CN105585961B - A kind of hydrogenation modification rosin tackifying resin and preparation method thereof - Google Patents
A kind of hydrogenation modification rosin tackifying resin and preparation method thereof Download PDFInfo
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- CN105585961B CN105585961B CN201610137768.2A CN201610137768A CN105585961B CN 105585961 B CN105585961 B CN 105585961B CN 201610137768 A CN201610137768 A CN 201610137768A CN 105585961 B CN105585961 B CN 105585961B
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- rosin
- resin
- autoclave
- hydrogenation modification
- tackifying resin
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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 221
- 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 221
- 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 221
- 239000011347 resin Substances 0.000 title claims abstract description 189
- 229920005989 resin Polymers 0.000 title claims abstract description 189
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 78
- 230000004048 modification Effects 0.000 title claims abstract description 77
- 238000012986 modification Methods 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000009835 boiling Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 238000010792 warming Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000013557 residual solvent Substances 0.000 claims abstract description 13
- 238000007599 discharging Methods 0.000 claims abstract description 12
- 238000006073 displacement reaction Methods 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 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 description 45
- 239000002253 acid Substances 0.000 claims description 27
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane Chemical compound CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 claims description 22
- HEVGGTGPGPKZHF-UHFFFAOYSA-N 1-(1,2-dimethyl-3-methylidenecyclopentyl)-4-methylbenzene Chemical compound CC1C(=C)CCC1(C)C1=CC=C(C)C=C1 HEVGGTGPGPKZHF-UHFFFAOYSA-N 0.000 claims description 18
- 230000006837 decompression Effects 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 13
- 238000004090 dissolution Methods 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 229930006728 pinane Natural products 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000007701 flash-distillation Methods 0.000 claims description 9
- 239000001293 FEMA 3089 Substances 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 230000008719 thickening Effects 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000003086 colorant Substances 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000003973 paint Substances 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 2
- 230000009967 tasteless effect Effects 0.000 abstract description 2
- -1 monoterpenes compound Chemical class 0.000 description 17
- 239000000203 mixture Substances 0.000 description 13
- 239000003963 antioxidant agent Substances 0.000 description 12
- 230000003078 antioxidant effect Effects 0.000 description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 12
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 12
- 239000003381 stabilizer Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229930003658 monoterpene Natural products 0.000 description 6
- 235000002577 monoterpenes Nutrition 0.000 description 6
- 235000019260 propionic acid Nutrition 0.000 description 6
- 239000001169 1-methyl-4-propan-2-ylcyclohexa-1,4-diene Substances 0.000 description 5
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 5
- 235000011613 Pinus brutia Nutrition 0.000 description 5
- 241000018646 Pinus brutia Species 0.000 description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 5
- 235000001510 limonene Nutrition 0.000 description 5
- 229940087305 limonene Drugs 0.000 description 5
- 150000007875 phellandrene derivatives Chemical class 0.000 description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229930006722 beta-pinene Natural products 0.000 description 4
- 125000002619 bicyclic group Chemical group 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- WTARULDDTDQWMU-UHFFFAOYSA-N β-pinene Chemical compound C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 4
- 239000004831 Hot glue Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004026 adhesive bonding Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000002940 palladium Chemical class 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical class CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- WNFDFOPVGKYQOF-UHFFFAOYSA-N C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)P(O)(O)O Chemical compound C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)P(O)(O)O WNFDFOPVGKYQOF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 235000019082 Osmanthus Nutrition 0.000 description 1
- 241000333181 Osmanthus Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 235000005128 Sapium sebiferum Nutrition 0.000 description 1
- 244000057114 Sapium sebiferum Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- VLTOSDJJTWPWLS-UHFFFAOYSA-N pent-2-ynal Chemical compound CCC#CC=O VLTOSDJJTWPWLS-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009736 wetting Methods 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
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses a kind of preparation method of hydrogenation modification rosin tackifying resin, comprising the following steps: by modified rosin resin, solvent investment autoclave, dissolves by heating, adds catalyst；Autoclave is vacuumized, with air in nitrogen displacement kettle, is re-filled with hydrogen；Start autoclave heating system and stirring system, be warming up to 180-260 DEG C, and fresh hydrogen is continuously replenished, Hydrogen Vapor Pressure in kettle is kept to react 1-4 hours in 5-15MPa；Stop heating, cooling, discharging filtering removes solvent, low-boiling point material, residual solvent.The method of the invention substantially reduces resin degree of unsaturation, the performances such as adhesiveness, stability increase by hydrogenation modification.Meanwhile the present invention also provides a kind of hydrogenation modification rosin tackifying resin, the hydrogenation modification rosin tackifying resin is colourless, tasteless, softening point is low, compatibility is good, can be widely used in the fields such as adhesive, paint of coating, ink.
Description
Technical field
The present invention relates to a kind of modified rosin tackifying resin and preparation method thereof, especially a kind of hydrogenation modification rosin thickening
Resin and preparation method thereof.
Background technique
Pine tree is resourceful in China, and produced rosin is the most important product of China's chemistry of forest product industry, and pillar
Industry.Rosin resin is resin obtained from being reacted as rosin or modified rosin with alcohol or other modified materials, and the resin is
It is widely used in hot melt adhesive, pressure sensitive adhesive, shoes glue, Laminating adhesive, sealant；Rosin ester can also make the modifying agent of rubber and plastics.
Rosin resin and Petropols are all one of the primary raw materials in glue sticking field, and rosin resin, Petropols are to do
It is used inside gluing product for " tackifying resin ", increases just viscous, improve wetting and plasticity, promote the mixed of filler and polymer
It closes.It can all be used inside most of gluing product.The two purposes is substantially similar, aspect of performance analysis, at the beginning of rosin resin
It is sticky more preferable, and the ageing-resistant aspect of Petropols also has better performance.So many products are all to make the two together
With keeping properties of product more perfect the advantages of both can neutralizing.
Traditional rosin resin, Petropols have penetrating odor due to the micro- yellow or brown of appearance, largely
Limit their application.
In technical matters innovation, although there is petroleum modified rosin resin, so that resin has both rosin resin and petroleum tree
The advantages of both rouge, but still since there are a large amount of unsaturated bonds in resin, resin is in terms of color, ageing-resistant, compatibility
Performance there are biggish deficiencies, be not able to satisfy Vehicles Collected from Market technical requirements.
For dicyclic pentylene modified rosin resin, a kind of method is proposed in patent CN188728A.It is specifically prepared
Method is: 21 dicyclopentadienes: rosin=1:0.5-2 molal quantity ratio, under 240-260 DEG C, 0.5-1.3Mpa pressure, instead
It answers 6-10 hours, then depressurizes, distill out low fraction and dicyclic pentylene modified rosin resin product is made.Product colour obtained
For 6-9,110-140 DEG C of resin softening point.Another method that the present inventor proposes in patent CN201210567579.0.
Its specific preparation method is: into autoclave, rosin is added or rosin derivative, monoterpenes compound, dicyclopentadiene evaporate
Point and catalyst, be uniformly mixed, go out air with nitrogen or carbon dioxide replacement, then in 0.2~0.6Mpa of pressure, temperature 170
It reacts 1~30 hour at~290 DEG C, decompresses after reaction, remove low-boiling point material, be cooled to 200~230 DEG C up to modified
Rosin tackifying resin, product colour Wei≤6 obtained, Suan Zhi≤70mgKOH/g, 85-115 DEG C of resin softening point.
Dicyclic pentylene modified rosin resin is produced using above method, mainly there is following disadvantage: first is that when production
Pressure is big, the high requirements on the equipment；Second is that product colour is deep, it can be only applied to ink etc. and require color low place, in gluing
Agent field, requires the color of resin now higher and higher, then color of resin 6-9 color then limits its answering in this field
With；Third is that resin unsaturated bond is more, thermal stability is poor, in adhesive using also restrained.
Summary of the invention
A kind of hydrogenation modification rosin thickening is provided it is an object of the invention to overcome above-mentioned the deficiencies in the prior art place
Resin.Meanwhile the present invention also provides the preparation methods of hydrogenation modification rosin tackifying resin described above.
To achieve the above object, the technical scheme adopted by the invention is as follows: a kind of preparation of hydrogenation modification rosin tackifying resin
Method the described method comprises the following steps:
(1) it by modified rosin resin, solvent investment autoclave, dissolves by heating, autoclave then is added in catalyst again
In；
(2) autoclave is vacuumized, with air in nitrogen displacement kettle, is re-filled with hydrogen, adjusts Hydrogen Vapor Pressure in kettle；
(3) start autoclave heating system and stirring system, be warming up to 180-260 DEG C, and fresh hydrogen is continuously replenished, protect
Hydrogen Vapor Pressure in kettle is held to react 1-4 hours in 5-15MPa；
(4) after reaction, stop heating, open cooling system cooling, blowdown pressure letdown, discharging filtering is distilled off molten
Agent, low-boiling point material, residual solvent are to get hydrogenation modification rosin tackifying resin.
The preferred embodiment of preparation method as hydrogenation modification rosin tackifying resin of the present invention, the step
(1) modified rosin resin and modified rosin resin and the mass ratio of solvent gross mass are 30%~60% in.
The preferred embodiment of preparation method as hydrogenation modification rosin tackifying resin of the present invention, the step
(1) solvent in is at least one of pinane, 200# solvent naphtha, hexamethylene, normal heptane.
The preferred embodiment of preparation method as hydrogenation modification rosin tackifying resin of the present invention, the step
(1) catalyst in is support type palladium series catalyst or load-type nickel series catalysts.
The preferred embodiment of preparation method as hydrogenation modification rosin tackifying resin of the present invention, the support type
In palladium series catalyst, the mass percentage of palladium is 1~5%, and carrier is active carbon, SiO2、Al2O3Or Al2O3-SiO2；Institute
It states in load-type nickel series catalysts, the mass percentage of nickel is 35~70%, and carrier is active carbon, SiO2、Al2O3Or
Al2O3-SiO2.The preferred embodiment of preparation method as hydrogenation modification rosin tackifying resin of the present invention, the step
(1) catalyst used in can be for example D5H1A, D5-Al of Shaanxi Ruike New Materials Co., Ltd.2O3It or is upper
At least one of SN-5000P, SN-6000P, SN-6900P, SN-7000P of the triumphant Chemical Industry Science Co., Ltd of Hisoon etc..
The preferred embodiment of preparation method as hydrogenation modification rosin tackifying resin of the present invention, the step
(1) when the catalyst used in is support type palladium series catalyst, the mass ratio of the catalyst and modified rosin resin is 0.5%
~2.0%；When the catalyst used in the step (1) is support type nickel catalyst, the catalyst and modified rosin tree
The mass ratio of rouge is 3.0%~10.0%.
The preferred embodiment of preparation method as hydrogenation modification rosin tackifying resin of the present invention, the step
(1) by after modified rosin resin and solvent investment autoclave in, 100~150 DEG C of dissolutions are heated to.
The preferred embodiment of preparation method as hydrogenation modification rosin tackifying resin of the present invention, the step
(4) cooling system is opened in cools to 130 DEG C hereinafter, solvent, 230 DEG C of vacuum decompression distillations are distilled off using 180-230 DEG C
0.5~2 hour removing low-boiling point material and residual solvent.
Modification as the preferred embodiment of hydrogenation modification rosin tackifying resin of the present invention, in the step (1)
Rosin resin is prepared with the following method: into autoclave, rosin or rosin derivative, monoterpenes compound and double is added
Cyclopentadiene fraction is uniformly mixed, goes out air with nitrogen or carbon dioxide replacement, then in pressure 0.2-0.6Mpa, temperature
It reacts 1-30 hours at 170-290 DEG C, decompresses after reaction, remove low-boiling point material to get modified rosin tackifying resin.This
The preparation method of modified rosin resin described in application is compared with the method in CN201210567579.0, except being free of
Outside catalyst in CN201210567579.0 in method, rest materials and condition are all the same.Modified rosin resin described above
Preparation method in, it is preferable that the rosin be gum rosin or wood rosin；The rosin derivative is hydrogenated rosin, disproportionation pine
Fragrant or refined rosin.
Preferably, the monoterpenes compound is turpentine oil, phellandrene, dipentene, limonene, australene, nopinene, the moon
The addition of at least one of osmanthus alkene and ocimenum, the monoterpenes compound can make resin and metallocene catalyzed polyolefin phase
Capacitive significantly improves.
Preferably, the content of dicyclopentadiene is 50~100wt% in the dicyclopentadiene fraction；It is highly preferred that institute
The content for stating dicyclopentadiene in dicyclopentadiene fraction is 75~98wt%, and dicyclopentadiene fraction is from petroleum cracking second
What alkene by-product, coal oil refining byproduct or other approach obtained.
Preferably, the mass ratio of the additional amount of the dicyclopentadiene fraction and rosin or rosin derivative be 0.44~
1.22；The additional amount of the monoterpenes compound is that formula gross mass is (rosin or rosin derivative, monoterpenes compound, bicyclic
The quality of pentadiene fraction and catalyst and) 0~15%.
Preferably, the method for removing low-boiling point material is flash evaporation.
The point for the modified rosin resin that the above method is prepared is 80~110 DEG C, and acid value is 15~70mgKOH/g, face
Color is less than No. 16 colors of Ghana color number.
Preferably, for make the modified rosin resin preparation go hydrogenation modified rosin tackifying resin in application effect more
Good, the modified rosin resin that method described above is prepared has been additionally added antioxidant stabilizer, is then used further to subsequent hydrogenation and changes
The preparation of property rosin tackifying resin.Specifically antioxidant stabilizer is added in modified rosin resin, stirring and evenly mixing can be used to
The preparation of subsequent hydrogenation modified rosin tackifying resin.The additional amount of the antioxidant stabilizer is in modified rosin resin preparation process
The 0.2~0.5% of rosin or rosin derivative amount of substance.The antioxidant stabilizer is preferably 2,6- di-t-butyl -4- methylbenzene
Phenol, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butyl
Base phenol), β-(4- hydroxy phenyl -3,5- di-t-butyl) propionic acid n-octadecyl alcohol ester, 2,2 '-thiobis [3- (3,5- bis- tertiary fourths
Base -4- hydroxy phenyl) ethyl propionate] at least one of it is sub- with phosphorous acid three (nonyl phenyl ester), three (2,4- di-tert-butyl-phenyls)
The mixture of at least one of phosphate and triphenyl phosphite, but it is not limited to above-mentioned compound；It is furthermore preferred that described
Antioxidant stabilizer be four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and three (2,4- di-t-butyls
Phenyl) phosphite ester mixture, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and three (2,4-
Di-tert-butyl-phenyl) mass ratio of phosphorous acid is preferably 0.6~3:1.
In addition, the hydrogenation modification rosin tackifying resin is adopted the present invention also provides a kind of hydrogenation modification rosin tackifying resin
It is prepared with method as described above.
As the preferred embodiment of hydrogenation modification rosin tackifying resin of the present invention, the hydrogenation modification rosin thickening
The softening point of resin is 80~110 DEG C, and acid value is 15~70mgKOH/g, and color is less than No. 1 color of Ghana color number.
Hydrogenation modification rosin tackifying resin unsaturated bond of the present invention significantly reduces, and has more preferably ageing-resistant stabilization
Property, softening point is lower, compatibility is more preferable, color more preferably, can be widely applied to the fields such as adhesive, paint of coating, ink, especially
It is the application in metallocene catalyzed polyolefin adhesive area.
Hydrogenation modification rosin tackifying resin of the present invention has the beneficial effect that
(1) present invention prepares hydrogenation modification rosin tackifying resin relative to unhydrided bicyclic modified rosin resin, insatiable hunger
It is significantly reduced with key, resin has more preferably ageing-resistant stability.
(2) hydrogenation modification rosin tackifying resin softening point prepared by the present invention be 80~110 DEG C, acid value be 15~
70mgKOH/g, color is less than No. 1 color of Ghana color number, and the bicyclic modified rosin resin softening point of conventional invention is 110~140
DEG C, acid value is 5~30mgKOH/g, and 6~No. 9 colors of color Ghana color number, since resin softening point of the present invention is lower, compatibility is more
Good, more preferably, therefore application field is extensive, can be applied to the fields such as adhesive, paint of coating and ink for color.
(3) hydrogenation modification rosin tackifying resin prepared by the present invention and traditional rosin glycerides, pentalyn,
Bicyclic amylene resin and Abietyl modified bicyclic amylene resin are compared, and resin of the present invention is good with metallocene catalyzed polyolefin compatibility,
Changing rosin resin, bicyclic amylene resin and Abietyl modified bicyclic amylene resin at this stage cannot be using poly- with metallocene catalysis
The status of alkene.
(4) hydrogenation modification rosin tackifying resin prepared by the present invention, since rosin contains carboxyl polar group, so that same
The hot melt adhesive for using the resin to prepare under equal formulas is than non-poles such as the hot melt adhesive prepared with terpene resin, C5 Petropols and PP, PET
Property material has more preferably wetability and adhesive force.
The preparation method of hydrogenation modification rosin tackifying resin of the present invention makes resin degree of unsaturation by hydrogenation modification
It substantially reduces, the performances such as adhesiveness, stability increase.The hydrogenation modification pine being prepared using the method for the invention
Fragrant tackifying resin, it is colourless, tasteless, softening point is low, compatibility is good, the neck such as adhesive, paint of coating, ink can be widely used in
Domain.
Specific embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
D5H1A, the D5-Al selected in embodiment2O3Purchased from Shaanxi Ruike New Materials Co., Ltd., SN-5000P,
SN-6000P, SN-6900P, SN-7000P are purchased from the triumphant Chemical Industry Science Co., Ltd of upper Hisoon.
Embodiment 1
A kind of embodiment of the preparation method of hydrogenation modification rosin tackifying resin of the present invention, hydrogenation modification described in the present embodiment
Rosin tackifying resin is prepared using following methods:
(1) by modified rosin resin, pinane investment 1L autoclave, it is heated to 100-150 DEG C of dissolution, it then again will catalysis
Agent D5H1A is added in autoclave；Wherein modified rosin resin and modified rosin resin and the mass ratio of pinane gross mass are 30%,
The mass ratio of catalyst and modified rosin resin is 1.0%；
(2) autoclave is vacuumized, with air in nitrogen displacement kettle, is re-filled with hydrogen, adjusts Hydrogen Vapor Pressure in kettle；
(3) start autoclave heating system and stirring system, be warming up to 260 DEG C, and fresh hydrogen is continuously replenished, keep kettle
Interior Hydrogen Vapor Pressure reacts 4 hours in 10MPa；
(4) after reaction, stop heating, open cooling system and cool to 130 DEG C, blowdown pressure letdown, discharging is filtered, filtrate
Into boiler, 180-230 DEG C is distilled off solvent, then is distilled 0.5-2 hours using 230 DEG C of vacuum decompressions, removes low boiling point
Substance, residual solvent are to get hydrogenation modification rosin tackifying resin.
The softening point of the modified rosin resin used in step described in the present embodiment (1) is 80 DEG C, acid value 34.2
(mgKOH/g), color is Ghana's color 9.5, is prepared with the following method: essence is added into the autoclave that volume is 1L
The dicyclopentadiene fraction of rosin processed, dicyclopentadiene content 75wt%, wherein the additional amount of the dicyclopentadiene fraction with
The mass ratio of refined rosin is that 265 DEG C, pressure 0.60Mpa are warming up in 0.75,2 hours, is reacted 2 hours, and decompression, flash distillation removes
Low-boiling point material is removed, then cools to 220 DEG C, obtains modified rosin tackifying resin.The refined rosin selected in embodiment, acid value
181 (mgKOH/g), 80.6 DEG C of softening point, being dissolved in toluene to be made into Ghana's color of 50% solution is 2+.
Through detecting, the softening point of hydrogenation modification rosin tackifying resin obtained by the present embodiment is 90 DEG C, acid value 31.5
(mgKOH/g), color is Ghana color < 1.
Embodiment 2
A kind of embodiment of the preparation method of hydrogenation modification rosin tackifying resin of the present invention, hydrogenation modification described in the present embodiment
Rosin tackifying resin is prepared using following methods:
(1) by modified rosin resin, pinane investment 1L autoclave, it is heated to 100-150 DEG C of dissolution, it then again will catalysis
Agent D5H1A is added in autoclave；Wherein the mass ratio of modified rosin resin and modified rosin resin and pinane gross mass is
38.5%, the mass ratio of catalyst and modified rosin resin is 2.0%；
(2) autoclave is vacuumized, with air in nitrogen displacement kettle, is re-filled with hydrogen, adjusts Hydrogen Vapor Pressure in kettle；
(3) start autoclave heating system and stirring system, be warming up to 240 DEG C, and fresh hydrogen is continuously replenished, keep kettle
Interior Hydrogen Vapor Pressure reacts 3 hours in 15MPa；
(4) after reaction, stop heating, open cooling system and cool to 120 DEG C, blowdown pressure letdown, discharging is filtered, filtrate
Into boiler, 180-230 DEG C is distilled off solvent, then is distilled 0.5-2 hours using 230 DEG C of vacuum decompressions, removes low boiling point
Substance, residual solvent are to get hydrogenation modification rosin tackifying resin.
The softening point of the modified rosin resin used in step described in the present embodiment (1) is 105 DEG C, acid value 15
(mgKOH/g), color is Ghana's color 10+, is prepared with the following method: essence is added into the autoclave that volume is 1L
The dicyclopentadiene fraction of rosin processed, turpentine oil and dicyclopentadiene content 98wt%, wherein the dicyclopentadiene fraction
The mass ratio of additional amount and refined rosin is 1.12, and the terebinthine additional amount is formula gross mass (refined rosin, turpentine oil
With the quality of dicyclopentadiene fraction and) 1%, be warming up to 290 DEG C, pressure 0.55Mpa in 2 hours, react 1.0 hours,
Decompression, flash distillation remove low-boiling point material, then cool to 200 DEG C, obtain modified rosin tackifying resin.
Through detecting, the softening point of hydrogenation modification rosin tackifying resin obtained by the present embodiment is 100 DEG C, acid value 19.2
(mgKOH/g), color is Ghana color < 1.
Embodiment 3
A kind of embodiment of the preparation method of hydrogenation modification rosin tackifying resin of the present invention, hydrogenation modification described in the present embodiment
Rosin tackifying resin is prepared using following methods:
(1) by modified rosin resin, normal heptane investment 1L autoclave, it is heated to 100-150 DEG C of dissolution, then will be urged again
Agent SN-7000P is added in autoclave；The wherein mass ratio of modified rosin resin and modified rosin resin and normal heptane gross mass
It is 60.0%, the mass ratio of catalyst and modified rosin resin is 7%；
(2) autoclave is vacuumized, with air in nitrogen displacement kettle, is re-filled with hydrogen, adjusts Hydrogen Vapor Pressure in kettle；
(3) start autoclave heating system and stirring system, be warming up to 220 DEG C, and fresh hydrogen is continuously replenished, keep kettle
Interior Hydrogen Vapor Pressure reacts 3.5 hours in 8MPa；
(4) after reaction, stop heating, open cooling system and cool to 120 DEG C, blowdown pressure letdown, discharging is filtered, filtrate
Into boiler, 180-230 DEG C is distilled off solvent, then is distilled 0.5-2 hours using 230 DEG C of vacuum decompressions, removes low boiling point
Substance, residual solvent are to get hydrogenation modification rosin tackifying resin.
The softening point of the modified rosin resin used in step described in the present embodiment (1) is 90.2 DEG C, acid value 60.5
(mgKOH/g), color is Ghana's color 10, is prepared with the following method: hydrogen is added into the autoclave that volume is 1L
Change the dicyclopentadiene fraction of rosin, laurene and dicyclopentadiene content 50wt%, wherein the dicyclopentadiene fraction
The mass ratio of additional amount and hydrogenated rosin is 0.44, and the additional amount of the laurene is formula gross mass (hydrogenated rosin, laurene
With the quality of dicyclopentadiene fraction and) 6.9%, be warming up to 220 DEG C, pressure 0.58Mpa in 2 hours, reaction 4.0 is small
When, decompression, flash distillation removes low-boiling point material, then cools to 205 DEG C, obtains modified rosin tackifying resin.
Through detecting, the softening point of hydrogenation modification rosin tackifying resin obtained by the present embodiment is 84.3 DEG C, acid value 66.5
(mgKOH/g), color is Ghana color < 1.
Embodiment 4
A kind of embodiment of the preparation method of hydrogenation modification rosin tackifying resin of the present invention, hydrogenation modification described in the present embodiment
Rosin tackifying resin is prepared using following methods:
(1) by modified rosin resin, 200# solvent naphtha investment 1L autoclave, it is heated to 100-150 DEG C of dissolution, then again
Catalyst SN-5000P is added in autoclave；Wherein modified rosin resin and modified rosin resin and 200# solvent naphtha gross mass
Mass ratio be 50.0%, the mass ratio of catalyst and modified rosin resin is 10.0%；
(2) autoclave is vacuumized, with air in nitrogen displacement kettle, is re-filled with hydrogen, adjusts Hydrogen Vapor Pressure in kettle；
(3) start autoclave heating system and stirring system, be warming up to 180 DEG C, and fresh hydrogen is continuously replenished, keep kettle
Interior Hydrogen Vapor Pressure reacts 1 hour in 5MPa；
(4) after reaction, stop heating, open cooling system and cool to 110 DEG C, blowdown pressure letdown, discharging is filtered, filtrate
Into boiler, 180-230 DEG C is distilled off solvent, then is distilled 0.5-2 hours using 230 DEG C of vacuum decompressions, removes low boiling point
Substance, residual solvent are to get hydrogenation modification rosin tackifying resin.
The softening point of the modified rosin resin used in step described in the present embodiment (1) is 110 DEG C, acid value 70.0
(mgKOH/g), color be Ghana's color 11+, use method as described below to be prepared: toward volume in the autoclave of 1L add
Enter the dicyclopentadiene fraction of gum rosin, dicyclopentadiene alkene and dicyclopentadiene content 83wt%, wherein the dicyclopentadiene fraction
Additional amount and gum rosin mass ratio be 1.22；The additional amount of the dicyclopentadiene alkene be formula gross mass (gum rosin, dicyclopentadiene alkene and
The quality of dicyclopentadiene fraction and) 5%, 170 DEG C, pressure 0.20Mpa are warming up in 2 hours, is reacted 30.0 hours, solution
Pressure, flash distillation remove low-boiling point material, then cool to 230 DEG C, obtain modified rosin tackifying resin.Modified pine used in the present embodiment
Antioxidant stabilizer is additionally added in botany bar gum, the antioxidant stabilizer is four [β-(3,5- di-tert-butyl-hydroxy phenyl) third
Acid] pentaerythritol ester and three (2,4- di-tert-butyl-phenyl) phosphite esters mixture, four [β-(3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic acid] mass ratio of pentaerythritol ester and three (2,4- di-tert-butyl-phenyl) phosphorous acid is 3:1, the antioxidant stabilizer
It is added directly into modified rosin resin, stirs evenly, the additional amount of the antioxidant stabilizer is gum rosin quality
0.2%.
Through detecting, the softening point of hydrogenation modification rosin tackifying resin obtained by the present embodiment is 109 DEG C, acid value 19.2
(mgKOH/g), color is Ghana color < 1.
Embodiment 5
A kind of embodiment of the preparation method of hydrogenation modification rosin tackifying resin of the present invention, hydrogenation modification described in the present embodiment
Rosin tackifying resin is prepared using following methods:
(1) by modified rosin resin, normal heptane investment 1L autoclave, it is heated to 100-150 DEG C of dissolution, then will be urged again
Agent SN-6000P is added in autoclave；The wherein mass ratio of modified rosin resin and modified rosin resin and normal heptane gross mass
It is 60.0%, the mass ratio of catalyst and modified rosin resin is 5%；
(2) autoclave is vacuumized, with air in nitrogen displacement kettle, is re-filled with hydrogen, adjusts Hydrogen Vapor Pressure in kettle；
(3) start autoclave heating system and stirring system, be warming up to 240 DEG C, and fresh hydrogen is continuously replenished, keep kettle
Interior Hydrogen Vapor Pressure reacts 1.5 hours in 12MPa；
(4) after reaction, stop heating, open cooling system and cool to 120 DEG C, blowdown pressure letdown, discharging is filtered, filtrate
Into boiler, 180-230 DEG C is distilled off solvent, then is distilled 0.5-2 hours using 230 DEG C of vacuum decompressions, removes low boiling point
Substance, residual solvent are to get hydrogenation modification rosin tackifying resin.
The softening point of the modified rosin resin used in step described in the present embodiment (1) is 85.5 DEG C, acid value 65.5
(mgKOH/g), color is Ghana's color 10, is prepared with the following method: discrimination is added into the autoclave that volume is 1L
Change the dicyclopentadiene fraction of rosin, phellandrene and dicyclopentadiene content 50wt%, wherein the dicyclopentadiene fraction
The mass ratio of additional amount and disproportionated rosin is 0.5；The additional amount of the phellandrene is formula gross mass (disproportionated rosin, phellandrene
With the quality of dicyclopentadiene fraction and) 10%, be warming up to 250 DEG C, pressure 0.43Mpa in 2 hours, react 8 hours, solution
Pressure, flash distillation remove low-boiling point material, then cool to 210 DEG C, obtain modified rosin tackifying resin.Modified pine used in the present embodiment
Antioxidant stabilizer is additionally added in botany bar gum, the antioxidant stabilizer is four [β-(3,5- di-tert-butyl-hydroxy phenyl) third
Acid] pentaerythritol ester and three (2,4- di-tert-butyl-phenyl) phosphite esters mixture, four [β-(3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic acid] mass ratio of pentaerythritol ester and three (2,4- di-tert-butyl-phenyl) phosphorous acid is 0.6:1, the antioxygen is stablized
Agent is added directly into modified rosin resin, is stirred evenly, and the additional amount of the antioxidant stabilizer is disproportionated rosin quality
0.5%.
Through detecting, the softening point of hydrogenation modification rosin tackifying resin obtained by the present embodiment is 83.2 DEG C, acid value 63.2
(mgKOH/g), color is Ghana color < 1.
Embodiment 6
A kind of embodiment of the preparation method of hydrogenation modification rosin tackifying resin of the present invention, hydrogenation modification described in the present embodiment
Rosin tackifying resin is prepared using following methods:
(1) by the mixture of modified rosin resin, pinane and normal heptane (wherein the mass ratio of pinane and normal heptane is 1:1)
It puts into 1L autoclave, 100-150 DEG C of dissolution is heated to, then again by catalyst D5-Al2O3It is added in autoclave；Wherein it is modified
Rosin resin and modified rosin resin and the mass ratio of solvent (mixture of pinane and normal heptane) gross mass are 35%, catalyst
Mass ratio with modified rosin resin is 0.5%；
(2) autoclave is vacuumized, with air in nitrogen displacement kettle, is re-filled with hydrogen, adjusts Hydrogen Vapor Pressure in kettle；
(3) start autoclave heating system and stirring system, be warming up to 200 DEG C, and fresh hydrogen is continuously replenished, keep kettle
Interior Hydrogen Vapor Pressure reacts 2.5 hours in 9MPa；
(4) after reaction, stop heating, open cooling system and cool to 120 DEG C, blowdown pressure letdown, discharging is filtered, filtrate
Into boiler, 180-230 DEG C is distilled off solvent, then is distilled 0.5-2 hours using 230 DEG C of vacuum decompressions, removes low boiling point
Substance, residual solvent are to get hydrogenation modification rosin tackifying resin.
The softening point of the modified rosin resin used in step described in the present embodiment (1) is 108 DEG C, acid value 25.5
(mgKOH/g), color is Ghana's color 10, is prepared with the following method: into the autoclave that volume is 1L plus wood is loose
The mixture (wherein the mass ratio of ocimenum and laurene is 1:1) and dicyclopentadiene content of fragrant, ocimenum and laurene
The dicyclopentadiene fraction of 100wt%, wherein the mass ratio of the additional amount of the dicyclopentadiene fraction and wood rosin is 0.82；
The additional amount of the phellandrene and terebinthine mixture be formulated gross mass (wood rosin, ocimenum and laurene mixture,
The quality of dicyclopentadiene fraction and) 15.0%, 240 DEG C, pressure 0.60Mpa are warming up in 2 hours, is reacted 15 hours,
Decompression, flash distillation remove low-boiling point material, then cool to 210 DEG C, obtain modified rosin tackifying resin.
Through detecting, the softening point of hydrogenation modification rosin tackifying resin obtained by the present embodiment is 105 DEG C, acid value 23.6
(mgKOH/g), color is Ghana color < 1.
Embodiment 7
A kind of embodiment of the preparation method of hydrogenation modification rosin tackifying resin of the present invention, hydrogenation modification described in the present embodiment
Rosin tackifying resin is prepared using following methods:
(1) by the mixture of modified rosin resin hexamethylene and normal heptane (wherein the mass ratio of pinane and normal heptane is 1:
1.5) it puts into 1L autoclave, is heated to 100-150 DEG C of dissolution, then catalyst SN-6900P is added in autoclave again；Its
The mass ratio of middle modified rosin resin and modified rosin resin and solvent (mixture of hexamethylene and normal heptane) gross mass is
40%, the mass ratio of catalyst and modified rosin resin is 3.0%；
(2) autoclave is vacuumized, with air in nitrogen displacement kettle, is re-filled with hydrogen, adjusts Hydrogen Vapor Pressure in kettle；
(3) start autoclave heating system and stirring system, be warming up to 210 DEG C, and fresh hydrogen is continuously replenished, keep kettle
Interior Hydrogen Vapor Pressure reacts 4 hours in 6MPa；
(4) after reaction, stop heating, open cooling system and cool to 120 DEG C, blowdown pressure letdown, discharging is filtered, filtrate
Into boiler, 180-230 DEG C is distilled off solvent, then is distilled 0.5-2 hours using 230 DEG C of vacuum decompressions, removes low boiling point
Substance, residual solvent are to get hydrogenation modification rosin tackifying resin.
The softening point of the modified rosin resin used in step described in the present embodiment (1) is 80.5 DEG C, acid value 69.5
(mgKOH/g), color is Ghana's color 9, is prepared with the following method: into the autoclave that volume is 1L plus purification is loose
Mixture (wherein the mass ratio of limonene and australene is 1:2), the dicyclopentadiene content of fragrant, limonene and australene
The dicyclopentadiene fraction of 70wt%, wherein the mass ratio of the additional amount of the dicyclopentadiene fraction and refined rosin is 0.6；
The additional amount of the mixture of the limonene and australene is the formula gross mass (mixing of refined rosin, limonene and australene
Object, dicyclopentadiene fraction quality and) 8%, 265 DEG C, pressure 0.45Mpa are warming up in 2 hours, is reacted 15 hours,
Decompression, flash distillation remove low-boiling point material, then cool to 200 DEG C, obtain modified rosin tackifying resin.
Through detecting, the softening point of hydrogenation modification rosin tackifying resin obtained by the present embodiment is 79 DEG C, acid value 65.2
(mgKOH/g), color is Ghana color < 1.
Embodiment 8
A kind of embodiment of the preparation method of hydrogenation modification rosin tackifying resin of the present invention, hydrogenation modification described in the present embodiment
Rosin tackifying resin is prepared using following methods:
(1) by modified rosin resin, hexamethylene investment 1L autoclave, it is heated to 100-150 DEG C of dissolution, then again by palladium
Catalyst D5-Al2O3It is added in autoclave；The wherein quality of modified rosin resin and modified rosin resin and hexamethylene gross mass
Than being 45%, the mass ratio of catalyst and modified rosin resin is 0.8%；
(2) autoclave is vacuumized, with air in nitrogen displacement kettle, is re-filled with hydrogen, adjusts Hydrogen Vapor Pressure in kettle；
(3) start autoclave heating system and stirring system, be warming up to 230 DEG C, and fresh hydrogen is continuously replenished, keep kettle
Interior Hydrogen Vapor Pressure reacts 2 hours in 7MPa；
(4) after reaction, stop heating, open cooling system and cool to 120 DEG C, blowdown pressure letdown, discharging is filtered, filtrate
Into boiler, 180-230 DEG C is distilled off solvent, then is distilled 0.5-2 hours using 230 DEG C of vacuum decompressions, removes low boiling point
Substance, residual solvent are to get hydrogenation modification rosin tackifying resin.
The softening point of the modified rosin resin used in step described in the present embodiment (1) is 101 DEG C, acid value 23.5
(mgKOH/g), color is Ghana's color 11, is prepared with the following method: rouge is added into the autoclave that volume is 1L
The dicyclopentadiene fraction of rosin, nopinene and dicyclopentadiene content 93wt%, wherein the dicyclopentadiene fraction adds
The mass ratio for entering amount and gum rosin is 1.02, and the additional amount of the nopinene is formula gross mass (gum rosin, nopinene and bicyclic
The quality of pentadiene fraction and) 12%, 200 DEG C, pressure 0.32Mpa are warming up in 2 hours, is reacted 20 hours, is decompressed, is dodged
Low-boiling point material is evaporated off, then cools to 220 DEG C, obtains modified rosin tackifying resin.
Through detecting, the softening point of hydrogenation modification rosin tackifying resin obtained by the present embodiment is 100 DEG C, acid value 22
(mgKOH/g), color is Ghana color < 1.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (6)
1. a kind of preparation method of hydrogenation modification rosin tackifying resin, which is characterized in that the described method comprises the following steps:
(1) by modified rosin resin, pinane investment 1L autoclave, it is heated to 100-150 DEG C of dissolution, then again by catalyst
D5H1A is added in autoclave；Wherein modified rosin resin and modified rosin resin and the mass ratio of pinane gross mass are 38.5%,
The mass ratio of catalyst and modified rosin resin is 2.0%；
Wherein, the softening point of modified rosin resin is 105 DEG C, acid value 15mgKOH/g, color be greater than No. 10 colors of Ghana number,
It is prepared with the following method: refined rosin, turpentine oil and dicyclopentadiene is added into the autoclave that volume is 1L
The dicyclopentadiene fraction of content 98wt%, wherein the additional amount of the dicyclopentadiene fraction and the mass ratio of refined rosin are
1.12, the terebinthine additional amount is the 1% of the quality sum of refined rosin, turpentine oil and dicyclopentadiene fraction, in 2 hours
290 DEG C, pressure 0.55MPa are warming up to, is reacted 1.0 hours, decompression, flash distillation removes low-boiling point material, then cools to 200
DEG C, obtain modified rosin resin；
(2) autoclave is vacuumized, with air in nitrogen displacement kettle, is re-filled with hydrogen, adjusts Hydrogen Vapor Pressure in kettle；
(3) start autoclave heating system and stirring system, be warming up to 240 DEG C, and fresh hydrogen is continuously replenished, keep hydrogen in kettle
Atmospheric pressure reacts 3 hours in 15MPa；
(4) after reaction, stop heating, open cooling system and cool to 120 DEG C, blowdown pressure letdown, discharging is filtered, and filtrate enters
Boiler, 180-230 DEG C is distilled off solvent, then is distilled 0.5-2 hours using 230 DEG C of vacuum decompressions, removing low-boiling point material,
Residual solvent is to get hydrogenation modification rosin tackifying resin.
2. a kind of hydrogenation modification rosin tackifying resin being prepared using method as described in claim 1.
3. hydrogenation modification rosin tackifying resin as claimed in claim 2, which is characterized in that the hydrogenation modification rosin thickening tree
The softening point of rouge is 100 DEG C, acid value 19.2mgKOH/g, and color is less than No. 1 color of Ghana color number.
4. a kind of preparation method of hydrogenation modification rosin tackifying resin, which is characterized in that the described method comprises the following steps:
(1) modified rosin resin, normal heptane are put into 1 L autoclave, is heated to 100-150 DEG C of dissolution, it then again will catalysis
Agent SN-7000P is added in autoclave；Wherein the mass ratio of modified rosin resin and modified rosin resin and normal heptane gross mass is
60.0%, the mass ratio of catalyst and modified rosin resin is 7%；
Wherein, the softening point of modified rosin resin is 90.2 DEG C, and acid value 60.5mg, KOH/g, color is No. 10 colors of Ghana number,
It is prepared with the following method: hydrogenated rosin, laurene and dicyclopentadiene is added into the autoclave that volume is 1 L
The dicyclopentadiene fraction of content 50wt%, wherein the additional amount of the dicyclopentadiene fraction and the mass ratio of hydrogenated rosin are
0.44, the additional amount of the laurene is the 6.9% of the quality sum of hydrogenated rosin, laurene and dicyclopentadiene fraction, 2 hours
220 DEG C, pressure 0.58MPa are inside warming up to, is reacted 4.0 hours, decompression, flash distillation removes low-boiling point material, then cools to 205
DEG C, obtain modified rosin resin；
(2) autoclave is vacuumized, with air in nitrogen displacement kettle, is re-filled with hydrogen, adjusts Hydrogen Vapor Pressure in kettle；
(3) start autoclave heating system and stirring system, be warming up to 220 DEG C, and fresh hydrogen is continuously replenished, keep hydrogen in kettle
Atmospheric pressure reacts 3.5 hours in 8MPa；
(4) after reaction, stop heating, open cooling system and cool to 120 DEG C, blowdown pressure letdown, discharging is filtered, and filtrate enters
Boiler, 180-230 DEG C is distilled off solvent, then is distilled 0.5-2 hours using 230 DEG C of vacuum decompressions, removing low-boiling point material,
Residual solvent is to get hydrogenation modification rosin tackifying resin.
5. a kind of hydrogenation modification rosin tackifying resin being prepared using method as claimed in claim 4.
6. hydrogenation modification rosin tackifying resin as claimed in claim 5, which is characterized in that the hydrogenation modification rosin thickening tree
The softening point of rouge is 84.3 DEG C, acid value 66.5mgKOH/g, and color is less than No. 1 color of Ghana color number.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610137768.2A CN105585961B (en) | 2016-03-10 | 2016-03-10 | A kind of hydrogenation modification rosin tackifying resin and preparation method thereof |
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| CN201610137768.2A CN105585961B (en) | 2016-03-10 | 2016-03-10 | A kind of hydrogenation modification rosin tackifying resin and preparation method thereof |
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| 《Pd /C上歧化松香催化加氢反应研究》;郑文峰等;《广西大学学报（自然科学版）》;20140630;第39卷(第3期);507-512 * |
| 《松脂催化加氢制备氢化松香及高顺反比蒎烷》;陈小鹏等;《精细化工》;20021130;第19卷(第11期);654-657 * |
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