CN106398079A - High tensile strength unsaturated polyester resin for anchoring agents and preparation method thereof - Google Patents
High tensile strength unsaturated polyester resin for anchoring agents and preparation method thereof Download PDFInfo
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- CN106398079A CN106398079A CN201610743503.7A CN201610743503A CN106398079A CN 106398079 A CN106398079 A CN 106398079A CN 201610743503 A CN201610743503 A CN 201610743503A CN 106398079 A CN106398079 A CN 106398079A
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- Prior art keywords
- parts
- polyester resin
- unsaturated polyester
- high tensile
- anchor agent
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 44
- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004873 anchoring Methods 0.000 title abstract description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 108
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 67
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 44
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 42
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims abstract description 40
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 40
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 29
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 24
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 23
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001361 adipic acid Substances 0.000 claims abstract description 21
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 21
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 21
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 18
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 18
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 18
- 229960004063 propylene glycol Drugs 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 7
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims abstract 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 21
- 229910000077 silane Inorganic materials 0.000 claims description 21
- 239000005543 nano-size silicon particle Substances 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims description 17
- 230000008878 coupling Effects 0.000 claims description 17
- 238000010168 coupling process Methods 0.000 claims description 17
- 238000005859 coupling reaction Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 125000002619 bicyclic group Chemical group 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 abstract 1
- 239000006087 Silane Coupling Agent Substances 0.000 abstract 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 abstract 1
- 229910052901 montmorillonite Inorganic materials 0.000 abstract 1
- 235000013772 propylene glycol Nutrition 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 239000002383 tung oil Substances 0.000 abstract 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- -1 maleic acid Acid anhydride Chemical class 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000003642 hunger Nutrition 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Mining & Mineral Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Structural Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a high tensile strength unsaturated polyester resin for anchoring agents. The raw materials include: maleic anhydride, dibutyl phthalate, styrene, dicyclopentadiene, SBS792, SBS801, phthalic anhydride, 1, 2-propanediol, diethylene glycol, ethylene glycol, adipic acid, diisocyanate, hydroquinone, resorcinol, methyl ethyl ketone peroxide, cobalt naphthenate, benzoyl peroxide, N, N-dimethylaniline, tung oil, nano silica, nano montmorillonite, a silane coupling agent KH-570 and deionized water. The invention also provides a preparation method of the high tensile strength unsaturated polyester resin for anchoring agents. The unsaturated polyester resin prepared by the method provided by the invention can be applied to preparation of anchoring agents, has excellent tensile strength, and can endow anchoring agents with excellent tensile strength.
Description
Technical field
The invention belongs to unsaturated polyester resin technical field, more particularly, to a kind of insatiable hunger of Anchor Agent high tensile
With polyester resin and preparation method thereof.
Background technology
Metal bolts, deformed bar, riffled tube are securely seated between concrete, replace the side of embedded bar in rock datum hole
Method is referred to as " anchoring ".Anchoring process is generally divided into expansible anchor of metal method and chemical bonding method.Chemical bonding anchoring uses
With binding agent, metal rod and matrix are securely joined with into an entirety, binding agent used is referred to as resin anchoring agent.Resin
Anchor Agent is typically made up of Special Resin, high-strength filler, firming agent, accelerator and various auxiliary agent.
In prior art, the tensile strength of the unsaturated-resin for producing Anchor Agent cannot meet Anchor Agent Production requirement,
The unsaturated polyester resin therefore needing a kind of design Anchor Agent high tensile badly solves the problems of the prior art.
Content of the invention
For solving technical problem present in background technology, the present invention proposes a kind of insatiable hunger of Anchor Agent high tensile
With polyester resin and preparation method thereof, the unsaturated polyester resin preparing is applied to the preparation of Anchor Agent, has excellent
Tensile strength, can give Anchor Agent excellent tensile strength.
A kind of unsaturated polyester resin of Anchor Agent high tensile proposed by the present invention, its raw material wraps by weight
Include：Maleic anhydride 20-40 part, dibutyl phthalate 5-15 part, styrene 3-9 part, dicyclopentadiene 4-8 part,
SBS792 3-5 part, SBS801 3-6 part, phthalic anhydride 2-5 part, 1,2- propylene glycol 1-4 part, diethylene glycol 1-4 part, second
Glycol 2-5 part, adipic acid 2-4 part, diisocyanate 3-5 part, hydroquinone 1-4 part, resorcinol 2-5 part, peroxidating first and second
Ketone 2-4 part, cobalt naphthenate 1-4 part, benzoyl peroxide 2-5 part, N, accelerine 3-6 part, Oleum Verniciae fordii 1-5 part, nanometer two
Silicon oxide 2-4 part, nano imvite 3-6 part, Silane coupling reagent KH-570 3-6 part, deionized water 4-6 part.
Preferably, maleic anhydride, phthalic anhydride, styrene, dicyclopentadiene, 1,2-PD, diethyl two
The weight of alcohol, ethylene glycol, adipic acid and diisocyanate is than for 25-35：2.5-4.5：4-8：5-7：2-3：2-3：3-4：2.5-
3.5：3.5-4.5.
Preferably, the weight of maleic anhydride, phthalic anhydride, styrene, dicyclopentadiene, SBS792 and SBS801
Amount ratio is 25-35：3-4：4-8：5-7：3.5-4.5：4-5.
Preferably, methyl ethyl ketone peroxide, cobalt naphthenate, nano silicon, nano imvite and silane coupler KH-
570 weight is than for 2.5-3.5：2-3：2.5-3.5：4-5：4-5.
Preferably, its raw material includes by weight：Maleic anhydride 25-35 part, dibutyl phthalate 8-12 part,
Styrene 4-8 part, dicyclopentadiene 5-7 part, SBS792 3.5-4.5 part, SBS801 4-5 part, phthalic anhydride 3-4 part,
1,2- propylene glycol 2-3 part, diethylene glycol 2-3 part, ethylene glycol 3-4 part, adipic acid 2.5-3.5 part, diisocyanate 3.5-4.5
Part, hydroquinone 2-3 part, resorcinol 3-4 part, methyl ethyl ketone peroxide 2.5-3.5 part, cobalt naphthenate 2-3 part, benzoyl peroxide first
Acyl 3-4 part, N, accelerine 4-5 part, Oleum Verniciae fordii 2-4 part, nano silicon 2.5-3.5 part, nano imvite 4-5 part,
Silane coupling reagent KH-570 4-5 part, deionized water 4.5-5.5 part.
Preferably, its raw material includes by weight：30 parts of maleic anhydride, 10 parts of dibutyl phthalate, benzene second
6 parts of alkene, 3 parts of dicyclopentadiene, 4 parts of SBS792,4.5 parts of SBS801,3.5 parts of phthalic anhydride, 1,2- propylene glycol 2.5
Part, 2.5 parts of diethylene glycol, 3.5 parts of ethylene glycol, 3 parts of adipic acid, 4 parts of diisocyanate, 2.5 parts of hydroquinone, resorcinol
3.5 parts, 3 parts of methyl ethyl ketone peroxide, 2.5 parts of cobalt naphthenate, 3.5 parts of benzoyl peroxide, N, 4.5 parts of accelerine, paulownia
3 parts of oil, 3 parts of nano silicon, 4.5 parts of nano imvite, 4.5 parts of Silane coupling reagent KH-570,5 parts of deionized water.
A kind of preparation method of the unsaturated polyester resin of Anchor Agent high tensile of the present invention, walks including following
Suddenly：
S1, by maleic anhydride, diethylene glycol, ethylene glycol, adipic acid, phosphoric acid and deionized water mix homogeneously, be passed through
Nitrogen, stirs 20-40min, then Deca dicyclopentadiene in 5500-8500r/min, is warming up to 125-135 DEG C, is incubated 1-
3h, is subsequently adding phthalic anhydride, 1,2-PD and hydroquinone mix homogeneously, is warming up to 195-200 DEG C, when acid number fall
During to 60-70mg/g, it is cooled to 170-180 DEG C, is incubated 30-50min, add Oleum Verniciae fordii mix homogeneously, be warming up to 205-220 DEG C,
It is 30-40mg/g to acid number, is cooled to 150-160 DEG C, add resorcinol and diisocyanate mix homogeneously, then proceed to drop
Temperature, to 90-100 DEG C, is incubated 20-40min, adds styrene, SBS792 and SBS801 mix homogeneously, is cooled to room temperature and obtains thing
Material a；
S2, add nano silicon, nano imvite and Silane coupling reagent KH-570 in material a, in 3500-
5500r/min stirs 2-4h, is subsequently adding methyl ethyl ketone peroxide, cobalt naphthenate, benzoyl peroxide, dibutyl phthalate
And DMA, ultrasonic disperse 20-40min, then heat to 60-80 DEG C, be incubated 2-4h, be cooled to room temperature and obtain anchor
Gu the unsaturated polyester resin of agent high tensile.
A kind of unsaturated polyester resin of Anchor Agent high tensile of the present invention, its raw material includes maleic acid
Acid anhydride, dibutyl phthalate, styrene, dicyclopentadiene, SBS792, SBS801, phthalic anhydride, 1,2- propylene glycol,
Diethylene glycol, ethylene glycol, adipic acid, diisocyanate, hydroquinone, resorcinol, methyl ethyl ketone peroxide, cobalt naphthenate, mistake
BP, N, accelerine, Oleum Verniciae fordii, nano silicon, nano imvite, Silane coupling reagent KH-570 and go from
Sub- water.Wherein, using maleic anhydride and phthalic anhydride as acid reaction, with 1,2-PD, diethylene glycol and second
Glycol, as alcohol reactant, with styrenic crosslinker, adds SBS792 and SBS801 as thermoplastic elastomer (TPE), with peroxidating first
Ethyl ketone as initiator, using cobalt naphthenate as accelerator, using nano silicon and nano imvite as filler, through silicon
The graft modification of alkane coupling agent kh-570, imparts the excellent tensile strength of unsaturated polyester resin of the present invention, using add
Conjugated triene in Oleum Verniciae fordii, the unsaturated polyester resin that interpolation dicyclopentadiene prepares through hydrolyzed addition process has excellent
Tensile strength.The unsaturated polyester resin that the present invention prepares is applied to the preparation of Anchor Agent, has excellent stretching strong
Degree, can give Anchor Agent excellent tensile strength.
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 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25
Part, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40
Part；The weight portion of dibutyl phthalate can for 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14
Part, 15 parts；Cinnamic weight portion can be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts；The weight portion of dicyclopentadiene can
Think 4 parts, 5 parts, 6 parts, 7 parts, 8 parts；The weight portion of SBS792 can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；SBS801's
Weight portion can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；The weight portion of phthalic anhydride can for 2 parts,
2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The weight portion of 1,2- propylene glycol can for 1 part, 1.5 parts, 2 parts, 2.5 parts, 3
Part, 3.5 parts, 4 parts；The weight portion of diethylene glycol can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts；Ethylene glycol
Weight portion can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The weight portion of adipic acid can for 2 parts, 2.5 parts, 3
Part, 3.5 parts, 4 parts；The weight portion of diisocyanate can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The weight portion of hydroquinone
Can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts；The weight portion of resorcinol can for 2 parts, 2.5 parts, 3 parts,
3.5 parts, 4 parts, 4.5 parts, 5 parts；The weight portion of methyl ethyl ketone peroxide can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts；Aphthenic acids
The weight portion of cobalt can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts；The weight portion of benzoyl peroxide can be 2
Part, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；N, the weight portion of accelerine can for 3 parts, 3.5 parts, 4 parts,
4.5 parts, 5 parts, 5.5 parts, 6 parts；The weight portion of Oleum Verniciae fordii can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts；The weight of nano silicon
Part can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts；The weight portion of nano imvite can for 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5
Part, 5.5 parts, 6 parts；The weight portion of Silane coupling reagent KH-570 can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；
The weight portion of deionized water can be 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts.
Embodiment 1
A kind of unsaturated polyester resin of Anchor Agent high tensile proposed by the present invention, its raw material wraps by weight
Include：30 parts of maleic anhydride, 10 parts of dibutyl phthalate, 6 parts of styrene, 3 parts of dicyclopentadiene, 4 parts of SBS792,
4.5 parts of SBS801,3.5 parts of phthalic anhydride, 2.5 parts of 1,2- propylene glycol, 2.5 parts of diethylene glycol, 3.5 parts of ethylene glycol, oneself two
3 parts of acid, 4 parts of diisocyanate, 2.5 parts of hydroquinone, 3.5 parts of resorcinol, 3 parts of methyl ethyl ketone peroxide, cobalt naphthenate 2.5
Part, 3.5 parts of benzoyl peroxide, N, 4.5 parts of accelerine, 3 parts of Oleum Verniciae fordii, 3 parts of nano silicon, nano imvite
4.5 parts, 4.5 parts of Silane coupling reagent KH-570,5 parts of deionized water.
Embodiment 2
A kind of unsaturated polyester resin of Anchor Agent high tensile proposed by the present invention, its raw material wraps by weight
Include：20 parts of maleic anhydride, 15 parts of dibutyl phthalate, 3 parts of styrene, 8 parts of dicyclopentadiene, 3 parts of SBS792,
6 parts of SBS801,2 parts of phthalic anhydride, 4 parts of 1,2- propylene glycol, 1 part of diethylene glycol, 5 parts of ethylene glycol, 2 parts of adipic acid, two different
5 parts of cyanate, 1 part of hydroquinone, 5 parts of resorcinol, 2 parts of methyl ethyl ketone peroxide, 4 parts of cobalt naphthenate, benzoyl peroxide 2
Part, N, 6 parts of accelerine, 1 part of Oleum Verniciae fordii, 4 parts of nano silicon, 3 parts of nano imvite, Silane coupling reagent KH-570 6
Part, 4 parts of deionized water.
A kind of preparation method of the unsaturated polyester resin of Anchor Agent high tensile of the present invention, walks including following
Suddenly：
S1, by maleic anhydride, diethylene glycol, ethylene glycol, adipic acid, phosphoric acid and deionized water mix homogeneously, be passed through
Nitrogen, stirs 40min, then Deca dicyclopentadiene in 5500r/min, is warming up to 125 DEG C, is incubated 3h, is subsequently adding adjacent benzene
Dicarboxylic acid anhydride, 1,2-PD and hydroquinone mix homogeneously, are warming up to 195 DEG C, when acid number drops to 70mg/g, are cooled to
170 DEG C, it is incubated 50min, adds Oleum Verniciae fordii mix homogeneously, be warming up to 205 DEG C, be 40mg/g to acid number, be cooled to 150 DEG C, add
Resorcinol and diisocyanate mix homogeneously, then proceed to be cooled to 100 DEG C, are incubated 20min, add styrene, SBS792
With SBS801 mix homogeneously, it is cooled to room temperature and obtains material a；
S2, add nano silicon, nano imvite and Silane coupling reagent KH-570 in material a, in 5500r/min
Stirring 2h, is subsequently adding methyl ethyl ketone peroxide, cobalt naphthenate, benzoyl peroxide, dibutyl phthalate and N, N- diformazan
Base aniline, ultrasonic disperse 40min, then heat to 60 DEG C, be incubated 4h, be cooled to room temperature and obtain Anchor Agent high tensile
Unsaturated polyester resin.
Embodiment 3
A kind of unsaturated polyester resin of Anchor Agent high tensile proposed by the present invention, its raw material wraps by weight
Include：40 parts of maleic anhydride, 5 parts of dibutyl phthalate, 9 parts of styrene, 4 parts of dicyclopentadiene, 5 parts of SBS792,
3 parts of SBS801,5 parts of phthalic anhydride, 1 part of 1,2- propylene glycol, 4 parts of diethylene glycol, 2 parts of ethylene glycol, 4 parts of adipic acid, two different
3 parts of cyanate, 4 parts of hydroquinone, 2 parts of resorcinol, 4 parts of methyl ethyl ketone peroxide, 1 part of cobalt naphthenate, benzoyl peroxide 5
Part, N, 3 parts of accelerine, 5 parts of Oleum Verniciae fordii, 2 parts of nano silicon, 6 parts of nano imvite, Silane coupling reagent KH-570 3
Part, 6 parts of deionized water.
A kind of preparation method of the unsaturated polyester resin of Anchor Agent high tensile of the present invention, walks including following
Suddenly：
S1, by maleic anhydride, diethylene glycol, ethylene glycol, adipic acid, phosphoric acid and deionized water mix homogeneously, be passed through
Nitrogen, stirs 20min, then Deca dicyclopentadiene in 8500r/min, is warming up to 135 DEG C, is incubated 1h, is subsequently adding adjacent benzene
Dicarboxylic acid anhydride, 1,2-PD and hydroquinone mix homogeneously, are warming up to 200 DEG C, when acid number drops to 60mg/g, are cooled to
180 DEG C, it is incubated 30min, adds Oleum Verniciae fordii mix homogeneously, be warming up to 220 DEG C, be 30mg/g to acid number, be cooled to 160 DEG C, add
Resorcinol and diisocyanate mix homogeneously, then proceed to be cooled to 90 DEG C, be incubated 40min, add styrene, SBS792 and
SBS801 mix homogeneously, is cooled to room temperature and obtains material a；
S2, add nano silicon, nano imvite and Silane coupling reagent KH-570 in material a, in 3500r/min
Stirring 4h, is subsequently adding methyl ethyl ketone peroxide, cobalt naphthenate, benzoyl peroxide, dibutyl phthalate and N, N- diformazan
Base aniline, ultrasonic disperse 20min, then heat to 80 DEG C, be incubated 2h, be cooled to room temperature and obtain Anchor Agent high tensile
Unsaturated polyester resin.
Embodiment 4
A kind of unsaturated polyester resin of Anchor Agent high tensile proposed by the present invention, its raw material wraps by weight
Include：25 parts of maleic anhydride, 12 parts of dibutyl phthalate, 4 parts of styrene, 7 parts of dicyclopentadiene, SBS792 3.5
Part, 5 parts of SBS801,3 parts of phthalic anhydride, 3 parts of 1,2- propylene glycol, 2 parts of diethylene glycol, 4 parts of ethylene glycol, adipic acid 2.5
Part, 4.5 parts of diisocyanate, 2 parts of hydroquinone, 4 parts of resorcinol, 2.5 parts of methyl ethyl ketone peroxide, 3 parts of cobalt naphthenate, peroxide
Change 3 parts of benzoyl, N, 5 parts of accelerine, 2 parts of Oleum Verniciae fordii, 3.5 parts of nano silicon, 4 parts of nano imvite, silane are even
5 parts of agent KH-570 of connection, 4.5 parts of deionized water.
A kind of preparation method of the unsaturated polyester resin of Anchor Agent high tensile of the present invention, walks including following
Suddenly：
S1, by maleic anhydride, diethylene glycol, ethylene glycol, adipic acid, phosphoric acid and deionized water mix homogeneously, be passed through
Nitrogen, stirs 35min, then Deca dicyclopentadiene in 5800r/min, is warming up to 128 DEG C, is incubated 2.5h, is subsequently adding neighbour
Phthalate anhydride, 1,2-PD and hydroquinone mix homogeneously, are warming up to 196 DEG C, when acid number drops to 68mg/g, are cooled to
172 DEG C, it is incubated 45min, adds Oleum Verniciae fordii mix homogeneously, be warming up to 206 DEG C, be 38mg/g to acid number, be cooled to 152 DEG C, add
Resorcinol and diisocyanate mix homogeneously, then proceed to be cooled to 98 DEG C, be incubated 25min, add styrene, SBS792 and
SBS801 mix homogeneously, is cooled to room temperature and obtains material a；
S2, add nano silicon, nano imvite and Silane coupling reagent KH-570 in material a, in 5200r/min
Stirring 2.5h, is subsequently adding methyl ethyl ketone peroxide, cobalt naphthenate, benzoyl peroxide, dibutyl phthalate and N, N- bis-
Monomethylaniline., ultrasonic disperse 35min, then heat to 65 DEG C, be incubated 3.5h, be cooled to room temperature and obtain the high stretching of Anchor Agent by force
The unsaturated polyester resin of degree.
Embodiment 5
A kind of unsaturated polyester resin of Anchor Agent high tensile proposed by the present invention, its raw material wraps by weight
Include：35 parts of maleic anhydride, 8 parts of dibutyl phthalate, 8 parts of styrene, 5 parts of dicyclopentadiene, 4.5 parts of SBS792,
4 parts of SBS801,4 parts of phthalic anhydride, 2 parts of 1,2- propylene glycol, 3 parts of diethylene glycol, 3 parts of ethylene glycol, 3.5 parts of adipic acid, two
3.5 parts of isocyanates, 3 parts of hydroquinone, 3 parts of resorcinol, 3.5 parts of methyl ethyl ketone peroxide, 2 parts of cobalt naphthenate, benzoyl peroxide
4 parts of formyl, N, 4 parts of accelerine, 4 parts of Oleum Verniciae fordii, 2.5 parts of nano silicon, 5 parts of nano imvite, silane coupler
4 parts of KH-570,5.5 parts of deionized water.
A kind of preparation method of the unsaturated polyester resin of Anchor Agent high tensile of the present invention, walks including following
Suddenly：
S1, by maleic anhydride, diethylene glycol, ethylene glycol, adipic acid, phosphoric acid and deionized water mix homogeneously, be passed through
Nitrogen, stirs 25min, then Deca dicyclopentadiene in 8200r/min, is warming up to 132 DEG C, is incubated 1.5h, is subsequently adding neighbour
Phthalate anhydride, 1,2-PD and hydroquinone mix homogeneously, are warming up to 199 DEG C, when acid number drops to 62mg/g, are cooled to
148 DEG C, it is incubated 35min, adds Oleum Verniciae fordii mix homogeneously, be warming up to 219 DEG C, be 32mg/g to acid number, be cooled to 158 DEG C, add
Resorcinol and diisocyanate mix homogeneously, then proceed to be cooled to 92 DEG C, be incubated 35min, add styrene, SBS792 and
SBS801 mix homogeneously, is cooled to room temperature and obtains material a；
S2, add nano silicon, nano imvite and Silane coupling reagent KH-570 in material a, in 3800r/min
Stirring 3.5h, is subsequently adding methyl ethyl ketone peroxide, cobalt naphthenate, benzoyl peroxide, dibutyl phthalate and N, N- bis-
Monomethylaniline., ultrasonic disperse 25min, then heat to 75 DEG C, be incubated 2.5h, be cooled to room temperature and obtain the high stretching of Anchor Agent by force
The unsaturated polyester resin of degree.
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 unsaturated polyester resin of Anchor Agent high tensile is it is characterised in that its raw material includes by weight：Suitable
Anhydride maleique 20-40 part, dibutyl phthalate 5-15 part, styrene 3-9 part, dicyclopentadiene 4-8 part, SBS792
3-5 part, SBS801 3-6 part, phthalic anhydride 2-5 part, 1,2- propylene glycol 1-4 part, diethylene glycol 1-4 part, ethylene glycol 2-5
Part, adipic acid 2-4 part, diisocyanate 3-5 part, hydroquinone 1-4 part, resorcinol 2-5 part, methyl ethyl ketone peroxide 2-4 part,
Cobalt naphthenate 1-4 part, benzoyl peroxide 2-5 part, N, accelerine 3-6 part, Oleum Verniciae fordii 1-5 part, nano silicon 2-4
Part, nano imvite 3-6 part, Silane coupling reagent KH-570 3-6 part, deionized water 4-6 part.
2. the unsaturated polyester resin of Anchor Agent high tensile according to claim 1 is it is characterised in that maleic
Dicarboxylic anhydride, phthalic anhydride, styrene, dicyclopentadiene, 1,2- propylene glycol, diethylene glycol, ethylene glycol, adipic acid and two are different
The weight of cyanate is than for 25-35：2.5-4.5：4-8：5-7：2-3：2-3：3-4：2.5-3.5：3.5-4.5.
3. the unsaturated polyester resin of Anchor Agent high tensile according to claim 1 and 2 is it is characterised in that suitable
Anhydride maleique, phthalic anhydride, styrene, dicyclopentadiene, the weight of SBS792 and SBS801 are than for 25-35：3-4：
4-8：5-7：3.5-4.5：4-5.
4. the unsaturated polyester resin of the Anchor Agent high tensile according to any one of claim 1-3, its feature exists
In the weight ratio of methyl ethyl ketone peroxide, cobalt naphthenate, nano silicon, nano imvite and Silane coupling reagent KH-570 is
2.5-3.5：2-3：2.5-3.5：4-5：4-5.
5. the unsaturated polyester resin of the Anchor Agent high tensile according to any one of claim 1-4, its feature exists
In its raw material includes by weight：Maleic anhydride 25-35 part, dibutyl phthalate 8-12 part, styrene 4-8 part,
Dicyclopentadiene 5-7 part, SBS792 3.5-4.5 part, SBS801 4-5 part, phthalic anhydride 3-4 part, 1,2- propylene glycol 2-3
Part, diethylene glycol 2-3 part, ethylene glycol 3-4 part, adipic acid 2.5-3.5 part, diisocyanate 3.5-4.5 part, hydroquinone 2-3
Part, resorcinol 3-4 part, methyl ethyl ketone peroxide 2.5-3.5 part, cobalt naphthenate 2-3 part, benzoyl peroxide 3-4 part, N, N- bis-
Monomethylaniline. 4-5 part, Oleum Verniciae fordii 2-4 part, nano silicon 2.5-3.5 part, nano imvite 4-5 part, silane coupler KH-
570 4-5 parts, deionized water 4.5-5.5 part.
6. the unsaturated polyester resin of the Anchor Agent high tensile according to any one of claim 1-5, its feature exists
In its raw material includes by weight：30 parts of maleic anhydride, 10 parts of dibutyl phthalate, 6 parts of styrene, bicyclic penta
3 parts of diene, 4 parts of SBS792,4.5 parts of SBS801,3.5 parts of phthalic anhydride, 2.5 parts of 1,2- propylene glycol, diethylene glycol 2.5
Part, 3.5 parts of ethylene glycol, 3 parts of adipic acid, 4 parts of diisocyanate, 2.5 parts of hydroquinone, 3.5 parts of resorcinol, peroxidating first and second
3 parts of ketone, 2.5 parts of cobalt naphthenate, 3.5 parts of benzoyl peroxide, N, 4.5 parts of accelerine, 3 parts of Oleum Verniciae fordii, nanometer titanium dioxide
3 parts of silicon, 4.5 parts of nano imvite, 4.5 parts of Silane coupling reagent KH-570,5 parts of deionized water.
7. the preparation of the unsaturated polyester resin of Anchor Agent high tensile described in a kind of any one according to claim 1-6
Method is it is characterised in that comprise the steps：
S1, by maleic anhydride, diethylene glycol, ethylene glycol, adipic acid, phosphoric acid and deionized water mix homogeneously, be passed through nitrogen,
Stir 20-40min, then Deca dicyclopentadiene in 5500-8500r/min, be warming up to 125-135 DEG C, be incubated 1-3h, then
Add phthalic anhydride, 1,2-PD and hydroquinone mix homogeneously, be warming up to 195-200 DEG C, when acid number drops to 60-
During 70mg/g, it is cooled to 170-180 DEG C, is incubated 30-50min, add Oleum Verniciae fordii mix homogeneously, be warming up to 205-220 DEG C, to acid number
For 30-40mg/g, it is cooled to 150-160 DEG C, add resorcinol and diisocyanate mix homogeneously, then proceed to be cooled to
90-100 DEG C, it is incubated 20-40min, add styrene, SBS792 and SBS801 mix homogeneously, be cooled to room temperature and obtain material a；
S2, add nano silicon, nano imvite and Silane coupling reagent KH-570 in material a, in 3500-5500r/
Min stirs 2-4h, is subsequently adding methyl ethyl ketone peroxide, cobalt naphthenate, benzoyl peroxide, dibutyl phthalate and N, N-
Dimethylaniline, ultrasonic disperse 20-40min, then heat to 60-80 DEG C, be incubated 2-4h, be cooled to room temperature and obtain Anchor Agent use
The unsaturated polyester resin of high tensile.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610743503.7A CN106398079A (en) | 2016-08-27 | 2016-08-27 | High tensile strength unsaturated polyester resin for anchoring agents and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610743503.7A CN106398079A (en) | 2016-08-27 | 2016-08-27 | High tensile strength unsaturated polyester resin for anchoring agents and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560133A (en) * | 2004-02-25 | 2005-01-05 | 华南理工大学 | Nano composite of unsaturation poly-ester/active rubber/montmorllonite and preparation process 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 |
| CN102757534A (en) * | 2012-07-18 | 2012-10-31 | 李秋印 | Pre-accelerated unsaturated resin for anchor bolt support and preparation method thereof |
-
2016
- 2016-08-27 CN CN201610743503.7A patent/CN106398079A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560133A (en) * | 2004-02-25 | 2005-01-05 | 华南理工大学 | Nano composite of unsaturation poly-ester/active rubber/montmorllonite and preparation process 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 |
| CN102757534A (en) * | 2012-07-18 | 2012-10-31 | 李秋印 | Pre-accelerated unsaturated resin for anchor bolt support and preparation method thereof |
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