CN107936846A - A kind of modified rosin resin and its preparation method and application - Google Patents
A kind of modified rosin resin and its preparation method and application Download PDFInfo
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- CN107936846A CN107936846A CN201711401931.2A CN201711401931A CN107936846A CN 107936846 A CN107936846 A CN 107936846A CN 201711401931 A CN201711401931 A CN 201711401931A CN 107936846 A CN107936846 A CN 107936846A
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- China
- Prior art keywords
- rosin resin
- modified rosin
- resin
- modified
- rosin
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 104
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 104
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229920005989 resin Polymers 0.000 title claims abstract description 64
- 239000011347 resin Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000002118 epoxides Chemical class 0.000 claims abstract description 25
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 24
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 24
- 239000011976 maleic acid Substances 0.000 claims abstract description 24
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 23
- -1 hydroxyl ether compound Chemical class 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 claims description 7
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 claims description 3
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 3
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 claims description 3
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 claims description 3
- LZDXRPVSAKWYDH-UHFFFAOYSA-N 2-ethyl-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)COCC=C LZDXRPVSAKWYDH-UHFFFAOYSA-N 0.000 claims description 3
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical class OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 3
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000019282 butylated hydroxyanisole Nutrition 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000004255 Butylated hydroxyanisole Substances 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 2
- 229940043253 butylated hydroxyanisole Drugs 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000010426 asphalt Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 230000010148 water-pollination Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 239000012429 reaction media Substances 0.000 abstract description 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000005711 Benzoic acid Substances 0.000 description 6
- 235000010233 benzoic acid Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001846 repelling effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical class COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/08—Printing inks based on natural resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
- C09D193/04—Rosin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
- C09J193/04—Rosin
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
The present invention provides a kind of modified rosin resin and its preparation method and application, wherein, the modified rosin resin is reacted by rosin, the carboxylic acid with phenyl ring, epoxide, maleic acid and its derivative, hydroxyl ether compound to be made.Modified rosin resin provided by the invention, by introducing hydrophobic grouping phenyl ring in rosin molecule, and uses the hydroxyl ether compound ester group low with hydrophilic groups reaction generation hydrophily, substantially increases the water-resistance of rosin resin；And the dissolvent residual defect of environmental pollution and product, safety and environmental protection are avoided organic solvent is not used as reaction medium in modified rosin resin preparation process.
Description
Technical field
The present invention relates to Abietyl modified field, more particularly to a kind of modified rosin resin and its preparation method and application.
Background technology
China is rosin production big country, and gum rosin produces more than 500,000 tons per year, occupies first place in the world.Rosin has many excellent
Characteristic, such as anti-corrosion, moisture-proof, insulation, bonding, emulsification, softening, are widely used in each industrial department.Wherein, the one of rosin
A main application is to be used in ink printing industry as binder.
Binder is that the film forming matter after base-material, main mobile phase and the ink setting of toner is ground in ink manufacture,
The performance and printing effect of ink are directly decide, such as viscosity, adhesive force, glossiness and drying property.The technology of link stuff
Innovation decides the technological innovation of ink, it directly affects the performance and printing effect of ink.
But the design feature of rosin causes its performance there is some defects, for example, crystallization tendency is big, softening point is low and
Acid number is higher etc., these shortcomings limit its application in ink.Therefore, optimum process condition is selected to two activity of rosin
Center synthesis carries out chemical modification, and tool is of great significance.The chemical modification of rosin is generally based on one in its structure
First carboxylic acid and carbon-carbon double bond, it is modified to achieve the purpose that to introduce other functional groups using the two reactive groups.
Take charge of in the research of early period at me (a kind of 201710180667.8 modified rosin resins, preparation method and use this change
The ink of property rosin resin), employ epoxy resin, maleic anhydride is modified rosin resin, being prepared can ultraviolet light
Cured modified rosin resin, is applied to UV curable ink by it, show preferable compatibility, pigment wettability and compared with
Fast rate of drying.But go deep into research, find the modified rosin tree prepared by rosin, epoxy resin, maleic anhydride
Fat, due to carrying hydrophilic carboxyl on its strand, when as ink adhesive, has a water resisting property the shortcomings that poor.Oil
Ink connecting material water-resistance is poor, and after ink contact water, water, which is easily accessible in ink, causes ink emulsification, viscosity to decline, and destroys oil
The structure of ink, changes the performance of ink, it may occur that corresponding printing trouble.
Therefore, the water repelling property of rosin resin is improved, it is this to research and develop a kind of modified rosin resin of function admirable
Field urgent problem to be solved, also always scientific research personnel's focus of attention.
The content of the invention
The purpose of the present invention is overcome shortcoming of the prior art, there is provided a kind of modified rosin resin and its preparation
Methods and applications, the modified rosin resin have an excellent water repelling property, good ultraviolet light curable, in preparation process
Organic solvent need not be additionally added, it is environmentally protective.
To achieve the above object, the application provides following technical solution：
In a first aspect, the present invention provides a kind of modified rosin resin, by rosin, the carboxylic acid with phenyl ring, epoxide,
Maleic acid and its derivative, the reaction of hydroxyl ether compound are made.
Preferably, the modified rosin resin by rosin, the carboxylic acid with phenyl ring, epoxide, maleic acid and its spreads out
Biological, hydroxyl ether compound reacts under the action of catalyst to be made.
It is further preferred that the catalyst includes the one or more in triphenylphosphine, triethylamine.
It is further preferred that the rosin, the carboxylic acid with phenyl ring and epoxide gross mass and the catalyst
Mass ratio be 1：0.001~0.02 (more preferably 1:0.002~0.008).
Preferably, the rosin includes the one or more in gum rosin, newtrex, disproportionated rosin.
Preferably, the carboxylic acid with phenyl ring includes benzoic acid, M-phthalic acid, one kind in phthalic acid or more
Kind.
Preferably, the epoxide includes epoxy resin DER331, ethylene glycol diglycidylether, propane diols two
One or more in glycidol ether, butanediol diglycidyl ether.
Preferably, the derivative in the maleic acid and its derivative is maleic anhydride.
Preferably, the hydroxyl ether compound includes p-hydroxyanisole, butylated hydroxy anisole, 4- hydroxyl fourths
One or more in base vinyl ethers, trimethylolpropane allyl ether.
Preferably, the molar ratio of the rosin and the epoxide is 0.5~1.5:1.
It is further preferred that the molar ratio of the rosin and the epoxide is 1:1.
Preferably, the molar ratio of the carboxylic acid with phenyl ring and the epoxide is 0.5~1.5:1.
It is further preferred that the molar ratio of the carboxylic acid with phenyl ring and the epoxide is 1:1.
Preferably, the molar ratio of the maleic acid and its derivative and the epoxide is 1~2:1.
It is further preferred that the molar ratio of the maleic acid and its derivative and the epoxide is 2:1.
Preferably, the molar ratio of the hydroxyl ether compound and the maleic acid and its derivative is 0.5
~1:1.
It is further preferred that the molar ratio of the hydroxyl ether compound and the maleic acid and its derivative
For 1:1.
Second aspect, the present invention provides a kind of preparation method of modified rosin resin, includes the following steps：
(1) rosin, the carboxylic acid with phenyl ring, epoxide and catalyst are uniformly mixed, react 2 at 90~110 DEG C
~4h, obtains reaction intermediate；
(2) the reaction intermediate and hydroxyl ether compound obtained by step (1), maleic acid and its derivative are mixed
Close, 2~4h is reacted at 140~160 DEG C, obtains modified rosin resin.
It is understood that the present invention is to the method for mixing rosin, epoxide and catalyst described in step (1)
It is not particularly limited, using the technical solution of mixing well known to those skilled in the art.
Preferably, in the step (1), the rosin include gum rosin, newtrex, one kind in disproportionated rosin or
It is a variety of.
Preferably, in the step (1), the carboxylic acid with phenyl ring includes benzoic acid, M-phthalic acid, O-phthalic
One or more in acid.
Preferably, in the step (1), the epoxide includes epoxy resin DER331, ethylene glycol two shrinks
One or more in glycerin ether, propylene glycol diglycidylether, butanediol diglycidyl ether.
Preferably, in the step (1), the catalyst includes the one or more in triphenylphosphine, triethylamine.
Preferably, in the step (1), the molar ratio of the rosin and the epoxide is 0.5~1.5:
1。
It is further preferred that in the step (1), the molar ratio of the rosin and the epoxide is 1:1.
Preferably, in the step (1), the molar ratio of the carboxylic acid with phenyl ring and the epoxide is
0.5~1.5:1.
It is further preferred that in the step (1), mole of the carboxylic acid with phenyl ring and the epoxide
Than for 1:1.
Preferably, in the step (1), the rosin, the carboxylic acid with phenyl ring and epoxide gross mass with it is described
The mass ratio of catalyst is 1：0.001~0.02 (more preferably 1:0.002~0.008).
Preferably, in the step (1), reaction temperature is 100 DEG C.
Preferably, in the step (1), reaction time 3h.
Preferably, in the step (2), the hydroxyl ether compound includes p-hydroxyanisole, butyl hydroxyl
One or more in base anisole, 4- hydroxy butyl vinyl ethers, trimethylolpropane allyl ether.
Preferably, in the step (2), the derivative in the maleic acid and its derivative is maleic anhydride.
Preferably, in the step (2), the maleic acid and its derivative and the epoxy compound described in step (1)
The molar ratio of thing is 1~2:1.
It is further preferred that in the step (2), the maleic acid and its derivative and the ring described in step (1)
The molar ratio of oxygen compound is 2:1.
Preferably, in the step (2), the hydroxyl ether compound and the maleic acid and its derivative
Molar ratio be 0.5~1:1.
It is further preferred that in the step (2), the hydroxyl ether compound and the maleic acid and its
The molar ratio of derivative is 1:1.
Preferably, in the step (2), reaction temperature is 150 DEG C.
Preferably, in the step (2), reaction time 3h.
Preferably, the modified rosin resin described in first aspect present invention is using modified pine described in second aspect of the present invention
The preparation method of botany bar gum is made.
The principle of the present invention：The present invention provides a kind of modified rosin resin, first under catalyst action, utilizes rosin
Reacted with the epoxide group on the carboxyl and epoxide on the carboxylic acid with phenyl ring, obtain the intermediate with hydroxyl；
Add hydroxyl ether compound, maleic acid and its derivative, maleic acid and its derivative directly with intermediate and ethers
Hydroxyl reaction in compound, obtains modified rosin resin.Because introducing hydrophobic grouping phenyl ring in modified rosin resin molecule,
And the carboxyl in system reacts completely with hydroxyl, the low ester group of generation hydrophily, so the water repelling property of modified rosin resin
It is greatly improved.
The third aspect, the present invention provides a kind of modified rosin resin as described in relation to the first aspect to prepare ink, coating
Application in paint or adhesive.
Beneficial effects of the present invention are as follows：
(1) present invention provides a kind of modified rosin resin, by introducing hydrophobic group (phenyl ring) in rosin resin strand,
And hydrophilic radical (carboxyl) is reacted by the low ester group of generation hydrophily using hydroxyl ether compound, improve rosin
The water-resistance of resin；
(2) rosin resin method of modifying provided by the invention, reaction process do not use organic solvent to be avoided as reaction medium
The dissolvent residual defect of environmental pollution and product, and product is outer is generated without other accessory substances, so need not be carried out to product
Extra postprocessing working procedures, preparation process energy consumption is low, pollution-free, realizes the synthesis of environmentally protectiveization.
Brief description of the drawings
In order to illustrate the technical solutions in the embodiments of the present application or in the prior art more clearly, below will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of application, for those of ordinary skill in the art, without creative efforts, can be with
Other attached drawings are obtained according to these attached drawings.
The water-pickup of ink plan that Fig. 1 is provided by the embodiment of the present invention.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical solution in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is
Part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
The all other embodiments obtained on the premise of creative work is not made, belong to the scope of protection of the invention.
Embodiment 1
An embodiment of the present invention provides a kind of preparation method of modified rosin resin, comprise the following steps：
(1) in churned mechanically 500mL three-necked bottles, 30.2g (0.1mol) gum rosin and 34g (0.1mol) are added
Epoxy resin DER331, is warming up to 140 DEG C, takes out negative pressure and promotes reactant melting, then is cooled to 100 DEG C, adds triphenylphosphine
0.76g and benzoic acid 12.2g (0.1mol), when stirring reaction 3 is small at 100 DEG C；
(2) 24.80g (0.2mol) p-hydroxyanisole and 23.2g (0.2mol) maleic acid are added, it is anti-at 150 DEG C
3h is answered, obtains modified rosin resin one.
Test result shows that the structural formula of modified rosin resin one is as follows：
Embodiment 2
An embodiment of the present invention provides a kind of preparation method of modified rosin resin, comprise the following steps：
(1) in churned mechanically 500mL three-necked bottles, 45.3g (0.15mol) gum rosin and 34g are added
(0.1mol) epoxy resin DER331, is warming up to 140 DEG C, takes out negative pressure and promotes reactant melting, then is cooled to 90 DEG C, adds triphen
Base phosphine 0.76g and M-phthalic acid 8.3g (0.05mol), when stirring reaction 4 is small at 90 DEG C；
(2) 27g (0.15mol) butylated hydroxy anisoles and 17.4g (0.15mol) maleic acid are added, it is anti-at 140 DEG C
4h is answered, obtains modified rosin resin two.
Embodiment 3
An embodiment of the present invention provides a kind of preparation method of modified rosin resin, comprise the following steps：
(1) in churned mechanically 500mL three-necked bottles, 60.5g (0.1mol) newtrexes and 17.4g are added
(0.1mol) ethylene glycol diglycidylether, is warming up to 140 DEG C, takes out negative pressure and promotes reactant melting, then is cooled to 110 DEG C, adds
Enter triphenylphosphine 0.76g and phthalic acid 8.3g (0.05mol), when stirring reaction 2 is small at 110 DEG C；
(2) 11.6g (0.1mol) 4- hydroxy butyl vinyl ethers and 11.6g (0.1mol) maleic acid are added, at 160 DEG C
2h is reacted, obtains modified rosin resin three.
Embodiment 4
An embodiment of the present invention provides a kind of preparation method of modified rosin resin, comprise the following steps：
(1) in churned mechanically 500mL three-necked bottles, 30.25g (0.05mol) newtrexes and 18.8g are added
(0.1mol) propylene glycol diglycidylether, is warming up to 140 DEG C, takes out negative pressure and promotes reactant melting, then is cooled to 100 DEG C, adds
Enter triethylamine 0.76g and benzoic acid 18.3g (0.15mol), when stirring reaction 4 is small at 100 DEG C；
(2) 21.4g (0.1mol) trimethylolpropane allyl ethers and 23.2g (0.2mol) maleic acid are added,
2h is reacted at 150 DEG C, obtains modified rosin resin four.
Embodiment 5
An embodiment of the present invention provides a kind of preparation method of modified rosin resin, comprise the following steps：
(1) in churned mechanically 500mL three-necked bottles, 30.4g (0.1mol) disproportionated rosins and 20.2g are added
(0.1mol) butanediol diglycidyl ether, is warming up to 140 DEG C, takes out negative pressure and promotes reactant melting, then is cooled to 90 DEG C, adds
Triethylamine 0.76g and benzoic acid 12.2g (0.1mol), when stirring reaction 3 is small at 90 DEG C；
(2) 24.8g (0.2mol) p-hydroxyanisole and 19.6g (0.2mol) maleic anhydride are added, it is anti-at 160 DEG C
3h is answered, obtains modified rosin resin five.
Embodiment 6
An embodiment of the present invention provides a kind of preparation method of modified rosin resin, comprise the following steps：
(1) in churned mechanically 500mL three-necked bottles, 30.4g (0.1mol) disproportionated rosins and 34g are added
(0.1mol) epoxy resin DER331, is warming up to 140 DEG C, takes out negative pressure and promotes reactant melting, then is cooled to 100 DEG C, adds three
Phenylphosphine 0.76g and benzoic acid 12.2g (0.1mol), when stirring reaction 3 is small at 100 DEG C；
(2) 42.8g (0.2mol) trimethylolpropane allyl ethers and 19.6g (0.2mol) maleic anhydride are added,
3h is reacted at 150 DEG C, obtains modified rosin resin six.
Embodiment 7
An embodiment of the present invention provides a kind of preparation method of modified rosin resin, comprise the following steps：
(1) in churned mechanically 500mL three-necked bottles, 60.5g (0.2mol) gum rosin and 34g (0.1mol) are added
Epoxy resin DER331, is warming up to 140 DEG C, takes out negative pressure and promotes reactant melting, then is cooled to 100 DEG C, adds triphenylphosphine
0.76g, when stirring reaction 3 is small at 100 DEG C；
(2) 23.2g (0.2mol) maleic acid is added, 3h is reacted at 150 DEG C, obtains modified rosin resin seven.
Test result shows that the structural formula of modified rosin resin seven is as follows：
Embodiment 8
In order to further illustrate beneficial effects of the present invention, the modified rosin resin that embodiment 1-7 is prepared respectively
It is configured to ink and the solidification effect and emulsifiability of test ink.
The specific method that modified rosin resin is configured to ink is as follows：By 27.5g modified rosin resins, the third oxygen of 47.5g
Change glycerol tri-acrylate, after stirring and dissolving, add 4g 2- methyl isophthalic acids-[4- methyl mercaptos phenyl] -2- morpholinyl -1- acetone, 1g
2- isopropyl thioxanthones and 20g BASF 57：1 paratonere L4BH, under 300 revs/min of rotating speed, stirs 20min, then
UV curable ink sample is configured to by three-roller grinding.
Curing rate test method is as follows：The ink sample of configuration printability instrument is coated with about 15 micron thickness in sky
On blank sheet of paper, with the ultraviolet lamp with adjustable filtering device that power is 50W/CM linear heat generation rates, under 320-420 wave-length coverages, with 100
M/min speed is cured, and record obtains good surface and thoroughly cures number of pass times under required lamp, as a result such as following table
Shown in 1.
The UV radiation curing effect measuring result of table 1
Emulsifiability test method is as follows：Using grease exclusion principle, the ink sample of 100g and 100g are moistened
Version liquid mixing, high-speed stirred mixture, within a certain period of time, forms the stabilization saturation state of ink sample and fountain solution, then
Remove the damping water to dissociate in ink sample as far as possible, it is accurate to weigh the fountain solution weight remained in ink sample, then with damping
The total amount of liquid, which is divided by, draws emulsification rate numerical value, test data such as table 2 and Fig. 1.
The emulsification rate test data of 2 ink of table
It can be seen that the oil being configured to using the embodiment 1-6 modified rosin resins prepared from solidification effect test data
Ink, is fully cured and is required through number as 3~4 times, the ink that modified rosin resin prepared by embodiment 7 is configured to is fully cured
Number is required through as 4 times, the two difference is little.This explanation, after adding the carboxylic acid with phenyl ring and hydroxyl ether compound,
The curing rate of ink is influenced little.
It can be seen that the oil being configured to using the embodiment 1-6 modified rosin resins prepared from emulsifiability test data
Ink, emulsification rate is below 30% after 60min, is respectively provided with higher water-resistance.In modified rosin resin prepared by embodiment 7, not
The carboxylic acid with phenyl ring and hydroxyl ether compound are added, it can clearly be seen that emulsification rate is 40.6% after 60min, is far above
Modified rosin resin prepared by embodiment 1-6.This explanation, after adding the carboxylic acid with phenyl ring and hydroxyl ether compound, system
Standby obtained modified rosin resin water-resistance is improved.
Finally it should be noted that：Obviously, above-described embodiment is only intended to clearly illustrate the application example, and simultaneously
The non-restriction to embodiment.For those of ordinary skill in the field, can also do on the basis of the above description
Go out other various forms of variations or change.There is no necessity and possibility to exhaust all the enbodiments.And thus drawn
Among the obvious changes or variations that Shen goes out is still in the protection domain of the application.
Claims (10)
1. a kind of modified rosin resin, it is characterised in that by rosin, the carboxylic acid with phenyl ring, epoxide, maleic acid and its spread out
Biological, hydroxyl ether compound reaction is made.
2. a kind of modified rosin resin as claimed in claim 1, it is characterised in that the rosin includes gum rosin, polymerization
One or more in rosin, disproportionated rosin.
3. a kind of modified rosin resin as claimed in claim 1, it is characterised in that the carboxylic acid with phenyl ring includes benzene first
One or more in acid, M-phthalic acid, phthalic acid.
4. a kind of modified rosin resin as claimed in claim 1, it is characterised in that the epoxide includes asphalt mixtures modified by epoxy resin
One kind or more in fat DER331, ethylene glycol diglycidylether, propylene glycol diglycidylether, butanediol diglycidyl ether
Kind.
A kind of 5. modified rosin resin as claimed in claim 1, it is characterised in that the hydroxyl ether compound bag
Include one kind in p-hydroxyanisole, butylated hydroxy anisole, 4- hydroxy butyl vinyl ethers, trimethylolpropane allyl ether
It is or a variety of.
6. a kind of modified rosin resin as claimed in claim 1, it is characterised in that the rosin and the epoxy compound
The molar ratio of thing is 0.5~1.5:1.
A kind of 7. modified rosin resin as claimed in claim 1, it is characterised in that the carboxylic acid with phenyl ring with it is described
The molar ratio of epoxide is 0.5~1.5:1.
A kind of 8. modified rosin resin as claimed in claim 1, it is characterised in that the hydroxyl ether compound with
The maleic acid and its molar ratio of derivative are 0.5~1:1.
9. a kind of preparation method of modified rosin resin, includes the following steps：
(1) rosin, the carboxylic acid with phenyl ring, epoxide and catalyst are uniformly mixed, 2~4h are reacted at 90~110 DEG C,
Obtain reaction intermediate；
(2) reaction intermediate obtained by step (1) and hydroxyl ether compound, maleic acid and its derivative are mixed,
2~4h is reacted at 140~160 DEG C, obtains modified rosin resin.
A kind of 10. application of the modified rosin resin in ink, paint of coating or adhesive is prepared as claimed in claim 1.
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| CN201711401931.2A CN107936846B (en) | 2017-12-22 | 2017-12-22 | Modified rosin resin and preparation method and application thereof |
| PCT/CN2018/117104 WO2019120036A1 (en) | 2017-12-22 | 2018-11-23 | Modified rosin resin, preparation method therefor, and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019120036A1 (en) * | 2017-12-22 | 2019-06-27 | 惠州市华泓新材料股份有限公司 | Modified rosin resin, preparation method therefor, and application thereof |
| CN110713797A (en) * | 2018-07-12 | 2020-01-21 | 常州强力电子新材料股份有限公司 | Epoxy grafted rosin, preparation method thereof, composition containing epoxy grafted rosin and application of composition |
| CN112126356A (en) * | 2020-09-27 | 2020-12-25 | 广东科茂林产化工股份有限公司 | Modified rosin resin for ultraviolet curing ink and preparation method thereof |
| CN116200123A (en) * | 2022-12-30 | 2023-06-02 | 江苏燕山光伏设备有限公司 | Erosion-resistant ultraviolet photovoltaic bracket, coating composition and preparation method of coating composition |
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| JPH04292637A (en) * | 1991-03-20 | 1992-10-16 | Mitsubishi Rayon Co Ltd | Composite material |
| CN102558574A (en) * | 2012-01-04 | 2012-07-11 | 江苏博特新材料有限公司 | Surface modification method of carboxyl-containing high-water-absorbability resin |
| CN106905151A (en) * | 2017-03-24 | 2017-06-30 | 惠州市华泓新材料有限公司 | A kind of modified rosin resin, preparation method and the ink using the modified rosin resin |
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| JPH0812944A (en) * | 1994-07-04 | 1996-01-16 | Shinnakamura Kagaku Kogyo Kk | Carboxylated rosin ester and its production |
| CN104211908A (en) * | 2014-08-14 | 2014-12-17 | 广西众昌树脂有限公司 | Preparation method of rosin modified epoxy ester resin |
| CN107936846B (en) * | 2017-12-22 | 2020-09-08 | 惠州市华泓新材料股份有限公司 | Modified rosin resin and preparation method and application thereof |
-
2017
- 2017-12-22 CN CN201711401931.2A patent/CN107936846B/en active Active
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2018
- 2018-11-23 WO PCT/CN2018/117104 patent/WO2019120036A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04292637A (en) * | 1991-03-20 | 1992-10-16 | Mitsubishi Rayon Co Ltd | Composite material |
| CN102558574A (en) * | 2012-01-04 | 2012-07-11 | 江苏博特新材料有限公司 | Surface modification method of carboxyl-containing high-water-absorbability resin |
| CN106905151A (en) * | 2017-03-24 | 2017-06-30 | 惠州市华泓新材料有限公司 | A kind of modified rosin resin, preparation method and the ink using the modified rosin resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019120036A1 (en) * | 2017-12-22 | 2019-06-27 | 惠州市华泓新材料股份有限公司 | Modified rosin resin, preparation method therefor, and application thereof |
| CN110713797A (en) * | 2018-07-12 | 2020-01-21 | 常州强力电子新材料股份有限公司 | Epoxy grafted rosin, preparation method thereof, composition containing epoxy grafted rosin and application of composition |
| CN112126356A (en) * | 2020-09-27 | 2020-12-25 | 广东科茂林产化工股份有限公司 | Modified rosin resin for ultraviolet curing ink and preparation method thereof |
| CN116200123A (en) * | 2022-12-30 | 2023-06-02 | 江苏燕山光伏设备有限公司 | Erosion-resistant ultraviolet photovoltaic bracket, coating composition and preparation method of coating composition |
| CN116200123B (en) * | 2022-12-30 | 2024-03-01 | 江苏燕山光伏设备有限公司 | Erosion-resistant ultraviolet photovoltaic bracket, coating composition and preparation method of coating composition |
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| WO2019120036A1 (en) | 2019-06-27 |
| CN107936846B (en) | 2020-09-08 |
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