a add benzenetriol, be warming up to 202 DEG C, be incubated 1.5h, control vacuum continuously take out for 0.18Gpa
Vacuum 1.5h controls acid number to stop evacuation after 28mgKOH/g and start to be cooled to 178 DEG C of input hydroquinone mix homogeneously,
Cold go to obtain material b to room temperature；
S3, in material b add styrene, be warming up to 142 DEG C, be incubated 0.8h, then in 550r/min stir 35min,
Then it is cooled to 75 DEG C, is incubated 0.8h, is subsequently added into phosphate ester tripolycyanamide, stir 18min in 320r/min, be cooled to room temperature
Obtain material c；
S4, in material c add aluminium hydroxide, nano silicon, Nano diamond and attapulgite modified mixing equal
Even, stir 35min in 2200r/min, be subsequently added into methyl ethyl ketone peroxide and chaulmoogric acid cobalt mix homogeneously, ultrasonic disperse 18min
Obtain Anchor Agent high-tenacity unsaturated polyester resin.
Embodiment 5
A kind of Anchor Agent high-tenacity unsaturated polyester resin proposed by the present invention, its raw material includes by weight：Along fourth
32 parts of enedioic acid acid anhydride, 3 parts of isophthalic anhydride, 7 parts of propylene glycol, 2 parts of D-33 monomer, 5 parts of benzenetriol, 3.5 parts of hydroquinone, benzene
3 parts of ethylene, 5 parts of phosphate ester tripolycyanamide, 5 parts of methyl ethyl ketone peroxide, 2 parts of chaulmoogric acid cobalt, 4 parts of aluminium hydroxide, nanometer titanium dioxide
2 parts of silicon, 4.5 parts of Nano diamond, attapulgite modified 5 parts, 12 parts of ethylene glycol.
Attapulgite modified it is prepared by following technique：Dehydrated alcohol, silane coupler KH-560 and distilled water are mixed
Close uniformly, be then placed in heating 32min in water-bath, be subsequently added into attapulgite, ultrasonic disperse 12min, then adjust pH to
3.2, it is then placed in heating 28min in water-bath, then carries out solid-liquid separation, by the distilled water wash 4 times of the solid after separation, so
Add n-butyl alcohol to carry out distillation dehydration afterwards, then put into the powder after dehydration in 105 DEG C of baking ovens and 2.5h is dried, be cooled to room temperature
Obtain attapulgite modified.Wherein, the mol ratio of attapulgite and silane coupler KH-560 is 5：1.5.
A kind of preparation method of Anchor Agent high-tenacity unsaturated polyester resin of the present invention, comprises the steps：
S1, by ethylene glycol, propylene glycol and isophthalic anhydride mix homogeneously, be warming up to 215 DEG C insulation 1.5h, then lower the temperature
To 158 DEG C, add maleic anhydride and D-33 monomer mix homogeneously, then heat to 182 DEG C, be incubated 3.5h, be cooled to room
Temperature obtains material a；
S2, in material a add benzenetriol, be warming up to 202 DEG C, be incubated 1.5h, control vacuum continuously take out for 0.18Gpa
Vacuum 1.5h controls acid number to stop evacuation after 28mgKOH/g and start to be cooled to 178 DEG C of input hydroquinone mix homogeneously,
Cold go to obtain material b to room temperature；
S3, in material b add styrene, be warming up to 142 DEG C, be incubated 0.8h, then in 550r/min stir 35min,
Then it is cooled to 75 DEG C, is incubated 0.8h, is subsequently added into phosphate ester tripolycyanamide, stir 18min in 320r/min, be cooled to room temperature
Obtain material c；
S4, in material c add aluminium hydroxide, nano silicon, Nano diamond and attapulgite modified mixing equal
Even, stir 35min in 2200r/min, be subsequently added into methyl ethyl ketone peroxide and chaulmoogric acid cobalt mix homogeneously, ultrasonic disperse 18min
Obtain Anchor Agent high-tenacity unsaturated polyester resin.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any those familiar with the art the invention discloses technical scope in, technology according to the present invention scheme and its
Inventive concept equivalent or change in addition, all should be included within the scope of the present invention.
Claims (7)
1. a kind of Anchor Agent high-tenacity unsaturated polyester resin is it is characterised in that its raw material includes by weight：Maleic two
Anhydride 25-35 part, isophthalic anhydride 2-5 part, propylene glycol 4-8 part, D-33 monomer 1-5 part, benzenetriol 2-6 part, hydroquinone
3-5 part, styrene 1-4 part, phosphate ester tripolycyanamide 4-8 part, methyl ethyl ketone peroxide 3-6 part, chaulmoogric acid cobalt 1-4 part, hydroxide
Aluminum 2-5 part, nano silicon 1-6 part, Nano diamond 3-5 part, attapulgite modified 4-8 part, ethylene glycol 5-15 part.
2. Anchor Agent high-tenacity unsaturated polyester resin according to claim 1 is it is characterised in that attapulgite modified
It is prepared by following technique：It is then placed in dehydrated alcohol, silane coupler KH-560 and distilled water mix homogeneously in water-bath
Heating 25-35min, is subsequently added into attapulgite, ultrasonic disperse 10-20min, then adjusts pH to 2.5-3.5, is then placed in water
Heat 25-35min in bath, then carry out solid-liquid separation, distilled water wash 2-4 time of the solid after separation is just subsequently adding
Butanol carries out distillation dehydration, then puts into the powder after dehydration in 100-120 DEG C of baking oven and 1-3h is dried, be cooled to room temperature and obtain
Attapulgite modified.
3. Anchor Agent high-tenacity unsaturated polyester resin according to claim 1 and 2 is it is characterised in that modification is concavo-convex
In the preparation process of rod soil, the mol ratio of attapulgite and silane coupler KH-560 is 3-6：1-3.
4. the Anchor Agent high-tenacity unsaturated polyester resin according to any one of claim 1-3 is it is characterised in that hydrogen-oxygen
Change aluminum, nano silicon, Nano diamond and attapulgite modified weight ratio for 3-4：2-5：3.5-4.5：5-7.
5. the Anchor Agent high-tenacity unsaturated polyester resin according to any one of claim 1-4 is it is characterised in that it is former
Material includes by weight：Maleic anhydride 28-32 part, isophthalic anhydride 3-4 part, propylene glycol 5-7 part, D-33 monomer 2-4
Part, benzenetriol 3-5 part, hydroquinone 3.5-4.5 part, styrene 2-3 part, phosphate ester tripolycyanamide 5-7 part, methyl ethyl ketone peroxide
4-5 part, chaulmoogric acid cobalt 2-3 part, aluminium hydroxide 3-4 part, nano silicon 2-5 part, Nano diamond 3.5-4.5 part, modification
Attapulgite 5-7 part, ethylene glycol 8-12 part.
6. the Anchor Agent high-tenacity unsaturated polyester resin according to any one of claim 1-5 is it is characterised in that it is former
Material includes by weight：30 parts of maleic anhydride, 3.5 parts of isophthalic anhydride, 6 parts of propylene glycol, 3 parts of D-33 monomer, benzene three
4 parts of phenol, 4 parts of hydroquinone, 2.5 parts of styrene, 6 parts of phosphate ester tripolycyanamide, 4.5 parts of methyl ethyl ketone peroxide, chaulmoogric acid cobalt 2.5
Part, 3.5 parts of aluminium hydroxide, 3.5 parts of nano silicon, 4 parts of Nano diamond, attapulgite modified 6 parts, 10 parts of ethylene glycol.
7. the preparation method of the Anchor Agent high-tenacity unsaturated polyester resin described in a kind of any one according to claim 1-6,
It is characterized in that, comprise the steps：
S1, by ethylene glycol, propylene glycol and isophthalic anhydride mix homogeneously, be warming up to 180-220 DEG C insulation 1-3h, then lower the temperature
To 150-160 DEG C, add maleic anhydride and D-33 monomer mix homogeneously, then heat to 180-190 DEG C, be incubated 2-4h,
It is cooled to room temperature and obtain material a；
S2, in material a add benzenetriol, be warming up to 195-205 DEG C, be incubated 1-3h, control vacuum be 0.1-0.2Gpa company
Continuous evacuation 1-3h controls acid number to stop evacuation after 20-30mgKOH/g and start to be cooled to 175-185 DEG C of input to benzene two
Phenol mix homogeneously, cold goes to obtain material b to room temperature；
S3, in material b add styrene, be warming up to 125-145 DEG C, be incubated 0.5-1.5h, then stir in 400-600r/min
Mix 30-50min, be then cooled to 60-80 DEG C, be incubated 0.5-1.5h, be subsequently added into phosphate ester tripolycyanamide, in 250-350r/
Min stirs 15-25min, is cooled to room temperature and obtains material c；
S4, add aluminium hydroxide, nano silicon, Nano diamond and attapulgite modified mix homogeneously in material c, in
1500-2500r/min stirs 30-50min, is subsequently added into methyl ethyl ketone peroxide and chaulmoogric acid cobalt mix homogeneously, ultrasonic disperse 10-
20min obtains Anchor Agent high-tenacity unsaturated polyester resin.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109589947A (en) * | 2018-11-27 | 2019-04-09 | 艾美科健（中国）生物医药有限公司 | One kind macroporous adsorbent resin preparation method thereof of polystyrene containing polyphenol hydroxyl and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212172A (en) * | 2011-02-17 | 2011-10-12 | 安徽淮河化工股份有限公司 | Resin special for anchoring agent and preparation method thereof |
| CN102391632A (en) * | 2011-09-14 | 2012-03-28 | 中国林业科学研究院林产化学工业研究所 | Graphene oxide/unsaturated polyester composite material and preparation method thereof |
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2016
- 2016-08-27 CN CN201610737495.5A patent/CN106397680A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212172A (en) * | 2011-02-17 | 2011-10-12 | 安徽淮河化工股份有限公司 | Resin special for anchoring agent and preparation method thereof |
| CN102391632A (en) * | 2011-09-14 | 2012-03-28 | 中国林业科学研究院林产化学工业研究所 | Graphene oxide/unsaturated polyester composite material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109589947A (en) * | 2018-11-27 | 2019-04-09 | 艾美科健（中国）生物医药有限公司 | One kind macroporous adsorbent resin preparation method thereof of polystyrene containing polyphenol hydroxyl and application |
| CN109589947B (en) * | 2018-11-27 | 2021-11-30 | 艾美科健（中国）生物医药有限公司 | Preparation method and application of polystyrene macroporous adsorption resin containing polyphenol hydroxyl groups |
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Application publication date: 20170215 |